WO2019020086A1 - 碳包覆过渡金属纳米复合材料、其制备及应用 - Google Patents

碳包覆过渡金属纳米复合材料、其制备及应用 Download PDF

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WO2019020086A1
WO2019020086A1 PCT/CN2018/097303 CN2018097303W WO2019020086A1 WO 2019020086 A1 WO2019020086 A1 WO 2019020086A1 CN 2018097303 W CN2018097303 W CN 2018097303W WO 2019020086 A1 WO2019020086 A1 WO 2019020086A1
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Prior art keywords
nanocomposite
carbon
transition metal
coated
acid
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PCT/CN2018/097303
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English (en)
French (fr)
Inventor
荣峻峰
吴耿煌
谢婧新
宗明生
林伟国
于鹏
纪洪波
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to US16/630,906 priority Critical patent/US11224859B2/en
Priority to EP18837328.6A priority patent/EP3659725A4/en
Priority to JP2020504126A priority patent/JP7182604B2/ja
Priority to KR1020207006067A priority patent/KR102524420B1/ko
Publication of WO2019020086A1 publication Critical patent/WO2019020086A1/zh

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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to the field of carbon-coated metal nanocomposites, in particular to a nanocomposite comprising carbon-coated transition metal particles, a preparation method thereof and an application thereof.
  • nanocarbon materials have the advantages of acid and alkali corrosion resistance and chemical stability.
  • the active sites of nanocarbon catalysts are mainly structural defects of carbon materials and hetero atom functional groups. Therefore, in order to improve the catalytic activity of nanocarbon materials, it is necessary to increase the structural defects and the number of hetero atom functional groups, but this will lead to the stability of the materials themselves. Sexual decline.
  • Transition metal nanomaterials have attracted extensive attention due to their excellent optical, electrical, magnetic and catalytic properties. However, due to the high activity of transition metal nanoparticles, they are prone to agglomeration or oxidation, and even spontaneous combustion in the air, greatly affecting The properties and applications of such materials.
  • transition metal nanomaterials have high catalytic activity but poor stability, while the nanocarbon materials have good chemical stability but need to further improve the catalytic activity. If the two are combined in an appropriate manner, new synergistic effects may be generated. To make it show new and unique features.
  • nano-carbon coated metal composite materials have become a hot spot of concern.
  • This kind of material consists of a single layer to several layers of curved graphitized carbon layer, which is a metal nanoparticle with a shell tightly wrapped around the core, which isolates the metal nanoparticles from the outside and greatly improves the stability of the composite. Therefore, this unique core-shell nanomaterial has broad application prospects in the fields of catalytic materials, absorbing materials, information storage materials, magneto-optical materials, biomedical materials, and lubricant additives.
  • known methods for producing carbon-coated metal nanoparticles include arc method, chemical vapor deposition (CVD), high temperature pyrolysis, and sol-gel method.
  • the equipment used in the arc method is complicated, the operability is poor, and the energy consumption is high, which is not conducive to large-scale preparation of materials.
  • the CVD method has lower cost and higher yield and yield, but the difficulty lies in the need to prepare particles of uniform size and well-dispersed nano-metal or its compound, and the carbon nanotubes are often accompanied by late products. And the formation of particles of amorphous carbon.
  • the pyrolysis method has the advantages of simple process, low cost, high yield and controllable metal content, and is one of the methods for large-scale preparation.
  • the pyrolysis method can be mainly divided into two categories.
  • the first method directly combines a carbon source containing nitrogen atoms (usually dicyandiamide, melamine, urea which easily forms melamine at high temperature, etc.), and the metal source is mixed and then placed in an inert state.
  • High temperature pyrolysis is carried out under a reducing atmosphere.
  • the method has low graphitization efficiency, large use amount of cyanamide ligand, and unsatisfactory coating effect.
  • the method also facilitates the formation of carbon nanotubes.
  • Another method is to form a crystalline solid material (ie, metal-organic framework compound, MOF) having a periodic structure by a self-assembled connection between a metal ion and a nitrogen-containing organic ligand under a characteristic reaction as a precursor.
  • MOF metal-organic framework compound
  • the metal in MOF is considered to be a more ideal pyrolysis precursor due to its uniform dispersion at the atomic level, which has become a research hotspot in this field in recent years.
  • the preparation of such a precursor requires the use of an organic solvent, and it is necessary to carry out a high temperature and high pressure reaction in the reaction vessel.
  • CN105965009A discloses a precursor prepared by coordinating with Ni 2+ under high temperature and high pressure with aspartic acid, 4,4'-bipyridine as a ligand, methanol and water as solvents.
  • the self-assembled precursor is also prepared under high temperature and high pressure conditions, and the carbon-coated nickel nanoparticles are further prepared by pyrolysis under Ar atmosphere.
  • the literature MOF-derived Ni-based nanocomposites as robust catalyst for chemoselective hydrogenation of functionalized nitro compounds Bo Tang et.al., RSC Advances, 2017, 7, 1531-1539 discloses the use of a nitrogen-free organic ligand first in A method of assembling a metal organic framework precursor (MOF) under high temperature and high pressure, and then pyrolyzing a porous carbon-coated nickel nanoparticle composite material at a high temperature.
  • MOF metal organic framework precursor
  • the conditions for preparing MOFs are generally strict, the ligands required are expensive, and mass production is difficult.
  • a weak acid is formed into a chelate compound with certain cations, and then a solid polymer resin is formed by polymerizing a chelate compound with a polyhydric alcohol, and then the resin is calcined to prepare a powder.
  • a solid polymer resin is formed by polymerizing a chelate compound with a polyhydric alcohol, and then the resin is calcined to prepare a powder.
  • CN105032424A discloses a pechini-type sol-gel method in which a precursor of an active metal is first dispersed in water containing a complex compound, a polyol aqueous solution and a polymer auxiliary agent are added, and then a carrier is added, and the mixture is stirred and dispersed.
  • the hydrothermal reaction separates the lower solid and calcines under an inert atmosphere to obtain a carbon-coated active metal catalyst.
  • the sol-gel method also requires the preparation of a solid coordination polymer in a solvent, and the coating of the composite material prepared by the method is not tightly coated.
  • the method requires the use of a polymer auxiliary agent, and the process is cumbersome.
  • Mesoporous materials generally refer to a class of porous materials having a pore structure having a pore size between 2 and 50 nm. Mesoporous materials can play a better role in the separation, adsorption, and catalytic reactions of macromolecules, and may become a limited-domain catalyzed microreactor. Due to its high hydrothermal stability, strong hydrophobicity, and organic matter, the mesoporous carbon material exhibits unique advantages in hydrogenation, oxidation, decomposition and other reactions. If a mesoporous structure can be fabricated in a carbon-coated transition metal material, the mass transfer efficiency can be significantly improved, the use performance can be improved, and the application range can be expanded. At present, the preparation methods of mesoporous carbon materials are mainly catalytic activation method, organogel carbonization method and template method, but the preparation process of these methods is still too complicated.
  • the carbon-coated transition metal materials known in the prior art and their preparation methods have their respective disadvantages. Therefore, there is still a need for a carbon-coated transition metal nanomaterial having a carbon layer coated with a core metal and a low pickling loss rate, and it is more desirable that the material also has a rich mesoporous structure;
  • VOCs volatile organic compounds
  • Commonly used are, for example, alkanes, aromatic hydrocarbons, ether alcohols, Halogenated hydrocarbons, etc.
  • the production and emission of VOCs are the most important, and it is easy to encounter in life (renovation produces formaldehyde, etc.).
  • VOCs have become one of the main causes of photochemical smog. They are used together with nitrogen oxides and respirable particulate matter as important control pollutants for air quality. In addition, they are also highly toxic and carcinogenic. Therefore, there is an urgent need for a catalytic oxidation material excellent in performance for treating volatile organic compounds.
  • the catalyst for catalyzing the hydrogenation of nitrobenzene in the prior art is a noble metal catalyst such as platinum (Pt), palladium (Pd) and rhodium (Rh), and copper (Cu), nickel (Ni), lead (Zn).
  • a noble metal catalyst such as platinum (Pt), palladium (Pd) and rhodium (Rh), and copper (Cu), nickel (Ni), lead (Zn).
  • Non-precious metal catalysts such as molybdenum (Mo) are mainly used. Due to its low price and relatively high catalytic activity, Raney Ni catalyst is the most commonly used catalyst for industrially catalyzed hydrogenation reduction of nitrobenzene compounds to aniline compounds. However, the Raney Ni catalyst still has many disadvantages. For example, the framework nickel is easily ignited in the air and cannot be stored.
  • Hydrogen is present in the hydrogenation plant, which is prone to explosion; the amount of reaction by-products is large, the product yield is low, and the catalytic activity is high. Lower and so on. Therefore, there is still a need for a catalytic material having high stability and catalytic activity suitable for catalytic hydrogenation reduction, particularly nitrobenzene hydrogenation.
  • the present invention provides a nanocomposite comprising a carbon-coated transition metal particle having a core-shell structure, wherein the graphitized carbon shell layer is tightly coated to the core of the transition metal nanoparticle, so that The loss rate of the core transition metal in the application is reduced, the material performance is kept stable and the safety is ensured, and in particular, the material can also have a rich mesoporous structure, thereby improving mass transfer efficiency.
  • the present invention also provides a simple, green, and highly efficient method for preparing a carbon-coated transition metal nanocomposite, which can obtain a precursor of a desired nanocomposite by simply mixing under normal pressure, and the precursor The preparation of the body can be carried out in a pure aqueous phase.
  • the present invention provides a nanocomposite comprising carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and/or nitrogen,
  • the inner core is a transition metal nanoparticle, wherein the nanocomposite is a porous material having at least one mesoporous distribution peak.
  • the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • the nanocomposite has a pickling loss rate of ⁇ 40%, more preferably ⁇ 30%, particularly preferably ⁇ 10%.
  • the nanocomposite further comprises an amorphous carbon substrate, the carbon coated transition metal particles being dispersed in the amorphous carbon substrate; more preferably, the nanocomposite is composed of an amorphous carbon substrate And consisting of the carbon-coated transition metal particles dispersed therein.
  • the ratio of mesoporous volume to total pore volume of the nanocomposite is greater than about 50%, more preferably greater than about 80%, further preferably greater than about 90%, particularly preferably greater than about 95%, and most preferably about 100%. More preferably, the nanocomposite has a mesopore volume of from about 0.05 to 1.25 cm 3 /g.
  • the present invention provides a nanocomposite comprising carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and/or nitrogen
  • the core is a transition metal nanoparticle, wherein the nanocomposite has a pickling loss rate of ⁇ 10%.
  • the nanocomposite is a porous material having at least one mesoporous distribution peak, more preferably a porous material having two or more mesoporous distribution peaks.
  • the nanocomposite further comprises an amorphous carbon substrate, the carbon coated transition metal particles being dispersed in the amorphous carbon substrate; more preferably, the nanocomposite is composed of an amorphous carbon substrate And consisting of the carbon-coated transition metal particles dispersed therein.
  • the ratio of mesoporous volume to total pore volume of the nanocomposite is greater than about 50%, more preferably greater than about 80%, further preferably greater than about 90%, particularly preferably greater than about 95%, and most preferably about 100%.
  • the nanocomposite has a mesopore volume of from about 0.05 to 1.25 cm 3 /g.
  • the nanocomposite of the present invention contains a closely packed graphitized carbon layer/metal core shell structure, and has no pores or defects that can bring the reactants close to the center of the transition metal, so that the transition metal material of the core is very stable, not self-igniting, and resistant to acid. Corrosion, low risk, suitable for storage and transportation, thus ensuring the safety of composite materials.
  • the nanocomposite of the present invention has a rich mesoporous structure, which is favorable for mass transfer and diffusion of reactants and products in the reaction; the carbon material in the nanocomposite itself has catalytic activity and plays a synergistic role with the transition metal.
  • the mass transfer efficiency of the nanocomposite is made higher; in particular, the nanocomposite can have a multi-level mesoporous structure, thereby giving the material more functions, making it suitable for more applications.
  • the nanocomposite of the present invention contains a ferromagnetic metal core coated with a graphitized carbon layer and a rich pore structure, so that the magnetic separation function and the adsorption function are better combined, making it particularly suitable for the adsorption separation field. .
  • the nanocomposite of the present invention can be used as a catalyst for various organic reactions, which is advantageous for improving the efficiency of the catalytic reaction.
  • the material When used in catalytic hydrogenation reaction, the material exhibits good reproducibility, high activity, high selectivity, etc., and has good industrial application prospects.
  • the material When used as a catalytic oxidation catalyst, the material exhibits good low temperature activity, which is important for the complete removal of volatile organic compounds in industrial waste gas by catalytic combustion.
  • the nanocomposite of the invention is not self-igniting in air, and can be stored in the air for a long time as a common commodity, without affecting its performance in catalytic oxidation, catalytic hydrogenation and the like.
  • the content of the doping element is adjustable, and the introduction of oxygen element by means of nitric acid treatment is not required, and the electronic properties of the graphitized carbon layer can be adjusted to make it suitable for catalyzing different reactions.
  • the present invention provides a method of preparing a nanocomposite comprising carbon coated transition metal particles, comprising the steps of:
  • step iii) is treated with a non-oxidizing strong acid.
  • the mixture used in step i) of the method further comprises a nitrogen-containing organic compound and/or an oxygen-containing organic compound different from the polybasic organic carboxylic acid, wherein the nitrogen-containing organic compound is preferably selected from the group consisting of urea One or more of melamine, dicyandiamide, hexamethylenetetramine, and an amino acid, preferably selected from the group consisting of a polyol and an organic carboxylic acid such as lactic acid.
  • the nitrogen-containing organic compound is preferably selected from the group consisting of urea One or more of melamine, dicyandiamide, hexamethylenetetramine, and an amino acid, preferably selected from the group consisting of a polyol and an organic carboxylic acid such as lactic acid.
  • the transition metal source is selected from one or more of an organic acid salt, a carbonate, a basic carbonate, an oxide and a hydroxide of a transition metal; more preferably an organic acid of the transition metal
  • the salt is a heteroatom-free organic carboxylate of the transition metal, such as an acetate.
  • the polybasic organic carboxylic acid is selected from one or more of the group consisting of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, EDTA, and dipicolinic acid.
  • the non-oxidizing strong acid used in step iv) is selected from one or more of hydrofluoric acid, hydrochloric acid, nitric acid and sulfuric acid, more preferably hydrochloric acid and/or sulfuric acid.
  • the nanocomposite preparation method of the present invention can realize one or more of the following advantages:
  • the method of the invention is simpler and more efficient, and the high-temperature pyrolysis precursor is directly obtained by uniformly mixing a transition metal source and a polybasic organic carboxylic acid in a solvent (which may be water), and the atomic utilization ratio of the precursor transition metal can reach 100%.
  • the method of the invention overcomes the shortcomings of the prior art for preparing the metal-organic framework precursor, the self-assembly of the high-temperature and high-pressure reactor, the large waste of the organic solvent, and the cumbersome purification steps, while achieving better coating effect.
  • the method of the invention does not require a polymer aid, which simplifies the reaction step.
  • the nano metal particles are coated with the graphitized carbon layer to be more tight and can be used under more severe conditions.
  • the content of the doping element of the graphitized carbon layer is adjustable, and the introduction of oxygen element by means of nitric acid treatment is not required, and the electronic properties of the graphitized carbon layer can be adjusted, so that the obtained nanocomposite material is suitable for different catalysis. Reaction.
  • the present invention provides a nanocomposite comprising carbon coated transition metal particles prepared in accordance with the method of the present invention.
  • the invention provides the use of a nanocomposite according to the invention as a catalyst for the treatment of volatile organic compounds and its use in hydrogenation reduction reactions.
  • the use in treating a volatile organic compound comprises contacting the volatile organic compound with the nanocomposite for catalytic oxidation reaction.
  • the use in the hydrogenation reduction reaction comprises the use in a reaction selected from the group consisting of hydrogenation of p-chloronitrobenzene to p-chloroaniline, hydrogenation of nitrobenzene to aniline, and nitro Hydrogenation of phenol to produce aminophenol, reaction of hydrogenation of p-nitroanisole to p-aminoanisole, reaction of hydrogenation of phenol to cyclohexanol, reaction of olefin hydrogenation, hydrogenation of aromatic hydrocarbon to produce cyclohexane
  • Figure 1-1 is an X-ray diffraction (XRD) pattern of the precursor prepared in Example 1-1.
  • Example 1-1 is a photograph of a magnetic test of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • Example 1-1 are transmission electron microscope (TEM) images of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • Example 1-1 are XRD patterns of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • Example 1-5A is a N 2 adsorption-desorption isotherm diagram of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • Example 1-5B is a pore distribution curve of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • Example 1-6 are TEM images of the carbon-coated nickel nanocomposite prepared in Example 1-2.
  • Example 1-7 are XRD patterns of carbon-coated nickel nanocomposites prepared in Example 1-2.
  • 1-8 are graphs showing pore distribution of the carbon-coated nickel nanocomposite prepared in Example 1-2.
  • 1 to 11 are pore distribution curves of the carbon-coated cobalt nanocomposites prepared in Examples 1-3.
  • 1-16 are pore distribution curves of the carbon-coated nickel and cobalt nanocomposites prepared in Examples 1-6.
  • Figure 1-22 is a TEM image of the carbon coated nickel nanocomposite prepared in Examples 1-9.
  • 1 to 27 are pore distribution curves of the carbon-coated nickel nanocomposites prepared in Examples 1-10.
  • Figure 2-1 is a photograph of the magnetic test of the carbon-coated nickel nanocomposite prepared in Example 2-1.
  • Example 2-2 is a TEM image of the carbon-coated nickel nanocomposite prepared in Example 2-1.
  • Example 2-3 is an XRD pattern of the carbon-coated nickel nanocomposite prepared in Example 2-1.
  • Example 2-4A is a N 2 adsorption-desorption isotherm diagram of the carbon-coated nickel nanocomposite prepared in Example 2-1.
  • 2-4B is a pore distribution curve of the carbon-coated nickel nanocomposite prepared in Example 2-1.
  • Example 2-5 are TEM images of the carbon-coated nickel nanocomposite prepared in Example 2-2.
  • Example 2-6 are XRD patterns of the carbon-coated nickel nanocomposite prepared in Example 2-2.
  • Example 2-7 are graphs showing pore distribution of the carbon-coated nickel nanocomposite prepared in Example 2-2.
  • 2-10 are graphs showing pore distribution of the carbon-coated cobalt nanocomposite prepared in Example 2-3.
  • 2-13 are XRD patterns of carbon-coated nickel and cobalt nanocomposites prepared in Examples 2-4.
  • 2-14 are graphs showing pore distribution of carbon-coated nickel and cobalt nanocomposites prepared in Examples 2-4.
  • 2-23 are graphs showing pore distribution of carbon-coated nickel nanocomposites prepared in Examples 2-8.
  • 2-26 are graphs showing pore distribution of the carbon-coated nickel nanocomposites prepared in Examples 2-9.
  • 2-28 are TEM images of the carbon-coated nickel nanocomposites prepared in Examples 2-10.
  • 2-29 are XRD patterns of the carbon-coated nickel nanocomposites prepared in Examples 2-10.
  • Figure 3-1 is an XRD pattern of the carbon-coated nickel nanocomposite P2 prepared in Example 3-1.
  • 3-2A is a N 2 adsorption-desorption isotherm diagram of the carbon-coated nickel nanocomposite P2 prepared in Example 3-1.
  • 3-2B is a graph showing the pore size distribution of the carbon-coated nickel nanocomposite P2 prepared in Example 3-1.
  • 3-3 is a scanning electron microscope (SEM) and a transmission electron microscope (TEM) image of the carbon-coated nickel nanocomposite P2 prepared in Example 3-1.
  • thermogravimetric-differential thermal analysis curve (TG-DTA) of the precursor prepared in Example 3-2.
  • Example 3-5 are XRD patterns of the carbon-coated nickel nanocomposite P4 prepared in Example 3-2.
  • 3-6 are X-ray photoelectron spectroscopy (XPS) images of the carbon-coated nickel nanocomposite P4 prepared in Example 3-2.
  • XPS X-ray photoelectron spectroscopy
  • 3-7A is a N 2 adsorption-desorption isotherm curve of the carbon-coated nickel nanocomposite P4 prepared in Example 3-2.
  • 3-7B is a pore size distribution diagram of the carbon-coated nickel nanocomposite P4 prepared in Example 3-2.
  • any matters or matters not mentioned are directly applicable to those known in the art without any change other than those explicitly stated.
  • any of the embodiments described herein can be freely combined with one or more other embodiments described herein, and the resulting technical solution or technical idea is considered to be part of the original disclosure or original description of the present invention, and should not be It is considered to be new content that has not been disclosed or anticipated herein, unless it is apparent to those skilled in the art that the combination is clearly unreasonable.
  • nanocomposite comprising carbon-coated transition metal particles
  • carbon-coated transition metal nanocomposite are used interchangeably and are meant to include carbon-coated transition metal particles having a “core-shell structure”. Nanocomposites.
  • core-shell structure means that the core formed by the graphitized carbon material coated on the outer surface of the transition metal nanoparticles is a transition metal nanoparticle, and the shell layer (ie, the outer layer) is a graphitized carbon layer.
  • Composite structure means that the core formed by the graphitized carbon material coated on the outer surface of the transition metal nanoparticles is a transition metal nanoparticle, and the shell layer (ie, the outer layer) is a graphitized carbon layer.
  • graphitized carbon layer refers to a carbon structure in which a layered structure is clearly observed under high-resolution transmission electron microscopy, rather than an amorphous structure, with a layer spacing of about 0.34 nm.
  • the composite material formed by coating the transition metal nanoparticles with the graphitized carbon layer is generally spherical or spheroidal.
  • a graphitized carbon layer doped with oxygen and/or nitrogen means that the graphitized carbon layer is a “graphitized carbon layer doped with oxygen” or a graphitized carbon layer doped with oxygen and nitrogen. "Generally, it is also doped with a small amount of hydrogen.
  • oxygen in the “oxygenated graphitized carbon layer” means an oxygen element including an oxygen element contained in any form contained in the graphitized carbon layer.
  • oxygen content of the nanocomposite means the content of oxygen element, that is, the total content of oxygen elements present in various forms.
  • oxygen in the “doped oxygen and nitrogen graphitized carbon layer” means an oxygen element
  • nitrogen means a nitrogen element, including any form contained in the graphitized carbon layer. Oxygen and nitrogen present.
  • oxygen content refers to the content of oxygen element, that is, the total content of oxygen elements present in various forms; likewise, the “nitrogen content” of the nanocomposite refers to the content of nitrogen element, that is, The total content of nitrogen elements present in various forms.
  • pores refers to pores having a pore size in the range of 2-50 nm.
  • a pore having a pore diameter of less than 2 nm is defined as a micropore, and a pore having a pore diameter of more than 50 nm is defined as a macroporous.
  • mesoporous distribution peak refers to a mesoporous distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
  • carbon coating rate is used to reflect the proportion of transition metal nanoparticles that are effectively coated by a graphitized carbon layer, which can be observed by high resolution transmission electron microscopy (HRTEM).
  • carbon coating stringency is used to reflect the ratio of transition metal nanoparticles that are isolated from the external environment by the graphitized carbon layer, which can be characterized by pickling experiment results.
  • the term "acid treatment” refers to the treatment of a product obtained by pyrolysis of a high temperature with a non-oxidizing strong acid after the high temperature pyrolysis step in the preparation of the carbon-coated transition metal nanocomposite.
  • pickling refers to a step of treating a carbon-coated transition metal nanocomposite with an aqueous solution of sulfuric acid to measure its "acid wash loss rate", which does not constitute the carbon-coated transition metal nanoparticle. Part of the preparation process of the composite.
  • the term "acid wash loss rate” refers to the loss ratio of the transition metal of the carbon-coated transition metal nanocomposite after pickling, which is used to reflect the tightness of the coating of the transition metal nanoparticles by the graphitized carbon layer. . If the graphitized carbon layer is not tightly coated with the transition metal nanoparticles, after the acid washing, the transition metal in the core is dissolved by the acid and is lost. The higher the pickling loss rate, the lower the tightness of the coating of the transition metal nanoparticles by the graphitized carbon layer; on the contrary, the smaller the pickling loss rate, the tighter coverage of the transition metal nanoparticles by the graphitized carbon layer. The higher the degree.
  • a nanocomposite with a pickling loss rate of ⁇ 10% is defined as a "rigidly coated nanocomposite".
  • the pickling loss rate ⁇ 10% indicates that the carbon-coated transition metal particles contained in the nanocomposite have a tightly packed core-shell structure, that is, the transition metal nanoparticles are tightly coated by the graphitized carbon layer, and substantially not Contact with the outside world.
  • the present invention provides a nanocomposite comprising carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and/or nitrogen
  • the core is a transition metal nanoparticle
  • the nanocomposite is a porous material having at least one mesoporous distribution peak, that is, the nanocomposite is calculated according to the Barrett-Joyner-Halenda (BJH) method. On the pore distribution curve, there is at least one mesoporous distribution peak.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and is not doped with elements other than hydrogen and oxygen.
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and is not doped with other elements than hydrogen, oxygen, and nitrogen.
  • the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • the nanocomposite has a pickling loss rate of ⁇ 40%, and may be, for example, about 10%-20%, about 20%-30%, or about 30%-40%, preferably ⁇ 30%, More preferably ⁇ 10%.
  • the pickling loss rate reflects the tightness of the coating of the transition metal core by the graphitized carbon layer, and the smaller the pickling loss rate, the higher the tightness of the coating.
  • the nanocomposite further comprises an amorphous carbon substrate dispersed in the amorphous carbon substrate. More preferably, the nanocomposite consists of an amorphous carbon substrate and the carbon-coated transition metal particles dispersed therein.
  • the nanocomposites according to the invention do not contain carbon nanotubes.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and the nanocomposites are respectively in a pore size range of 2-7 nm and a pore size range of 8-20 nm.
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the nanocomposite is in a pore size range of 2-5 nm and 6-15 nm
  • the pore sizes has a mesoporous distribution peak, and further preferably, the ratio of the mesoporous volume in the nanocomposite having a pore diameter in the range of 2 to 5 nm to the total pore volume is greater than about 5%, such as from about 10% to 30%.
  • the ratio of mesoporous volume to total pore volume of the nanocomposite is greater than about 50%, more preferably greater than about 80%, further preferably greater than about 90%, particularly preferably greater than about 95%, most preferably It is about 100%.
  • the composite material has a rich mesoporous structure, thereby achieving higher mass transfer efficiency.
  • the nanocomposite has a mesopore volume of from about 0.05 to 1.25 cm 3 /g.
  • the nanocomposite when the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, the nanocomposite may have a mesopore volume of about 0.30-0.50 cm 3 /g. In other embodiments, when the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, the mesoporous volume of the nanocomposite may be about 0.10-0.30 cm 3 / g.
  • the nanocomposite surface area greater than about 140m 2 / g, preferably greater than about 200m 2 / g.
  • the nanocomposite has a carbon content of about 10.0% to 60.0% and a transition metal content of about 30.0% to 85.0% by mass percent.
  • the carbon content of the nano-composite may be about 15.0%-40.0%.
  • the transition metal content may be about 50.0%-80.0%; or, when the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, the carbon content of the nanocomposite may be about 30.0%-50.0%, the transition metal content may be about 30.0%-60.0%.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and the nanocomposite has an oxygen content of less than about 15.0% by mass, preferably about 1.0% to 10.0%, more preferably from about 0.2% to 5.0%; or, the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the nanometer is in mass percentage
  • the total content of nitrogen and oxygen in the composite material is less than about 15.0%, preferably from about 0.2% to about 12.0%, more preferably from about 0.5% to about 10.0%; further preferably, the nitrogen content is from about 0.1% to about 10%, particularly preferably about 1-5%.
  • the graphitized carbon layer is also doped with hydrogen, and the nanocomposite has a hydrogen content of about 0.2 to 2% by mass percent.
  • the transition metal element in the nanocomposite according to the invention is present in a reduced state, such as a zero valence state, ie there is no transition metal element present in the form of an oxidation state such as an oxide.
  • the sum of the contents of the components in the nanocomposite according to the present invention is 100%.
  • the graphitized carbon layer has a thickness of from about 0.3 to 6.0 nm, more preferably from about 0.3 to 3 nm, and particularly preferably from about 1 to 3 nm.
  • the carbon-coated transition metal particles having a core-shell structure have a particle diameter of from about 1 to 200 nm, more preferably from about 3 to 100 nm, still more preferably from about 4 to 50 nm.
  • the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), more preferably iron, One or more of cobalt, nickel and copper, most preferably nickel (Ni).
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen
  • the lattice structure of the transition metal nanoparticles is a face-centered cubic lattice structure (fcc And / or close-packed hexagonal lattice structure (hcp), that is, there may be only a face-centered cubic lattice structure, or only a close-packed cubic lattice structure, or a face-centered cubic lattice structure and a close-packed hexagonal Lattice structure.
  • the nanocomposite according to the first aspect of the present invention is considered to be a transition from an amorphous carbon substrate and a "graphite-coated carbon layer that is closely packed (substantially not in contact with the outside).
  • a metal nanoparticle" and a “transition metal nanoparticle that can be in contact with the outside” constitute a composite material having a mesoporous structure.
  • the nanocomposite has a rich defect surface on the surface of the graphitized carbon layer doped with oxygen and/or nitrogen, and the carbon material itself has catalytic activity, and cooperates with the transition metal nano particles to make the nano composite material better. Catalytic properties.
  • the nanocomposite according to the first aspect of the present invention has a rich mesoporous structure, which facilitates the diffusion of reactants and products, and makes the nanocomposite more efficient in mass transfer, thereby having more excellent catalytic performance.
  • the nanocomposite has a multi-level mesoporous structure with different pore size ranges, it can exhibit more unique properties and can be applied to a wider range of applications.
  • the nanocomposite according to the first aspect of the present invention is doped with oxygen and/or nitrogen in the graphitized carbon layer, and the oxygen content can be adjusted by additionally introducing an oxygen-containing organic compound such as a polyol in the preparation process, and the nitrogen content can be passed. Additional nitrogen-containing organic compounds, such as hexamethylenetetramine, are introduced during the preparation to adjust. By adjusting the nitrogen and oxygen contents in the nanocomposite, the catalytic performance of the carbon layer can be adjusted to make it suitable for catalyzing different reactions.
  • the present invention provides a nanocomposite comprising carbon-coated transition metal particles having a core-shell structure, the shell layer being graphitized carbon doped with oxygen and/or nitrogen
  • the core is a transition metal nanoparticle, wherein the nanocomposite has a pickling loss rate of ⁇ 10%, which is a tightly coated nanocomposite.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and is not doped with elements other than hydrogen and oxygen.
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and is not doped with other elements than hydrogen, oxygen, and nitrogen.
  • the nanocomposite is a porous material having at least one mesoporous distribution peak. More preferably, the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • the nanocomposite further comprises an amorphous carbon substrate dispersed in the amorphous carbon substrate. More preferably, the nanocomposite consists of an amorphous carbon substrate and the carbon-coated transition metal particles dispersed therein.
  • the nanocomposites according to the invention do not contain carbon nanotubes.
  • the ratio of mesoporous volume to total pore volume of the nanocomposite is greater than about 50%, more preferably greater than about 80%, further preferably greater than about 90%, particularly preferably greater than about 95%, most preferably It is about 100%.
  • the nanocomposite has a mesopore volume of about 0.05-1.25 cm 3 /g. In some embodiments, the nanocomposite may have a mesopore volume of about 0.30-0.50 cm 3 . /g. In other embodiments, the nanocomposite may have a mesopore volume of from about 0.10 to 0.30 cm 3 /g.
  • the nanocomposite surface area greater than about 140m 2 / g, preferably greater than about 200m 2 / g.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and the nanocomposites are respectively in a pore size range of 2-7 nm and a pore size range of 8-20 nm.
  • the shell of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the nanocomposite is in a pore size range of 2-5 nm and 6-16 nm
  • the pore sizes has a mesoporous distribution peak, and further preferably, the ratio of the mesoporous volume in the nanocomposite having a pore diameter in the range of 2 to 5 nm to the total pore volume is greater than about 5%, such as from about 10% to 30%.
  • the nanocomposite has a carbon content of about 15.0% to 60.0% and a transition metal content of about 30.0% to 80.0% by mass percent. In some embodiments, the nanocomposite may have a carbon content of about 30-60 wt% and a transition metal content of about 30-60 wt%, by mass percent.
  • the shell layer of the carbon-coated transition metal particles is an oxygen-doped graphitized carbon layer, and the oxygen content in the nanocomposite is less than about 15.0% by mass percentage, preferably About 1.0% to 10.0%, more preferably about 0.2% to 5.0%; or, the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and in terms of mass percentage,
  • the total content of nitrogen and oxygen in the nanocomposite is less than about 15.0%, preferably from about 0.2% to about 12.0%, more preferably from about 0.5% to 10.0%; further preferably, the nitrogen content is from about 0.1% to about 10%, particularly preferably About 1-5%.
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the nanocomposite has a nitrogen content of about 2 in mass percent 8%.
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the oxygen content of the nanocomposite is about 3 in mass percent 9%.
  • the graphitized carbon layer is also doped with hydrogen, and the nanocomposite has a hydrogen content of about 0.2 to 2% by mass percent.
  • the transition metal element in the nanocomposite according to the invention is present in a reduced state, such as a zero valence state, ie there is no transition metal element present in the form of an oxidation state such as an oxide.
  • the sum of the contents of the components in the nanocomposite according to the present invention is 100%.
  • the graphitized carbon layer has a thickness of from about 0.3 to 6.0 nm, more preferably from about 0.3 to 3 nm, and particularly preferably from about 1 to 3 nm.
  • the carbon-coated transition metal particles having a core-shell structure have a particle diameter of from about 1 to 200 nm, more preferably from about 3 to 100 nm, still more preferably from about 4 to 50 nm.
  • the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), more preferably iron, One or more of cobalt, nickel and copper, most preferably nickel (Ni).
  • the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen
  • the lattice structure of the transition metal nanoparticles is a face-centered cubic lattice structure (fcc And/or close-packed hexagonal lattice structure (hcp).
  • the nanocomposite according to the second aspect of the present invention is considered to be a transition from an amorphous carbon substrate and a "graphitized carbon layer that is dispersed therein (substantially not in contact with the outside).
  • the tightly coated nanocomposites can better ensure the loss rate of the core transition metal in the application, thereby better exerting the function of the composite.
  • the active center of the catalytic hydrogenation reaction is a transition metal, and the reactant must be brought into contact with the metal center regardless of the specific structure of the catalyst.
  • the nanocomposites in which the transition metal nanoparticles of the present invention are closely coated with a graphitized carbon layer still have an excellent ability to catalytically hydrogenate and reduce organic compounds.
  • the nanocomposite according to the second aspect of the present invention has a rich mesoporous structure, which facilitates the diffusion of reactants and products, and makes the nanocomposite more efficient in mass transfer, thereby having more excellent catalytic performance.
  • the nanocomposite has a multi-level mesoporous structure with different pore size ranges, it can exhibit more unique properties and can be applied to a wider range of applications.
  • the nanocomposite according to the second aspect of the present invention is doped with oxygen and/or nitrogen in the graphitized carbon layer, and the oxygen content can be adjusted by additionally introducing an oxygen-containing organic compound such as a polyol in the preparation process, and the nitrogen content can be passed. Additional nitrogen-containing organic compounds, such as hexamethylenetetramine, are introduced during the preparation to adjust.
  • the catalytic performance of the carbon layer can be adjusted to make it suitable for catalyzing different reactions.
  • the present invention provides a method of preparing a nanocomposite comprising carbon coated transition metal particles, comprising the steps of:
  • step iii) is treated with a non-oxidizing strong acid.
  • the mass ratio of the transition metal source to the polyorganocarboxylic acid in the mixture used in step i) is from about 1: 0.1 to 10, more preferably from about 1: 0.5 to 5, particularly preferably from about 1: 0.8. -3.
  • the mixture used in step i) further comprises a nitrogen-containing organic compound and/or an oxygen-containing organic compound different from the polybasic organic carboxylic acid.
  • the mass ratio of the transition metal source, the polyorganocarboxylic acid and the nitrogen-containing organic compound in the mixture used in step i) is from about 1:0.1 to 100:0.1-100, more It is preferably from about 1:0.5 to 5:0.5 to 5, particularly preferably from about 1:0.8 to 2:1-2.
  • the nitrogen-containing organic compound is selected from one or more of urea, melamine, dicyandiamide, hexamethylenetetramine, and an amino acid
  • the oxygen-containing organic compound is selected from the group consisting of Alcohols and organic carboxylic acids such as lactic acid.
  • the mixture used in step i) may further comprise other organic compounds than the polybasic organic carboxylic acid, the nitrogen-containing organic compound, and the oxygen-containing organic compound.
  • Any organic compound which can supplement the carbon source required in the product and which does not contain other dopant atoms can be used, preferably an organic compound which does not have a volatile property. More preferably, the mass ratio of the other organic compound to the transition metal source in the mixture is from about 0 to about 10:1, more preferably from about 0 to about 3:1.
  • the transition metal is selected from one or more of the group consisting of iron, cobalt, nickel, copper and zinc, more preferably one or more of iron, cobalt, nickel and copper, most preferably It is nickel.
  • the transition metal source is selected from one or more of the organic acid salts, carbonates, basic carbonates, oxides and hydroxides of the transition metal.
  • the transition metal organic acid salt of the present invention is not particularly limited as long as it can be mixed with the polybasic organic carboxylic acid in a solvent to form a homogeneous solution.
  • the transition metal organic acid salt includes, but is not limited to, a hetero atom-free organic carboxylate of the transition metal, such as acetate or the like.
  • the polybasic organic carboxylic acid of the present invention is not particularly limited as long as it can be mixed with the transition metal organic acid salt in a solvent to form a homogeneous solution.
  • the polybasic organic carboxylic acid may be a nitrogen-containing or nitrogen-free polybasic organic carboxylic acid, and in the case of using a nitrogen-containing polybasic organic carboxylic acid, corresponds to a combination of a nitrogen-free polybasic organic carboxylic acid and a nitrogen-containing organic compound.
  • the polybasic organic carboxylic acid used is a nitrogen-containing polybasic organic carboxylic acid, no additional nitrogen-containing organic compound may be added, and such an embodiment is also within the scope of the present invention.
  • the polybasic organic carboxylic acid is selected from one or more of the group consisting of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, EDTA, and dipicolinic acid.
  • the dipicolinic acid may be 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3, 4-pyridinedicarboxylic acid and/or 3,5-pyridinedicarboxylic acid.
  • the mixture used in step i) comprises a transition metal source and a nitrogen-containing organic polycarboxylic acid, optionally comprising an oxygen-containing organic compound and/or other organic compound.
  • the organic polycarboxylic acid includes, but is not limited to, citric acid
  • the nitrogen-containing organic polycarboxylic acid includes, but is not limited to, ethylenediaminetetraacetic acid (EDTA)
  • the transition metal source includes Not limited to acetates of transition metals, including but not limited to hexamethylenetetramine, including but not limited to organic polyols.
  • the solvent used in step i) is selected from one or more of the group consisting of water, methanol, ethanol, n-propanol and isopropanol, more preferably selected from the group consisting of water, ethanol or a combination thereof, most preferably water. .
  • the solvent in step ii), can be removed by, for example, evaporation, for example, spray drying at 80-120 ° C, or drying in an oven.
  • the precursor formed after removal of the solvent may be a mixture, and the mixture may be water soluble.
  • the inert protective atmosphere is nitrogen or argon
  • the reducing atmosphere is a mixed gas of inert gas and hydrogen
  • the high temperature pyrolysis process includes a heating section and a constant temperature section. Wherein in the heating section, the temperature is raised to a constant temperature section at a rate of about 0.5-30 ° C / min, the constant temperature period is about 20-600 min in the constant temperature section, and the temperature of the constant temperature section is about 400-800 ° C.
  • the heating rate of the temperature rising section is about 0.5-10 ° C / min, further preferably about 1-10 ° C / min, particularly preferably about 2.5-10 ° C / min, and most preferably about 1-5 ° C / min;
  • the thermostating period is maintained at a constant temperature of about 30 to 480 minutes, more preferably about 60 to 300 minutes; the temperature of the thermostatic section is about 500 to 800 ° C, and more preferably about 500 to 700 ° C.
  • the non-oxidizing strong acid used in step iv) includes, but is not limited to, one or a combination of two or more of hydrofluoric acid, hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid and/or sulfuric acid.
  • the acid treatment of step iv) is carried out at a temperature of about 30-100 ° C for at least about 1 h, preferably at a temperature of about 60-100 ° C for about 1-20 h, more preferably It is treated at a temperature of about 70-90 ° C for about 1-10 h.
  • the transition metal element in the nanocomposite prepared according to the method of the present invention exists in a reduced state (eg, a zero valence state), ie, there is no transition metal element present in an oxidized state (eg, an oxide).
  • a reduced state eg, a zero valence state
  • an oxidized state eg, an oxide
  • the method of making a nanocomposite according to the present invention comprises the steps of:
  • the product obtained by pyrolysis at elevated temperature is treated with an acid.
  • the process and conditions for evaporating the solvent may be by any feasible prior art, for example, spray drying at about 80-120 ° C, or drying in an oven.
  • the transition metal source, the nitrogen-free polyorganocarboxylic acid, the nitrogen-containing organic compound, and optionally the oxygen-containing organic compound and other organic compounds are mixed in a solvent in step i).
  • the transition metal source, the nitrogen-containing polyorganocarboxylic acid, and optionally the oxygen-containing organic compound and the other organic compound are mixed in a solvent in step i).
  • the nano composite material preparation method of the invention is simple and efficient, and the high temperature pyrolysis precursor directly comprises a transition metal source and a polybasic organic carboxylic acid and optionally a nitrogen-containing organic compound, an oxygen-containing organic compound and others.
  • the organic compound is directly mixed in an aqueous solution to prepare, and the atomic utilization ratio of the obtained precursor to the transition metal can reach 100%.
  • Overcoming the prior art preparation of the metal organic skeleton structure precursor requires self-assembly using a high-temperature and high-pressure reactor, and wastes a large amount of carbon. Source precursors, extensive use of organic solvents, and cumbersome purification steps.
  • the method of the invention does not need to form a metal-organic framework compound, and is easy to adjust the doping element content in the graphitized carbon layer during the preparation process, thereby conveniently adjusting the catalytic performance of the nanocomposite material to be suitable for different catalytic reactions.
  • a rich mesoporous structure is formed in the composite material.
  • the method of the present invention not only achieves these objectives, but also further forms a rich multi-level mesoporous structure in the composite material while producing a tightly packed core-shell structure.
  • the present invention also provides a nanocomposite comprising carbon coated transition metal particles prepared according to the method of the present invention.
  • the carbon-coated transition metal particles of the nanocomposite prepared according to the method of the present invention have a core-shell structure, the shell layer is a graphitized carbon layer doped with oxygen and/or nitrogen, and the core is a transition metal nanoparticle.
  • the carbon-coated transition metal particles are spherical or spheroidal, having a particle size of from about 1 to 200 nm, preferably from about 3 to 100 nm, more preferably from about 4 to 50 nm.
  • the transition metal element in the nanocomposite prepared according to the method of the present invention exists in a reduced state (eg, a zero valence state), ie, there is no transition metal element present in an oxidized state (eg, an oxide).
  • a reduced state eg, a zero valence state
  • an oxidized state eg, an oxide
  • the nanocomposite prepared according to the method of the present invention further comprises an amorphous carbon substrate dispersed in the amorphous carbon substrate; more preferably, the The nanocomposite consists of an amorphous carbon substrate and the carbon coated transition metal particles dispersed therein.
  • the nanocomposite has at least one mesoporous distribution peak, preferably two or more mesoporous distribution peaks.
  • the ratio of mesoporous volume to total pore volume of the nanocomposite is greater than about 50%, more preferably greater than about 80%, further preferably greater than about 90%, particularly preferably greater than about 95%, most preferably It is about 100%.
  • the nanocomposite has a pickling loss rate of ⁇ 40%, more preferably ⁇ 30%, particularly preferably ⁇ 10%.
  • the lattice structure of the transition metal nanoparticles is a face-centered cubic lattice structure and/or a close-packed hexagonal lattice structure.
  • the nanocomposite material has those features as defined above for the nanocomposite according to the first aspect of the invention.
  • the nanocomposite material has those features as defined above for the nanocomposite according to the second aspect of the invention.
  • the nanocomposite prepared according to the method of the present invention does not contain carbon nanotubes.
  • the nanocomposite prepared by the method of the invention has rich mesoporous structure, is favorable for diffusion of reactants and products, and has higher mass transfer efficiency of the nanocomposite, thereby having more excellent catalytic performance.
  • such composites produced in a single batch have two distribution peaks in the mesoporous range; such as mixing multiple batches of composite material, there may be more distribution peaks in the mesoporous range.
  • the nanocomposite has a multi-level mesoporous structure with different pore size ranges, it can exhibit more unique properties, and the multi-stage mesoporous structure can be applied to a wider range of applications.
  • the nanocomposite prepared according to the method of the present invention is doped with oxygen and/or nitrogen in the graphitized carbon layer, and the oxygen content can be adjusted by additionally introducing an oxygen-containing organic compound, such as a polyol, in the preparation process, and the nitrogen content can be An additional nitrogen-containing organic compound, such as hexamethylenetetramine, is introduced during the preparation to adjust.
  • an oxygen-containing organic compound such as a polyol
  • An additional nitrogen-containing organic compound such as hexamethylenetetramine
  • the nanocomposites prepared according to the method of the present invention can be widely used in the fields of catalytic materials, absorbing materials, information storage materials, magneto-optical materials, biomedical materials, and lubricating oil additives.
  • the transition metal is iron, cobalt, nickel, or copper
  • the composite material can be used for hydrogenating p-chloronitrobenzene to produce p-chloroaniline, hydrogenation of nitrobenzene to produce aniline, hydrogenation of nitrophenol to produce aminophenol, Hydrogenation of p-nitroanisole to produce p-aminoanisole, hydrogenation of phenol to produce cyclohexanol, hydrogenation of olefins, hydrogenation of aromatic hydrocarbons to produce cyclohexane derivatives, hydrogenation of aldehydes to produce alcohols, hydrogenation of ketones to produce alcohols, etc. Catalyst.
  • the present invention also provides the use of a nanocomposite according to the present invention as a catalyst for treating a volatile organic compound, comprising: contacting the volatile organic compound with the nanocomposite to perform a catalytic oxidation reaction .
  • the volatile organic compound is a volatile organic compound contained in industrial waste gas.
  • the volatile organic compound comprises butane, and the butane comprises from about 0.01% to about 2% by volume of the industrial waste gas.
  • the catalytic oxidation reaction is carried out at a temperature of from about 200 to 500 ° C, more preferably at a temperature of from about 300 to 400 ° C, particularly preferably at a temperature of from about 350 to 400 ° C.
  • the catalytic space velocity of the catalytic oxidation reaction is from about 2000 to 5000 ml of industrial off-gas / (hours per gram of the catalyst).
  • the industrial waste gas is an industrial waste gas produced by oxidation of n-butane to maleic anhydride.
  • the use of the nanocomposite of the present invention as a catalyst for the catalytic oxidation reaction of volatile organic compounds can reduce the severity of the reaction.
  • the butane component in the exhaust gas produced by the maleic anhydride production process may be catalytically oxidized to CO 2 in an amount of about 0.01 to 2 vol%, and the elimination rate may be 90% by volume or more at about 400 ° C.
  • the butane component can be completely catalytically oxidized to CO 2 .
  • the reaction temperature can be lowered, the reaction space velocity can be increased, and the low-concentration butane in the exhaust gas generated by the chemical production process can be completely oxidized at a relatively low temperature, which has a good industrial application prospect.
  • the invention also provides the use of a nanocomposite according to the invention as a catalyst in a hydrogenation reduction reaction.
  • the hydrogenation reduction reaction is selected from the group consisting of a reaction of hydrogenating p-chloronitrobenzene to produce p-chloroaniline, a reaction of hydrogenating nitrobenzene to produce aniline, and a reaction of hydrogenating nitrophenol to produce aminophenol.
  • Hydrogenation of p-nitroanisole to produce p-aminoanisole reaction of phenol hydrogenation to cyclohexanol, reaction of olefin hydrogenation, hydrogenation of aromatic hydrocarbon to produce cyclohexane derivative, hydrogenation of aldehyde to produce alcohol
  • the nanocomposite of the invention tightly coats the transition metal core through the graphitized carbon layer, thereby ensuring its safety during transportation and use.
  • the graphitized carbon layer of the nanocomposite has an excellent ability to catalyze the hydrogenation reduction reaction of the organic compound, thereby facilitating further improvement of the catalytic performance of the composite.
  • the present invention provides the following technical solutions:
  • a nanocomposite comprising carbon-coated transition metal particles, the carbon-coated transition metal particles having a core-shell structure, the shell layer being an oxygen-doped graphitized carbon layer, and the inner core being transition metal nanoparticles, wherein The nanocomposite is a porous material having at least one mesoporous distribution peak.
  • nanocomposite according to item A1 wherein the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • A3 The nanocomposite according to item A1 or A2, wherein the ratio of the pore volume of the porous material to the total pore volume is greater than about 50%, preferably greater than about 80%.
  • nanocomposite according to any one of items A1 to A4, wherein the nanocomposite has a pickling loss rate of ⁇ 40%.
  • the carbon content is about 10.0%-60.0%, and the transition metal content is about 30.0%-85.0. %; in particular, the carbon content may be from about 15.0% to 40.0%, and the transition metal content may be from about 50.0% to 80.0%.
  • nanocomposite according to any one of items A1 to A6, wherein the nanocomposite has an oxygen content of less than about 15.0%, preferably about 0.2% to 5.0% by mass.
  • a nanocomposite comprising carbon-coated transition metal particles, the carbon-coated transition metal particles having a core-shell structure, the shell layer being an oxygen-doped graphitized carbon layer, and the inner core being transition metal nanoparticles, wherein The pickling loss rate of the nanocomposite is ⁇ 10%.
  • nanocomposite of item B1 wherein the nanocomposite is a porous material having at least one mesoporous distribution peak.
  • nanocomposite according to item B1 wherein the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • nanocomposite according to any one of items B1 to B4, wherein the nanocomposite has a mesopore volume of about 0.05 to 1.25 cm 3 /g.
  • nanocomposite according to any one of items B1 to B5, wherein the nanocomposite has a carbon content of about 15% to 60% and a transition metal content of about 30% to 80% by mass percentage.
  • the carbon content may be from about 30% to about 60%
  • the transition metal content may be from about 30% to about 60%.
  • nanocomposite according to any one of items B1 to B6, wherein the nanocomposite has an oxygen content of less than about 15.0%, preferably about 1.0% to 10.0% by mass.
  • a nanocomposite comprising carbon-coated transition metal particles, the carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and nitrogen, and the inner core being transition metal nanoparticles, Wherein the nano-composite material has a pickling loss rate of ⁇ 10%.
  • nanocomposite of item C1 wherein the nanocomposite is a porous material having at least one mesoporous distribution peak.
  • nanocomposite according to item C2 wherein the nanocomposite is a porous material having two or more mesoporous distribution peaks.
  • nanocomposite according to any one of items C1 to C4, wherein the nanocomposite has a carbon content of about 15 to 60% by weight and a transition metal content of about 30 to 80% by weight.
  • a nanocomposite comprising carbon-coated transition metal particles, the carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and nitrogen, and the inner core being transition metal nanoparticles, Wherein the nanocomposite is a porous material having at least one mesoporous distribution peak.
  • the carbon content is about 10.0%-60.0%, and the transition metal content is about 30.0%-85.0. %; in particular, the carbon content may be from about 30.0% to 50.0%, and the transition metal content may be from about 30.0% to 60.0%.
  • nanocomposite according to any one of items D1 to D6, wherein the nanocomposite has a pickling loss rate of ⁇ 40%.
  • a method for preparing a carbon-coated transition metal nanocomposite comprising the steps of:
  • transition metal is one or more of iron, cobalt, nickel, and copper.
  • the transition metal salt is one or more of an organic acid salt, a carbonate salt and a basic carbonate salt of a transition metal; preferably the organic of the transition metal
  • the acid salt is a heteroatom-free organic carboxylate of the transition metal, such as an acetate salt.
  • any one of items E1 to E4, wherein the mass ratio of the transition metal salt to the polybasic organic carboxylic acid is from about 1: 0.1 to 10, preferably from about 1: 0.5 to 5, more preferably about 1. : 0.8-3.
  • the inert protective atmosphere is nitrogen or argon
  • the high temperature pyrolysis is at a rate of about 0.5-30 ° C / min Warming up to a constant temperature section, maintaining a constant temperature period of about 20-600 minutes in the constant temperature section, and the temperature of the constant temperature section is about 400-800 ° C; preferably, the heating rate is about 1-10 ° C / min, and maintaining a constant temperature in the constant temperature section
  • the time is 60-480 min and the temperature of the constant temperature section is about 500-800 °C.
  • the constant temperature section is maintained at a constant temperature of about 20-600 minutes, and the temperature of the constant temperature section is about 400-800 ° C; preferably, the temperature rising rate is about 1-10 ° C / min, and the constant temperature period is kept at a constant temperature of about 60-480 min.
  • the temperature of the constant temperature section is about 500-800 °C.
  • nanocomposite according to item E10 wherein the nanocomposite has at least one mesoporous distribution peak, preferably having two or more mesoporous distribution peaks.
  • nanocomposite according to any one of items E10 to E12, wherein the nanocomposite has a pickling loss rate of ⁇ 40%, preferably ⁇ 30%, more preferably ⁇ 10%.
  • a method for preparing a carbon-coated transition metal nanocomposite comprising the steps of:
  • transition metal is one or more selected from the group consisting of iron, cobalt, nickel, and copper.
  • the transition metal salt is one or more of an organic acid salt, a carbonate salt, a basic carbonate salt of the transition metal; preferably the transition metal
  • the organic acid salt is a heteroatom-free organic carboxylate of the transition metal, such as an acetate salt.
  • polybasic organic carboxylic acid is selected from the group consisting of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, EDTA, One or more of pyridine dicarboxylic acids.
  • any one of items F1 to F4 wherein the nitrogen-containing organic compound is one or more selected from the group consisting of urea, melamine, dicyandiamide, hexamethylenetetramine, and amino acids. .
  • any one of items F1 to F5 wherein the mass ratio of the transition metal salt, the polybasic organic carboxylic acid, and the nitrogen-containing organic compound is about 1:0.1-100:0.1-100 Preferably, it is from about 1:0.5 to 5:0.5 to 5, more preferably from about 1:0.8 to 2:1-2.
  • the inert protective atmosphere is nitrogen or argon
  • the high temperature pyrolysis is at a rate of about 0.5-30 ° C / min Warming up to a constant temperature section, maintaining a constant temperature period of about 20-600 minutes in the constant temperature section, and the temperature of the constant temperature section is about 400-800 ° C; preferably, the heating rate is about 1-10 ° C / min, and maintaining a constant temperature in the constant temperature section
  • the time is about 60-480 minutes and the temperature of the constant temperature section is about 500-800 °C.
  • any one of items F1 to F7 wherein the reducing atmosphere is a mixed gas of an inert gas and a hydrogen gas, and the high temperature pyrolysis is heated to a constant temperature section at a rate of about 0.5-30 ° C / min,
  • the constant temperature section is maintained at a constant temperature of about 20-600 minutes, and the temperature of the constant temperature section is about 400-800 ° C; preferably, the temperature rising rate is about 1-10 ° C / min, and the temperature of the constant temperature section is about 500-800 ° C .
  • nanocomposite according to item F11, wherein the nanocomposite has at least one mesoporous distribution peak, preferably having two or more mesoporous distribution peaks.
  • nanocomposite according to any one of items F11 to F13, wherein the nanocomposite has a pickling loss rate of ⁇ 40%, preferably ⁇ 30%, more preferably ⁇ 10%.
  • a method for hydrogenating p-chloroaniline by hydrogenating p-chloronitrobenzene comprising the step of hydrogenating p-chloronitrobenzene in the presence of a catalyst, wherein items A1-A10, B1-B10, C1-C10, The nanocomposite according to any one of D1-D11, E10-E14 and F11-F15 is used as the catalyst.
  • the method according to item G1 comprising the step of mixing the catalyst with p-chloronitrobenzene in a solvent, followed by hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. One or more.
  • H1 a method for hydrogenating nitrobenzene to produce aniline, comprising the step of hydrogenating and reducing nitrobenzene in the presence of a catalyst, wherein items A1-A10, B1-B10, C1-C10, D1-D11, E10-
  • a catalyst wherein items A1-A10, B1-B10, C1-C10, D1-D11, E10-
  • the nanocomposite according to any one of E14 and F11 to F15 is used as the catalyst.
  • a process for the hydrogenation of nitrophenol to produce an aminophenol comprising the step of hydrogenating a nitrophenol in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10 The nanocomposite according to any one of E14 and F11-F15 as the catalyst.
  • the method of item 11 comprising the step of mixing the catalyst with nitrophenol in a solvent and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • a method for hydrogenating p-aminoanisole by hydrogenating p-nitroanisole comprising the step of hydrogenating and reducing p-nitroanisole in the presence of a catalyst, wherein items A1-A10, B1-B10, The nanocomposite according to any one of C1-C10, D1-D11, E10-E14, and F11-F15 is used as the catalyst.
  • the method according to item J1 comprising the step of mixing the catalyst with p-nitroanisole in a solvent, followed by hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and One or more of the water.
  • K1 a method for hydrogenating phenol to produce cyclohexanol, comprising the step of hydrogenating and reducing phenol in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10-E14 and The nanocomposite according to any one of F11 to F15 is used as the catalyst.
  • the method according to item K1 comprising the step of mixing the catalyst with a phenolic compound in a solvent, and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • a method for hydrogenating an olefin comprising the step of hydrogenating and reducing an olefin in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D111, E10-E14 and F11-F15 Any of the nanocomposites described as the catalyst.
  • the method according to item L1 comprising the step of mixing the catalyst with the olefin in a solvent, and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • a process for the hydrogenation of an aromatic hydrocarbon to produce a cyclohexane derivative comprising the step of hydrogenating an aromatic hydrocarbon in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10-
  • the nanocomposite according to any one of E14 and F11 to F15 is used as the catalyst.
  • the method according to item M1 comprising the step of mixing the catalyst with the aromatic hydrocarbon in a solvent, and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • N1 a method for hydrogenating an aldehyde to produce an alcohol, comprising the step of hydrogenating the aldehyde in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10-E14 and The nanocomposite according to any one of F11 to F15 is used as the catalyst.
  • the method according to item N1 comprising the step of mixing the catalyst with the aldehyde in a solvent, and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • a method for hydrogenating a ketone to produce an alcohol comprising the step of hydrogenating the ketone in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10-E14 and The nanocomposite according to any one of F11 to F15 is used as the catalyst.
  • the method according to item O1 comprising the step of mixing the catalyst with the ketone in a solvent, and then performing a hydrogenation reduction, wherein the solvent is selected from the group consisting of alcohols, ethers, alkanes, and water. kind or more.
  • a method of treating volatile organic compounds comprising the step of catalytically oxidizing the volatile organic compounds in the presence of a catalyst, wherein the items A1-A10, B1-B10, C1-C10, D1-D11, E10-E14 and The nanocomposite according to any one of F11 to F15 is used as the catalyst.
  • the method according to item P1 wherein the volatile organic compound is a volatile organic compound contained in an industrial waste gas produced by industrial waste gas, in particular, n-butane oxidation to produce maleic anhydride.
  • a method for reducing an organic compound by catalytic hydrogenation characterized in that a catalyst having a core-shell structure is used, and hydrogen is used as a reducing agent to catalytically hydrogenate an organic compound; and the shell layer of the core-shell structure is graphite
  • the carbon layer is a transition metal; the core is tightly coated with a graphitized carbon layer.
  • transition metal is one of iron, cobalt, nickel, copper, and zinc, or any combination thereof.
  • a method for reducing an organic compound by catalytic hydrogenation characterized in that a catalyst having a core-shell structure is used, and hydrogen is used as a reducing agent to catalytically hydrogenate an organic compound; the shell layer of the core-shell structure is The graphitized carbon layer has a core as a transition metal; in the pore distribution diagram of the catalyst, there are more than one distribution peak in the mesoporous range.
  • transition metal is one of iron, cobalt, nickel, copper, and zinc, or any combination thereof.
  • a method for reducing nitrobenzene to aniline by catalytic hydrogenation characterized in that the catalytic hydrogenation of nitrobenzene is carried out by the method according to any one of items Q1 to Q8.
  • a method for reducing a halogenated nitrobenzene to a halogenated aniline by catalytic hydrogenation characterized by catalytic hydrogenation reduction of halonitrobenzene by the method according to any one of items Q1 to Q8 .
  • a method for reducing nitrophenol to aminophenol by catalytic hydrogenation characterized in that the catalytic hydrogenation of p-nitrophenol is carried out by the method according to any one of items Q1 to Q8.
  • a method for reducing nitroanisole to aminoanisole by catalytic hydrogenation characterized in that catalytic hydrogenation reduction of nitroanisole is carried out by the method according to any one of items Q1 to Q8. .
  • Q13 a composite material of carbon and transition metal, characterized in that it has a core-shell structure, the shell layer of the core-shell structure is a graphitized carbon layer, and the inner core is a transition metal; in the pore distribution diagram of the composite material, There are more than one distribution peak in the mesoporous range.
  • the composite material according to item Q13 characterized in that, in the pore distribution diagram of the composite material, there are two distribution peaks in the mesoporous range (for example, two distribution peaks appear at 1-7 nm and 8-16 nm) .
  • the composite material according to item Q13 or Q14 characterized in that the particle diameter of the transition metal is between a range formed by any two integer points of 1 nm to 200 nm (for example, 1, 5, 10, 15, 20) a range formed by any two points of 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200).
  • organic compound is an organic compound containing one of the following groups or any combination thereof: a nitro group, a carbonyl group and a carbon-carbon double bond.
  • the reagents used in this application are of analytical grade and the reagents used are commercially available, for example, from Sigma-Aldrich.
  • the model of the XRD diffractometer used is an XRD-6000 X-ray powder diffractometer (Shimadzu, Japan).
  • the surface topography of the material is characterized by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the model of the scanning electron microscope used was a Hitachi S-4800 cold field scanning transmitting electron microscope.
  • the scanning electron microscope was tested under the condition that the powder sample was fixed on the sample stage through a conductive adhesive, and the acceleration voltage was 5 kV.
  • the model of the high-resolution transmission electron microscope (HRTEM) used is JEM-2100 (HRTEM) (Japan Electronics Co., Ltd.).
  • the high-resolution transmission electron microscope is tested under the following conditions: an acceleration voltage of 200 kV.
  • the X-ray photoelectron spectroscopy (XPS) used is an ESCALab 220i-XL ray electron spectrometer equipped with Avantage V5.926 software manufactured by VG Scientifc.
  • X-ray photoelectron spectroscopy analysis conditions were as follows: the excitation source was monochromated A1K ⁇ X-ray, the power was 330 W, and the basic vacuum was 3 ⁇ 10 -9 mbar during the analysis.
  • the electron binding energy was corrected by the C1s peak (284.6 eV), and the post-peak processing software was XPSPEAK.
  • the carbon (C), hydrogen (H), and oxygen (O) elements are analyzed in Elementar. Performed on a Micro Cube elemental analyzer.
  • the specific operation methods and conditions are as follows: The sample is weighed 1-2mg in a tin cup, placed in an auto-injection tray, and burned into a combustion tube through a ball valve. The combustion temperature is 1000 ° C (in order to remove atmospheric interference during injection, helium is blown Sweep), and then reduce the burned gas with reduced copper to form carbon dioxide and water.
  • the mixed gas is separated by two desorption columns and sequentially detected by a TCD detector.
  • Oxygen is analyzed by pyrolysis, which converts oxygen in the sample to CO under the action of a carbon catalyst, and then detects CO by TCD. Since the composite material contains only carbon, hydrogen, oxygen and metal elements, the total content of the metal elements can be obtained from the total content of three elements of carbon, hydrogen and oxygen.
  • the shell of the carbon-coated transition metal particles is a nanocomposite of a graphitized carbon layer doped with oxygen and nitrogen, and carbon (C), hydrogen (H), oxygen (O), nitrogen (N) Analysis of the four elements was also performed on the Elementar Micro Cube elemental analyzer.
  • the specific operation methods and conditions are as follows: The sample is weighed 1-2mg in a tin cup, placed in an auto-injection tray, and burned into a combustion tube through a ball valve. The combustion temperature is 1000 ° C (in order to remove atmospheric interference during injection, helium is blown Sweep), and then reduce the burned gas with reduced copper to form nitrogen, carbon dioxide and water.
  • the mixed gas is separated by three desorption columns and sequentially detected by a TCD detector.
  • Oxygen is analyzed by pyrolysis, which converts oxygen in the sample to CO under the action of a carbon catalyst, and then detects CO by TCD. Since the composite contains only carbon, hydrogen, oxygen, nitrogen and metal elements, the total content of the metal elements can be obtained from the total content of four elements of carbon, hydrogen, oxygen and nitrogen.
  • the ratio between different metal elements is determined by an X-ray fluorescence spectrometer (XRF), and the total content of known elements of carbon, hydrogen, oxygen and nitrogen (if present) is calculated to compound different metal elements.
  • the content in the material is determined by an X-ray fluorescence spectrometer (XRF) used in the present application.
  • the model of the X-ray fluorescence spectrometer (XRF) used in the present application is a Rigaku 3013 X-ray fluorescence spectrometer.
  • the test conditions of X-ray fluorescence spectrometry were as follows: the scanning time was 100 s, and the atmosphere was air.
  • the pore structure properties of the sample were determined by a Quantachrome AS-6B type analyzer, the specific surface area and pore volume were obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve was according to the Barrett-Joyner-Halenda (BJH) method. The desorption curve was calculated.
  • the composition of the gas was analyzed by on-line gas chromatography, and the chromatographic model was Agilent GC 7890B with an accuracy of 10 -6 .
  • the test gas is passed from the inlet to the chromatogram, separated by a column, and each chromatographic peak is integrated to calculate the percentage of each gas component.
  • the "pickling loss rate” is measured and calculated as follows:
  • the ratio of 1 g of the sample was added to 20 mL of an aqueous sulfuric acid solution (1 mol/L), and the sample was treated at 90 ° C for 8 hours, then washed with deionized water to neutrality, dried, weighed, and analyzed. Calculate the pickling loss rate as follows:
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 650 ° C at a rate of 5 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 150 mL/min, and the temperature was raised to 600 ° C at a rate of 5 ° C/min, and the heating was stopped after the temperature was kept for 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 150 mL/min, and the temperature was raised to 600 ° C at a rate of 5 ° C/min, and the heating was stopped after the temperature was kept for 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated cobalt nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 550 ° C at a rate of 3 ° C/min, and the heating was stopped after a constant temperature of 8 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 6 ° C/min, and the heating was stopped after 1 h of constant temperature.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the fore body was placed in a porcelain boat, then the porcelain boat was placed in the constant temperature zone of the tube furnace, nitrogen gas with a flow rate of 150 mL/min was introduced, and the temperature was raised to 500 ° C at a rate of 5 ° C/min, and the heating was stopped after 2 hours of constant temperature. .
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel-cobalt nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 4 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 650 ° C at a rate of 5 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 4 ° C/min, and then the flow rate was 30 mL/
  • hydrogen is kept at a constant temperature for 2 hours, the hydrogen is turned off and the heating is stopped.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • Example 1-1 The procedure of Example 1-1 was repeated except that the acid treatment step was added after Example 1-1, that is, 2 g of the material obtained in Example 1-1 was added to 40 mL of an aqueous sulfuric acid solution (1 mol/L) at 90 ° C. Processed for 8h. It is then washed with deionized water to neutrality to obtain a tightly covered carbon-coated nickel nanocomposite.
  • Carbon-coated nano-nickel nanocomposites were prepared as disclosed in the document RSC Advances, 2017, 7, 1531-1539.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 40 mL/min, and the temperature was raised to 600 ° C at a rate of 10 ° C/min, and the heating was stopped after 1 h of constant temperature.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • Example 1-1 The procedure of Example 1-1 was repeated except that 10 g of nickel acetate was replaced with 10 g of nickel nitrate.
  • Example number Pickling loss rate (%) Example 1-1 36.2 Example 1-2 13.2 Examples 1-3 9.5 Examples 1-4 9.5 Examples 1-5 28.6 Example 1-6 23.1 Example 1-7 12.4 Example 1-8 29.4 Example 1-9 25.6 Examples 1-10 0.56 Comparative example 1-1 92 Comparative example 1-2 100 Comparative example 1-3 100 Comparative example 1-4 100
  • XPS X-ray photoelectron spectroscopy
  • Figure 1-1 is an XRD pattern of the precursor prepared in Example 1-1, illustrating that the precursor is an amorphous material
  • Figure 1-2 is the magnetic properties of the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • FIG. 1-3 is the carbon-coated nickel nanocomposite prepared in Example 1-1.
  • the TEM image of the material shows that the material is a composite material containing carbon-coated metal particles, and a carbon layer having a certain degree of graphitization is wrapped in the outer layer of the nickel nanoparticles to form a complete core-shell structure.
  • Example 1-1 is an XRD pattern of the carbon-coated nickel nanocomposite prepared in Example 1-1, and it can be seen that there is a diffraction peak corresponding to graphite carbon in the diffraction pattern of the material (the 2 ⁇ angle is 26°) And the diffraction peaks of nickel (fcc-Ni) corresponding to the face-centered cubic structure (2 ⁇ angles of 44.5°, 51.7°, and 76.4°), indicating that the material includes carbon with a certain degree of graphitization and exists in a face-centered cubic structure.
  • Nickel The average particle diameter of the carbon-coated nickel nanoparticles calculated by the Scherrer formula was 4.7 nm.
  • 1-6 are TEM images of carbon-coated nickel nanocomposites prepared in Example 1-2. It can be seen from Fig. 1-6 that the material contains a core-shell structure in which carbon as a core and metal having a certain degree of graphitization is a shell. In the XRD diffraction pattern of the material (Figs. 1-7), there are diffraction peaks corresponding to graphite carbon (2 ⁇ angle is 26°) and diffraction peaks corresponding to fcc-Ni (44.5°, 51.9°, and 76.2°), indicating The material includes carbon having a certain degree of graphitization and nickel present in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nickel nanoparticles calculated by the Scherrer formula was 34.5 nm.
  • the BET test showed that the material had a specific surface area of 137 m 2 /g and a pore volume of 0.343 cm 3 /g, wherein the mesopore volume was 0.323 cm 3 /g, which accounted for 94% of the total pore volume.
  • 1-8 are graphs showing pore distribution of the carbon-coated nickel nanocomposite prepared in Example 1-2. As can be seen from Figures 1-8, there are two mesoporous distribution peaks at 3.85 nm and 11.53 nm in the BJH pore size distribution curve of the material. After pickling experiments, the pickling loss rate of the material was 13.2%. On the basis of the foregoing method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-9 are TEM images of carbon-coated cobalt nanocomposites prepared in Examples 1-3.
  • the material contains a core-shell structure in which carbon as a core and metal having a certain degree of graphitization is a shell.
  • XRD diffraction pattern of the material Figs. 1-10
  • diffraction peaks corresponding to graphite carbon 2 ⁇ angle is 26°
  • diffraction peaks corresponding to fcc-Co 44.3°, 51.4°, and 75.9°
  • the average particle diameter of the carbon-coated cobalt nanoparticles was calculated by the Xie Le formula to be 24 nm.
  • the BET test showed that the material had a specific surface area of 192 m 2 /g and a pore volume of 0.398 cm 3 /g, wherein the mesopore volume was 0.394 cm 3 /g, which accounted for 99% of the total pore volume.
  • 1 to 11 are pore distribution curves of the carbon-coated cobalt nanocomposites prepared in Examples 1-3. As can be seen from Figures 1-11, there are two mesoporous distribution peaks at 3.38 nm and 8.98 nm in the BJH pore size distribution curve of the material. After pickling experiments, the pickling loss rate of the material was 9.5%. On the basis of the foregoing method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-12 are TEM images of carbon-coated nickel nanocomposites prepared in Examples 1-4.
  • the material contains a core-shell structure in which carbon as a core and a certain degree of graphitization of carbon as a shell.
  • the pickling loss rate of the material was 9.5%.
  • the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-13 are TEM images of carbon-coated nickel nanocomposites prepared in Examples 1-5.
  • the material forms a core-shell structure in which carbon as a core, metal having a certain degree of graphitization, and carbon as a shell.
  • the pickling loss rate of the material was 28.6%.
  • the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-14 are TEM images of carbon-coated nickel-cobalt nanocomposites prepared in Examples 1-6.
  • the material contains a core-shell structure in which carbon having a certain degree of graphitization is a shell with metal nickel or cobalt nanoparticles as a core.
  • XRD diffraction pattern of the material Figs. 1-15
  • diffraction peaks corresponding to graphite carbon 2 ⁇ angle is 25.6°
  • diffraction peaks corresponding to fcc-Ni and fcc-Co (44.3°, 51.7°, and 76.0).
  • ° indicating that the material includes carbon with a certain degree of graphitization and nickel and cobalt in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nanoparticles was calculated by Xie Le formula to be 39 nm.
  • the BET test showed that the material had a specific surface area of 159 m 2 /g and a pore volume of 0.208 cm 3 /g, wherein the mesopore volume was 0.196 cm 3 /g, which accounted for 94% of the total pore volume.
  • 1-16 are pore distribution curves of the carbon-coated nickel-cobalt nanocomposites prepared in Examples 1-6. As can be seen from Figures 1-16, there are two mesoporous distribution peaks at 3.25 nm and 8.94 nm in the BJH pore size distribution curve of the material. After pickling experiments, the pickling loss rate of the material was 23.1%. On the basis of the foregoing method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-17 are TEM images of the carbon-coated nickel nanocomposites prepared in Examples 1-7.
  • the material contains a core-shell structure in which carbon as a core and metal having a certain degree of graphitization is a shell.
  • Figs. 1-17 In the XRD diffraction pattern of the material (Figs.
  • the BET test showed that the material had a specific surface area of 228 m 2 /g and a pore volume of 0.293 cm 3 /g, wherein the mesopore volume was 0.293 cm 3 /g, which accounted for 100% of the total pore volume.
  • 1-19 are graphs showing pore distribution of the carbon-coated nickel nanocomposites prepared in Examples 1-7. As can be seen from Figures 1-19, there are two mesoporous distribution peaks at 3.97 nm and 6.39 nm in the BJH pore size distribution curve of the material. After pickling experiments, the pickling loss rate of the material was 12.4%. On the basis of the foregoing method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIG. 1-20 are TEM images of carbon-coated nickel nanocomposites prepared in Examples 1-8.
  • the material contains a core-shell structure with carbon as a shell with metal nickel nanoparticles as the core and a certain degree of graphitization.
  • XRD diffraction pattern of the material Fig. 1-21
  • diffraction peaks corresponding to graphite carbon 2 ⁇ angle is 25.8°
  • diffraction peaks corresponding to fcc-Ni 44.6°, 51.8°, and 76.4°
  • the average particle diameter of the carbon-coated nickel nanoparticles calculated by the Xie Le formula was 8.4 nm.
  • the pickling loss rate of the material was 29.4%.
  • the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • Figure 1-22 is a TEM image of the carbon coated nickel nanocomposite prepared in Examples 1-9.
  • the material contains a core-shell structure in which carbon is used as a core and metal having a certain degree of graphitization is a shell.
  • XRD diffraction pattern of the material Figs. 1-23
  • diffraction peaks corresponding to graphite carbon 2 ⁇ angle is 25.9°
  • diffraction peaks corresponding to fcc-Ni 44.4°, 51.7°, and 76.3°
  • the material includes carbon having a certain degree of graphitization and nickel present in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nickel nanoparticles calculated by the Xie Le formula was 7.5 nm. After pickling experiments, the pickling loss rate of the material was 25.6%. On the basis of the foregoing method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • FIGS. 1-24 are photographs of the magnetic test of the carbon-coated nickel nanocomposite prepared in Examples 1-10, after the magnet is attracted, the suspension of the carbon-coated nickel nanocomposite is rapidly cleared, indicating that the prepared The carbon coating material has strong magnetism.
  • Figure 1-25 is a TEM image of the nanocomposite. As can be seen from the figure, the material contains a core-shell structure with metal nickel nanoparticles as the core and a graphitized carbon layer as the shell.
  • the X-ray diffraction spectrum of the composite material is shown in Figure 1-26. It can be seen that there is a diffraction peak corresponding to graphite carbon in the diffraction pattern of the material (2 ⁇ angle is 25.7°) and corresponds to fcc-Ni.
  • the carbon-coated nickel nanocomposite prepared in Comparative Example 1-1 was tested by the above characterization, indicating that there is a diffraction peak corresponding to graphite carbon (26° angle of 26°) and diffraction corresponding to fcc-Ni in the XRD diffraction pattern of the material. Peaks (44.5°, 51.9°, and 76.2°) indicate that the material includes carbon with a certain degree of graphitization and nickel present in a face-centered cubic structure.
  • the BET test showed that the material had a specific surface area of 159 m 2 /g and a pore volume of 0.208 cm 3 /g, wherein a pore volume of >2 nm was 0.05 cm 3 /g, which accounted for 24% of the total pore volume. There is only one micropore distribution peak at 0.68 nm in the BJH pore size distribution curve of the material. After pickling experiments, the material had a pickling loss of 92%.
  • XRD patterns of sample materials prepared in Comparative Examples 1-4 from which it can be seen that there are diffraction peaks (44.2°, 51.6°, and 76.2°) corresponding to fcc-Ni in the diffraction pattern of the material.
  • the mass percentage of the elements contained in the material was determined by an elemental analyzer and an X-ray fluorescence spectrometer (XRF): carbon 1.34%, hydrogen 0.32%, oxygen 0.18%, and nickel 98.16%.
  • the method of the present invention enables the preparation of a tightly coated nanocomposite that allows the material to be used under more severe conditions. Furthermore, the method of the present invention is capable of preparing a tightly coated nanocomposite and having a rich mesoporous structure, particularly a multi-stage mesoporous structure, and is suitable for application in more fields.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 650 ° C at a rate of 5 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 150 mL/min, and the temperature was raised to 600 ° C at a rate of 5 ° C/min, and the heating was stopped after the temperature was kept for 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 700 ° C at a rate of 5 ° C/min, and the heating was stopped after 1 h of constant temperature.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated cobalt nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 4 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel-cobalt nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of the tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 700 ° C at a rate of 5 ° C/min, and the heating was stopped after 1 h of constant temperature.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 550 ° C at a rate of 3 ° C/min, and the heating was stopped after a constant temperature of 3 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 80 mL/min, and the temperature was raised to 800 ° C at a rate of 8 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 6 ° C/min, and the heating was stopped after 1 h of constant temperature.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • the precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 100 mL/min, and the temperature was raised to 600 ° C at a rate of 4 ° C/min, and the heating was stopped after a constant temperature of 2 hours.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite.
  • Example 2-1 The procedure of Example 2-1 was repeated except that an acid treatment step was added after Example 2-1, i.e., 2 g of the material obtained in Example 2-1 was added to 100 mL of 10 wt% hydrochloric acid, and treated at reflux temperature for 12 h. Then, it was washed with deionized water to neutrality and dried at 120 ° C to obtain a tightly covered carbon-coated nickel nanocomposite.
  • an acid treatment step was added after Example 2-1, i.e., 2 g of the material obtained in Example 2-1 was added to 100 mL of 10 wt% hydrochloric acid, and treated at reflux temperature for 12 h. Then, it was washed with deionized water to neutrality and dried at 120 ° C to obtain a tightly covered carbon-coated nickel nanocomposite.
  • Ni-MOF material Preparation of Ni-MOF material: Weigh 3.09g of nickel nitrate, 2.8g of terephthalic acid and 0.95g of triethylenediamine, add to 120mL of dimethylformamide, react at 120 ° C for 8h, then seal, at 120 °C is allowed to stand for 40h. After filtration, it was washed with dimethylformamide and methanol, and dried under vacuum to give Ni-MOF material.
  • Ni-doped carbon-coated nickel (Ni@CN) nanomaterials The obtained Ni-MOF was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, and nitrogen gas was introduced at a flow rate of 100 mL/min. And heated to 200 ° C at a rate of 4 ° C / min, constant temperature 2h, then warmed to 500 ° C, constant temperature 8h, stop heating. The mixture was cooled to room temperature under a nitrogen atmosphere to obtain a Ni@C-N nano material.
  • Example 2-1 The procedure of Example 2-1 was repeated except that 10 g of nickel acetate was replaced with 10 g of nickel nitrate.
  • 2-1 is a photograph of the magnetic test of the oxygen-nitrogen-doped carbon-coated nickel nanocomposite prepared in Example 2-1, and the suspension of the oxygen-nitrogen-doped carbon-coated nickel nanocomposite is rapidly attracted by the magnet. Clarification indicates that the composite has strong magnetic properties.
  • 2-2 is a TEM image of the oxygen-nitrogen-doped carbon-coated nickel nanocomposite prepared in Example 2-1. As can be seen from Fig. 2-2, the composite material comprises carbon-coated metal nickel particles, which encapsulate a carbon layer having a certain degree of graphitization on the outer layer of the nickel nanoparticles to form a complete core-shell structure.
  • FIG. 2-3 is an XRD pattern of the oxygen-nitrogen-doped carbon-coated nickel nanocomposite prepared in Example 2-1.
  • Fig. 2-3 in the diffraction pattern of the material, there are diffraction peaks corresponding to graphite carbon (2 ⁇ angle is 25.96°) and diffraction peaks corresponding to nickel (fcc-Ni) of the face centered cubic structure ( The 2 theta angles are 44.38°, 51.83°, and 76.42°), indicating that the material includes carbon having a certain degree of graphitization and nickel present in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nickel nanoparticles calculated by the Xie Le formula was 6.3 nm.
  • the BET test showed that the material had a specific surface area of 114 m 2 /g and a pore volume of 0.181 cm 3 /g, wherein the mesopore volume was 0.173 cm 3 /g, which accounted for 95.6% of the total pore volume.
  • Figures 2-4A and 2-4B show the N 2 adsorption-desorption isotherm curve and the BJH pore size distribution curve of the material, respectively. It can be seen that the composite material has two mesoporous distribution peaks at 3.75 nm and 10.03 nm. After pickling experiments, the material had a pickling loss of 14%.
  • Example 2-5 is a TEM image of the carbon-coated nickel nanocomposite prepared in Example 2-2, which shows that the material contains a core-shell structure in which carbon as a core with a certain degree of graphitization.
  • Fig. 2-6 XRD diffraction pattern of the material, there are diffraction peaks corresponding to graphite carbon (2 ⁇ angle is 25.8°) and diffraction peaks corresponding to fcc-Ni (2 ⁇ angles are 44.4°, 51.9°, and 76.5°).
  • 2-8 is a TEM image of the carbon-coated cobalt nanocomposite prepared in Example 2-3, which shows that the material contains a core-shell structure with carbon as a core and a certain degree of graphitization. There is a diffraction peak corresponding to cobalt (the angle of 2 ⁇ is 44.42°) in the XRD diffraction pattern (Fig. 2-9) of the material, indicating the presence of elemental cobalt in the material. The average particle diameter of the carbon-coated cobalt nanoparticles was calculated by Xie Le formula to be 17.5 nm.
  • the BET test showed that the material had a specific surface area of 140 m 2 /g and a pore volume of 0.158 cm 3 /g, wherein the mesopore volume was 0.158 cm 3 /g, which accounted for 100% of the total pore volume.
  • 2-11 are XRD patterns of the precursors prepared in Examples 2-4, illustrating that the synthesized precursor material is an amorphous material.
  • 2-12 are TEM images of the carbon-coated nickel-cobalt nanocomposite prepared in Example 2-4, which shows that the material contains a core shell of carbon with a certain degree of graphitization as a core of metallic nickel or cobalt nanoparticles. structure.
  • Fig. 2-13 In the XRD diffraction pattern of the material (Fig. 2-13), there are diffraction peaks corresponding to fcc-Ni and cobalt (2 ⁇ angles of 44.5°, 51.7°, and 76.2°), indicating that the material includes carbon having a certain degree of graphitization.
  • Nickel and/or cobalt present in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nanoparticles was calculated by Xie Le formula to be 24.4 nm.
  • the material had a specific surface area of 182 m 2 /g and a pore volume of 0.256 cm 3 /g, wherein the mesopore volume was 0.256 cm 3 /g, which accounted for 100% of the total pore volume.
  • the composite By measuring the N 2 adsorption-desorption isotherm curve and the BJH pore size distribution curve (Fig. 2-14) of the material, it was found that the composite had two mesoporous distribution peaks at 3.7 nm and 6.34 nm. After pickling experiments, the pickling loss rate of the material was 38.4%.
  • FIG. 2-15 are TEM images of the carbon-coated nickel nanocomposite prepared in Example 2-5, which shows that the material contains a core-shell structure in which carbon is a shell with metallic nickel nanoparticles as a core and a certain degree of graphitization.
  • Fig. 1 XRD diffraction pattern of the material
  • Example 2-19 are TEM images of the carbon-coated nickel nanocomposite prepared in Example 2-7, which shows that the material contains a core-shell structure in which carbon as a core with a certain degree of graphitization.
  • XRD diffraction pattern Fig. 2-20
  • the material includes carbon having a certain degree of graphitization and nickel present in a face-centered cubic structure.
  • the average particle diameter of the carbon-coated nanoparticles was calculated by Xie Le formula to be 4.7 nm. After pickling experiments, the pickling loss rate of the material was 16.7%.
  • FIG. 2-21 are TEM images of the carbon-coated nickel nanocomposites prepared in Examples 2-8, which show that the material contains a core-shell structure in which carbon is a shell with metallic nickel nanoparticles as a core and a certain degree of graphitization.
  • XRD diffraction pattern of the material Fig. 2-22
  • diffraction peaks corresponding to fcc-Ni 44.4°, 51.9°, and 76.3°
  • °, 47.5° and 62.6° indicating that the material includes carbon having a certain degree of graphitization and nickel present in a face-centered cubic structure and a close-packed hexagonal structure.
  • the average particle diameter of the carbon-coated nanoparticles was calculated by Xie Le formula to be 32.4 nm.
  • the BET test showed that the material had a specific surface area of 228 m 2 /g and a pore volume of 0.293 cm 3 /g, wherein the mesopore volume was 0.289 cm 3 /g, which accounted for 98.6% of the total pore volume.
  • the composite had a mesoporous distribution peak at 3.75 nm. After pickling experiments, the pickling loss rate of the material was 39.8%.
  • the BET test showed that the material had a specific surface area of 232 m 2 /g and a pore volume of 0.313 cm 3 /g, wherein the mesopore volume was 0.313 cm 3 /g, which accounted for 100% of the total pore volume.
  • FIG. 2-27 are photographs of the magnetic test of the carbon-coated nickel nano-composites prepared in Examples 2-10, after the magnet is attracted, the suspension of the carbon-coated nickel nanocomposite is rapidly cleared, indicating that the material is Has strong magnetic properties.
  • Figure 2-28 is a TEM image of the material. It can be seen that the material is a nanocomposite containing a carbon-coated metal core-shell structure, and a carbon layer having a certain degree of graphitization is wrapped in the outer layer of the nickel nanoparticle. Form a complete core-shell structure. The X-ray diffraction spectrum of the carbon-coated nickel nanocomposite is shown in Fig. 2-29.
  • the carbon-coated nickel nanocomposites prepared in Comparative Example 2-1 were tested by the above characterization, which indicated that the material formed a core-shell structure with metal nickel nanoparticles as the core and carbon as the shell, and the particle size was 28.2 nm. There are diffraction peaks corresponding to fcc-Ni (44.45°, 51.32°, and 76.16°) in the XRD diffraction pattern of the material, indicating that nickel is present in the material in a face-centered cubic structure. After pickling experiments, the pickling loss rate of the material was 64.2%.
  • the obtained precursor was placed in a porcelain boat, and then the porcelain boat was placed in a constant temperature zone of a tube furnace, nitrogen gas was introduced, the flow rate was 80 mL/min, and the temperature was raised to 725 ° C at a rate of 2.5 ° C/min, and the temperature was maintained for 3.5 hours. Stop heating. The mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite, No. P1.
  • the obtained carbon-coated nickel nanocomposite P1 was added to 50 mL of a 0.5 mol/L H 2 SO 4 solution, stirred at 90 ° C and refluxed for 6 hours, and then the solution was suction filtered and washed with deionized water until neutral. Then, the powder was dried in an oven at 100 ° C for 2 h to obtain a carbon-coated nickel nanocomposite, No. P2.
  • the obtained precursor is placed in a porcelain boat, and then the porcelain boat is placed in a constant temperature zone of the tube furnace, nitrogen gas is introduced, the flow rate is 100 mL/min, and the temperature is raised to 450 ° C at a rate of 5 ° C/min, and the temperature is stopped after 1 hour. heating.
  • the mixture was cooled to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite P3.
  • the obtained carbon-coated nickel nanocomposite P3 was added to 60 mL of a 1 mol/L HCl solution, stirred at 85 ° C and refluxed for 4 h, and then the solution was suction filtered and washed with deionized water until neutral. Then, the powder was dried in an oven at 100 ° C for 2 h to obtain a carbon-coated nickel nanocomposite P4.
  • Figure 3-1 is an XRD pattern of the material P2 obtained in Example 3-1.
  • Fig. 3-1 only the diffraction peak of the carbon material and the diffraction peaks of hcp-Ni and fcc-Ni exist, and the diffraction peaks of hcp-Ni at 42° and 62° almost disappear.
  • 3-2A is an N 2 adsorption-desorption isotherm diagram of the material P2 obtained in Example 3-1
  • FIG. 3-2B is a pore size distribution diagram of the material P2 obtained in Example 3-1.
  • Figure 3-2B shows that the pore size distribution of material P2 shows two distribution peaks at 3.7 nm and 10.0 nm.
  • Figure 3-3 is a SEM and TEM image of material P2. It can be seen from Fig. 3-3(a) that the material as a whole is a random block. It can be seen from Fig. 3-3(b) that the nickel nanoparticles are uniformly dispersed in the carbon substrate. It can be seen from Fig. 3-3(c) that the apparent graphite shell and the metal core directly prove the core-shell structure of the nanoparticles.
  • the elemental analyzer determined that the material P2 had a carbon content of 46.91 wt%, a hydrogen content of 0.42 wt%, a nitrogen content of 1.54 wt%, an oxygen content of 1.83 wt%, and a normalized nickel content of 49.30 wt%. According to the pickling loss rate measurement method described in the section "Reagents, Instruments and Tests" above, the pickling loss rate of the material P1 obtained in Example 3-1 was 40%, and the pickling loss rate of the material P2 was less than 2%. On the basis of this measurement method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • thermogravimetric-differential thermal analysis curve (TG-DTA) of the precursor material of Example 3-2. It can be seen from Figure 3-4 that there are two distinct endothermic peaks in the precursor during the heating process, wherein the endothermic peak at 366 °C corresponds to the high temperature pyrolysis carbonization of the precursor and the reduction of Ni 2+ to Ni element The process and the quality of the precursor is relatively stable after 400 °C.
  • 3-5 is an XRD pattern of the material P4 obtained in Example 3-2. The diffraction peak of the carbon material and the diffraction peak of fcc-Ni can be seen from Figures 3-5.
  • the average particle diameter of the nickel nanoparticles was 8.6 nm.
  • 3-6 is an XPS chart of the material P4 obtained in Example 3-2, from which the electron binding energy peaks of C, O, and Ni are apparent.
  • 3-7A is a N 2 adsorption-desorption isotherm diagram of the material P4 obtained in Example 3-2
  • the pore size distribution of material P4 showed two distribution peaks at 3.5 nm and 6.9 nm.
  • the material P4 had a specific surface area of 301 m 2 /g and a pore volume of 0.453 cm 3 /g, wherein the ratio of mesoporous volume to total pore volume was 100%.
  • the elemental analyzer determined that the material P4 had a carbon content of 39.80% by weight, a hydrogen content of 1.01% by weight, an oxygen content of 2.50% by weight, and a normalized nickel content of 56.69% by weight.
  • the pickling loss rate of material P3 obtained in Example 3-2 was 43%, and the pickling loss rate of material P4 was less than 1% as measured by the pickling loss rate measurement method described in the "Reagents, Instruments, and Tests" section above. On the basis of this measurement method, the pickling time is continuously increased, and the pickling loss rate remains substantially unchanged.
  • NiO nickel oxide
  • the materials prepared in the first part of the preparation examples and the comparative examples and the commercially available nickel oxide (NiO) were used as catalysts for industrial n-butane oxidation to prepare maleic anhydride.
  • NiO nickel oxide
  • the butane elimination rate of the corresponding catalyst was evaluated. Under the same conditions, the higher the butane elimination rate, the higher the catalyst activity.
  • the specific evaluation method is:
  • the collected butane-containing maleic anhydride production process off-gas is sent to a catalyst-loaded fixed bed reactor to be contacted with the catalyst and subjected to catalytic oxidation reaction, and the obtained reaction product is subjected to gas chromatography analysis, and the elimination rate of butane is calculated:
  • Butane elimination rate 100% - butane volume in the reaction product / butanane volume in the process gas production process x 100%.
  • the maleic anhydride production process exhaust gas contains about 1% by volume of butane, the rest is air and a very small amount of carbon monoxide and carbon dioxide, and the reaction space velocity is 5000 ml of industrial waste gas / (hour ⁇ g catalyst), and the evaluation time is 5 hours, and the specific reaction
  • the temperature and butane elimination rate data are shown in Table 4-1.
  • the nanocomposites prepared in Examples 1-1 to 1-3, 1-6 and 1-8 of the present invention can completely catalyze the oxidation of butane to CO 2 at 400 ° C or lower, wherein
  • the carbon-coated cobalt nanocomposite obtained in Examples 1-3 and the carbon-coated nickel-cobalt nanocomposite obtained in Examples 1-6 can be used in the process gas production process of maleic anhydride containing 1% by volume of butane at 350 ° C. The butane removal rate reached 100%.
  • the nanocomposite of the present invention can exhibit good low temperature activity when used as a catalytic oxidation catalyst, which completely removes volatile organic compounds in industrial waste gas by catalytic combustion. It is of great significance.
  • the graphitized carbon layer acts as a separation center for stabilizing the metal under the reaction conditions, effectively preventing the aggregation inactivation of the active center.
  • the nano composite material provided by the invention can greatly reduce the reaction temperature and reduce the energy consumption when applied to the waste gas treatment process of the maleic anhydride production process.
  • the second part of the preparation examples and the nanocomposites prepared in Comparative Examples 1-4 and commercially available nickel oxide (NiO) were used as catalysts for industrial industrialization. Alkoxylation to complete the complete catalytic elimination experiment of butane in the exhaust gas produced by the maleic anhydride production process.
  • the butane elimination rate evaluation of the corresponding catalyst is carried out, and the specific evaluation method is:
  • the collected butane-containing maleic anhydride production process off-gas is sent to a catalyst-loaded fixed bed reactor to be contacted with the catalyst and subjected to catalytic oxidation reaction, and the obtained reaction product is subjected to gas chromatography analysis, and the elimination rate of butane is calculated:
  • Butane elimination rate 100% - butane volume in the reaction product / butanane volume in the process gas production process x 100%.
  • the maleic anhydride production process exhaust gas contains about 1% by volume of butane, the rest is air and a very small amount of carbon monoxide and carbon dioxide, and the reaction space velocity is 5000 ml of industrial waste gas / (hour ⁇ g catalyst), and the evaluation time is 5 hours, and the specific reaction
  • the temperature and butane elimination rate data are shown in Table 4-2.
  • Example 2-1 The material obtained after the acid treatment of the material obtained in Example 2-1 was subjected to an acid treatment condition: 2.0 g of the nanocarbon composite material obtained in Preparation Example 2-1 was weighed, and washed with 80 mL of 1 M sulfuric acid at 90 ° C for 8 hours. Then, it was washed with deionized water to neutrality and dried at 120 °C.
  • the nanocomposites prepared in Examples 2-1 to 2-4 of the present invention can reduce the butane elimination rate in the exhaust gas of the maleic anhydride production process containing 1% by volume of butane at 350 ° C. At 100%, the desired temperature was significantly lower than the composites of Comparative Examples 1-4 and commercially available nickel oxide. It can be seen that the nanocomposite of the present invention, particularly the nanocomposite without the acid treatment step, can exhibit good low temperature activity when used as a catalytic oxidation catalyst, which completely removes volatile organic compounds in industrial waste gas by catalytic combustion. It is of great significance.
  • the graphitized carbon layer acts as a separation center for stabilizing the metal under the reaction conditions, effectively preventing the aggregation inactivation of the active center.
  • the nano composite material provided by the invention can greatly reduce the reaction temperature, maintain the stability of the catalyst and reduce the energy consumption when used in the treatment of the maleic anhydride production process.
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the reaction of hydrogenation of nitrobenzene to aniline.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the reaction of hydrogenation of nitrobenzene to aniline.
  • the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline.
  • the specific experimental steps were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the reaction of hydrogenation of nitrobenzene to aniline.
  • the specific experimental steps were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline.
  • the specific experimental procedures were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the hydrogenation of phenol to prepare cyclohexanol.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the hydrogenation of phenol to prepare cyclohexanol.
  • the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the hydrogenation of acetone to prepare isopropanol.
  • the specific experimental steps were as follows:
  • the reaction vessel was added 100 mL of cyclohexane, by replacing H 2 reactor 3, H 2 through the internal reactor pressure of 6MPa, heated with stirring, heated to 100 deg.] C, 12 hours .
  • the heating was stopped, the temperature was lowered to room temperature, the pressure was released, and the product was opened for gas chromatography analysis.
  • the conversion of acetone was 100%, and the selectivity of isopropanol was 97.3%.
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the hydrogenation of acetone to prepare isopropanol.
  • the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the reaction of hydrogenation of p-nitrophenol to p-aminophenol.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the reaction of hydrogenation of p-nitrophenol to p-aminophenol.
  • the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the reaction of hydrogenating p-nitroanisole to prepare p-aminoanisole.
  • the specific experimental procedures were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the reaction of hydrogenating p-nitroanisole to prepare p-aminoanisole.
  • the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the reaction of hydrogenation of olefin.
  • the specific experimental steps were as follows:
  • nanocomposite prepared in Examples 1-10 was used as a catalyst for the reaction of hydrogenation of olefins, and the specific experimental steps were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the hydrogenation of aromatic hydrocarbons to produce a cyclohexane derivative.
  • the specific experimental steps were as follows:
  • nanocomposites prepared in Examples 1-10 were used as catalysts for the hydrogenation of aromatic hydrocarbons to produce cyclohexane derivatives.
  • the specific experimental procedures were as follows:
  • Example 1-1 The nanocomposite prepared in Example 1-1 was used as a catalyst for the hydrogenation of aldehydes to produce alcohols.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 1-10 was used as a catalyst for the hydrogenation of aldehydes to produce alcohols.
  • the specific experimental steps were as follows:
  • the nanocomposite prepared in Examples 2-10 was used as a catalyst for the reaction of hydrogenation of nitrobenzene to aniline.
  • the specific experimental steps were as follows:
  • nanocomposites prepared in Examples 2-10 were used as catalysts for the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline.
  • the specific experimental procedures were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the hydrogenation of aldehydes to produce alcohols.
  • the specific experimental steps were as follows:
  • the composite material of 0.1g, 4.6mmol butyraldehyde, the reaction vessel was added 30 mL of cyclohexane, after replacing the H 2 through the reaction vessel 3, H 2 through the inner pressure of 3MPa reactor, heated with stirring, heated to 150 deg.] C, the reaction 2 hours. The heating was stopped, the temperature was lowered to room temperature, the pressure was released, and the product was opened for gas chromatography analysis.
  • the conversion of butyraldehyde was 99.1%, and the selectivity of n-butanol was 99.4%.
  • the nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of aldehydes to produce alcohols.
  • the specific experimental steps were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the hydrogenation of aromatic hydrocarbons to produce a cyclohexane derivative.
  • the specific experimental procedures were as follows:
  • nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of aromatic hydrocarbons to produce cyclohexane derivatives.
  • the specific experimental procedures were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the hydrogenation of phenol to produce cyclohexanol.
  • the specific experimental steps were as follows:
  • nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of phenol to produce cyclohexanol.
  • the specific experimental procedures were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the reaction of hydrogenation of p-nitrophenol to p-aminophenol.
  • the specific experimental procedures are as follows:
  • nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of p-nitrophenol to produce p-aminophenol.
  • the specific experimental procedures were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the reaction of hydrogenating p-nitroanisole to produce p-aminoanisole.
  • the specific experimental procedures were as follows:
  • the nanocomposite prepared in Examples 2-10 was used as a catalyst for the reaction of hydrogenating p-nitroanisole to produce p-aminoanisole.
  • the specific experimental steps were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the hydrogenation of ketones to produce alcohols.
  • the specific experimental steps were as follows:
  • the nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of ketones to produce alcohols.
  • the specific experimental steps were as follows:
  • Example 2-1 The nanocomposite prepared in Example 2-1 was used as a catalyst for the hydrogenation reaction of olefin.
  • the specific experimental steps were as follows:
  • nanocomposites prepared in Examples 2-10 were used as catalysts for the hydrogenation of olefins.
  • the specific experimental procedures were as follows:
  • the nanocomposite P2 prepared in Example 3-1 was used as a catalyst for the reaction of hydrogenation of p-chloronitrobenzene to p-chloroaniline.
  • the specific experimental steps were as follows:

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

一种包含碳包覆过渡金属颗粒的纳米复合材料以及其制备方法和应用，该纳米复合材料包含具有核壳结构的碳包覆过渡金属颗粒，其中核壳结构的壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，该材料是具有至少一个介孔分布峰的多孔材料。该纳米复合材料的制备方法包括如下步骤：i)将包含过渡金属源和多元有机羧酸的混合物与溶剂混合形成均相溶液；ii)除去所述均相溶液中的溶剂，从而形成前驱体；iii)在惰性保护气氛或还原气氛下将所述前驱体高温热解；以及iv)用非氧化性强酸对步骤iii)的热解产物进行处理。该纳米复合材料可用于催化各类加氢还原反应，或者作为催化氧化催化剂用于处理工业废气中的挥发性有机化合物。

Description

碳包覆过渡金属纳米复合材料、其制备及应用
本申请要求申请人于2017年7月28日提交的申请号为201710627278.5、名称为“碳与过渡金属的复合材料及其制备方法和应用”的专利申请的优先权，其内容经此引用全文并入本文。
技术领域
本发明涉及碳包覆金属纳米复合材料领域，具体涉及一种包含碳包覆过渡金属颗粒的纳米复合材料、其制备方法和应用。
背景技术
有研究表明，以碳纤维、纳米金刚石、碳纳米管、(氧化)石墨烯等为代表的纳米碳催化剂，对烃类的催化直接脱氢、氧化脱氢、卤化、羟基化、烷基化以及醛酮的液相氧化、缩合反应等一系列反应都有催化活性。同时，作为非金属材料，纳米碳材料具有耐酸碱腐蚀、化学性质稳定等优点。纳米碳催化剂的活性位点主要为碳材料自身的结构缺陷、杂原子官能团，因此为了提高纳米碳材料的催化活性，需要增加结构缺陷以及杂原子官能团的数量，但这样做又会导致材料自身稳定性的下降。
过渡金属纳米材料因具有优异的光学、电学、磁学及催化性能而受到广泛关注，但由于过渡金属纳米颗粒的活性较高，极易发生团聚或被氧化，甚至在空气中自燃，大大影响了这类材料的性能及应用。
可见，过渡金属纳米材料的催化活性较高但稳定性差，而纳米碳材料有较好的化学稳定性但需要进一步提高催化活性，若以恰当的方式将二者结合，则可能产生新的协同效应，使其展现出新的独特性能。
近年来，纳米碳包覆金属复合材料成为了人们关注的热点。这类材料由单层至数层弯曲石墨化碳层为壳紧密包裹内核的金属纳米颗粒，将金属纳米颗粒与外界进行隔绝，大大提高了复合材料的稳定性。因此，这种独特的核壳结构纳米材料在催化材料、吸波材料、信息存储材料、磁光材料、生物医学材料，以及润滑油添加剂等领域有着广阔的应用前景。
目前已有通过碳材料包覆过渡金属的相关文献报道，但现有的此 类材料在实际应用中仍存在各种问题，例如传质效率低、碳包覆不良导致使用时不稳定等问题；并且，在制造中还存在制造条件苛刻、工艺复杂、包覆率低、包覆不严密，以及引入含氧基团时需用硝酸处理，容易破坏碳包覆层、对金属内核造成不利影响等问题，无法适用于工业化生产和应用。
目前，已知的制造碳包覆金属纳米颗粒的方法主要有电弧法、化学气相沉积法(CVD)、高温热解法和溶胶凝胶法等。
电弧法所使用设备复杂，操作性差，能耗高，不利于材料的大规模制备。相比于电弧法，CVD法成本较低，产量及产率较高，但其难点在于需先制备尺寸均一、分散良好的纳米金属或其化合物的颗粒，并且后期产物中常常伴有碳纳米管和无定形碳的颗粒生成。
与CVD法相似，热解法的产物的结构与性能受前驱体材料影响较大。但热解法具有工艺简单、成本低、收率高、金属含量可控等优点，是目前具有大规模制备前景的方法之一。热解法主要可分为两大类，第一类方法直接将含氮原子的碳源(通常为二氰二胺、三聚氰胺以及高温下易生成三聚氰胺的尿素等)、金属源混合后置于惰性或还原气氛下进行高温热解。该方法的石墨化效率低、氰胺类配体使用量大，包覆效果不理想。此外，该方法还容易促进生成碳纳米管。另一类方法则先将金属离子与含氮的有机配体在特性反应下通过自组装连接形成具有周期性结构的晶态固体材料(即金属-有机骨架化合物，MOF)作为前驱体。与氰胺类的热解法不同，由于MOF中的金属形成了原子级别的均匀分散，因此被认为是一种更理想的热解前驱体，成为了该领域近年来的研究热点。通常制备这种前驱体需要使用有机溶剂，且需要在反应釜中进行高温、高压反应。例如，中国专利申请公开CN105965009A公开一种以天冬氨酸、4，4’-联吡啶为配体，甲醇、水为溶剂，在高温高压条件下与Ni 2+配位制备前驱体、并在惰性气氛下高温热解制备碳包覆镍纳米颗粒的方法。文献Mesoporous Ni@C hybrids for a high energy aqueousasymmetric supercapacitor device，Electronic Supplementary Material(ESI)for Journal of Materials Chemistry A，2016，4，9670-9676(DOI：10.1039/c6ta02339h)以亚氨基二乙酸为碳源，Ni(NO 3) 2为金属源，同样在高温高压条件下制备了自组装前驱体，并进一步在Ar气氛下高温热解制备了碳包覆镍纳米颗粒。 文献MOF-derived Ni-based nanocomposites as robust catalyst for chemoselective hydrogenation of functionalized nitro compounds，Bo Tang et.al.，RSC Advances，2017，7，1531-1539公开了一种采用不含氮的有机配体首先在高温高压下组装成金属有机框架前驱体(MOF)，然后高温热解合成多孔碳包覆镍纳米颗粒的复合材料的方法。但是，通常制备MOFs的条件比较严格，所需配体价格昂贵，并且很难进行大量生产。此外，这些方法需要消耗大量的碳源有机化合物，效率较低；且制备的碳包覆材料的碳层具有较多的孔隙，对内核金属的包覆不良，在酸洗下有较高的金属损失率，进而导致这些材料在使用时不稳定。
溶胶凝胶法是将某些弱酸与某些阳离子形成鳌合物，再通过鳌合物与多羟基醇聚合形成固体聚合物树脂，然后将树脂锻烧来制备粉体。在此类方法中，由于金属离子与有机酸发生化学反应而均匀地分散在聚合物树脂中，故能保证原子水平的混合。中国专利申请公开CN105032424A公开了一种pechini型溶胶凝胶法，该方法先将活性金属的前体分散于含配位化合物的水中，加入多元醇水溶液和高分子助剂，再添加载体，搅拌分散，水热反应，分出下层固体，惰性气氛下煅烧，得碳包覆活性金属的催化剂。与MOF法类似，溶胶凝胶法也需要在溶剂中制得固体的配位聚合物，且该方法制备的复合材料中对金属颗粒的包覆也不严密。并且，该方法需要采用高分子助剂，工艺繁琐。
介孔材料一般是指具有孔径介于2-50nm的孔道结构的一类多孔材料。介孔材料能够在大分子的分离、吸附、催化反应中发挥更好的作用，并且可能成为限域催化的微反应器。由于水热稳定性高、疏水性强、亲有机物等特点，使介孔碳材料在加氢、氧化、分解等反应中表现出独特的优势。如能在碳包覆过渡金属材料中制造出介孔结构，则可明显改善其传质效率，提高其使用性能，拓展其应用范围。目前，介孔碳材料的制备方法主要是催化活化法、有机凝胶碳化法和模板法，但这些方法的制备过程仍过于复杂。
现有技术中已知的碳包覆过渡金属材料及其制备方法具有各自的缺点。因此，仍然需要一种碳层对内核金属的包覆较好，酸洗损失率较低的碳包覆过渡金属纳米材料，更合意的是该材料还具有丰富的介孔结构；同时，也需要一种更为简单、成本更为低廉的制备碳包覆过 渡金属纳米材料的方法，其碳源前驱体消耗少，效率高，特别是能够实现纯水相、常压制备有机金属前驱体，更合意的是还能够通过高温热解制备具有丰富孔结构、特别是介孔结构的碳包覆过渡金属纳米材料。
此外，工业废气中常含有挥发性有机化合物(VOCs)，VOCs通常是指在常温下饱和蒸汽压约大于70Pa，常压下沸点低于250℃的有机化合物，常见的比如烷烃、芳烃、醚醇、卤代烃等。在化工和石化行业中，VOCs的产生和排放最为主要，生活中也易碰到(装修产生甲醛等)。例如，在以工业正丁烷为原料的生产路线生产顺酐过程中，原料与空气中的氧在催化剂作用下并不能100％转化为产品，会产生上述VOCs。VOCs已经成为光化学烟雾的主要原因之一，是和氮氧化物、可吸入颗粒物等共同作为大气质量的重要控制污染物，另外它还有高毒性、致癌等危害。因此，迫切需要一种适用于处理挥发性有机化合物的性能优异的催化氧化材料。
另外，现有技术中用于催化硝基苯加氢反应的催化剂以铂(Pt)、钯(Pd)和铑(Rh)等贵金属催化剂及铜(Cu)、镍(Ni)、铅(Zn)、钼(Mo)等非贵金属催化剂为主。雷尼Ni催化剂由于价格便宜且催化活性相对较高，是目前工业化催化硝基苯类化合物加氢还原生产苯胺类化合物使用最普遍的催化剂。然而，雷尼Ni催化剂仍具有很多缺点，例如，骨架镍在空气中极易着火，无法保存；加氢车间存在氢气，极易发生爆炸；反应副产物量较大，产品收率低且催化活性较低等等。因此，仍然需要一种适用于催化加氢还原反应、特别是硝基苯加氢反应的具有高稳定性和催化活性的催化材料。
需注意的是，前述背景技术部分公开的信息仅用于加强对本发明的背景理解，因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。
发明内容
针对现有技术存在的问题，本发明提供了一种包含具有核壳结构的碳包覆过渡金属颗粒的纳米复合材料，其中石墨化碳壳层对于过渡金属纳米颗粒内核的包覆较为严密，使得内核过渡金属在应用中的损失率降低，更好地保持了材料性能的稳定且保证了其安全性，特别地 该材料还可具有丰富的介孔结构，从而提高传质效率。同时，本发明还提供了一种简易、绿色、高效的制备碳包覆过渡金属纳米复合材料的方法，其通过在常压下简单混合即可得到所需纳米复合材料的前驱体，并且该前驱体的制备可以在纯水相中进行。
一方面，本发明提供了一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。
优选地，所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
优选地，所述纳米复合材料的酸洗损失率≤40％，更优选≤30％，特别优选≤10％。
优选地，所述纳米复合材料还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中；更优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
优选地，所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，更优选大于约80％，进一步优选大于约90％，特别优选大于约95％，最优选为约100％；更优选地，所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g。
另一方面，本发明提供了一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料的酸洗损失率≤10％。
优选地，所述纳米复合材料为具有至少一个介孔分布峰的多孔材料，更优选为具有两个或两个以上介孔分布峰的多孔材料。
优选地，所述纳米复合材料还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中；更优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
优选地，所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，更优选大于约80％，进一步优选大于约90％，特别优选大于约95％，最优选为约100％；优选地，所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g。
与现有技术的碳包覆过渡金属纳米复合材料相比，本发明的纳米复合材料可实现以下优点中的一个或多个：
1)本发明的纳米复合材料含有严密包覆的石墨化碳层/金属核壳结构，没有可使反应物接近过渡金属中心的孔道或缺陷，使内核的过渡金属材料十分稳定，不自燃，耐酸腐蚀，危险性低，适合保存与运输，从而保证了复合材料使用的安全性。
2)本发明的纳米复合材料具有丰富的介孔结构，有利于反应中反应物及产物的传质扩散；所述纳米复合材料中的碳材料本身就具有催化活性，与过渡金属协同发挥作用，使纳米复合材料的传质效率更高；特别地，所述纳米复合材料可具有多级介孔结构，从而赋予该材料更多样的功能，使之适用于更多的应用领域。
3)本发明的纳米复合材料含有被石墨化碳层包覆的强磁性金属内核和丰富的孔结构，使其将磁分离功能与吸附功能更好的结合起来，使其特别适合于吸附分离领域。
4)本发明的纳米复合材料可用作各类有机反应的催化剂，有利于提高催化反应的效率。用于催化加氢反应时，该材料表现出重复性好、高活性、高选择性等优点，具有良好的工业应用前景。用作催化氧化催化剂时，该材料表现出良好的低温活性，这对于通过催化燃烧彻底去除工业废气中的挥发性有机化合物具有重要意义。
5)本发明的纳米复合材料在空气中不自燃，可以如普通商品在空气中长时间储存，不影响其在催化氧化、催化加氢等反应中的使用性能。
6)本发明的纳米复合材料在制备时，掺杂元素的含量可调，不需要采取硝酸处理等手段引入氧元素，可以调节石墨化碳层的电子特性，使其适用于催化不同的反应。
又一方面，本发明提供了一种制备包含碳包覆过渡金属颗粒的纳米复合材料的方法，包括如下步骤：
i)将包含过渡金属源和多元有机羧酸的混合物与溶剂混合形成均相溶液；
ii)除去所述均相溶液中的溶剂，从而形成前驱体；
iii)在惰性保护气氛或还原气氛下将所述前驱体高温热解；以及
iv)任选地，用非氧化性强酸对步骤iii)的热解产物进行处理。
优选地，所述方法的步骤i)中所用的所述混合物进一步包含不同于所述多元有机羧酸的含氮有机化合物和/或含氧有机化合物，其中所述含氮有机化合物优选选自尿素、三聚氰胺、二氰二胺、六亚甲基四胺和氨基酸中的一种或多种，所述含氧有机化合物优选选自多元醇和有机羧酸，如乳酸。
优选地，所述过渡金属源选自过渡金属的有机酸盐、碳酸盐、碱式碳酸盐、氧化物和氢氧化物中的一种或多种；更优选所述过渡金属的有机酸盐为所述过渡金属的不含杂原子的有机羧酸盐，例如醋酸盐。
进一步优选地，所述多元有机羧酸选自柠檬酸、顺丁烯二酸、均苯三甲酸、对苯二甲酸、苹果酸、EDTA和吡啶二羧酸中的一种或多种。
优选地，步骤iv)中所用的非氧化性强酸选自氢氟酸、盐酸、硝酸和硫酸中的一种或多种，更优选盐酸和/或硫酸。
与现有的制备碳包覆过渡金属纳米复合材料的方法相比，本发明的纳米复合材料制备方法可实现以下优点中的一个或多个：
1)本发明方法更加简单高效，高温热解前驱体直接由过渡金属源与多元有机羧酸在溶剂(可以是水)中均匀混合而得，前驱体过渡金属的原子利用率可达100％。
2)本发明方法在取得更好的包覆效果的同时，克服了现有技术制备金属有机骨架结构前驱体需要使用高温高压反应釜自组装、大量浪费有机溶剂、提纯步骤繁琐等缺点。与溶胶凝胶法相比，本发明方法不需要高分子助剂，简化了反应步骤。
4)本发明方法制备的纳米复合材料中，纳米金属颗粒被石墨化碳层包覆的严密程度更高，能在更苛刻的条件下使用。
5)本发明方法中，石墨化碳层的掺杂元素的含量可调，不需要采取硝酸处理等手段引入氧元素，可以调节石墨化碳层的电子特性，使所得纳米复合材料适用于催化不同的反应。
又一方面，本发明提供了按照本发明方法制备得到的包含碳包覆过渡金属颗粒的纳米复合材料。
再一方面，本发明提供了根据本发明的纳米复合材料作为催化剂在处理挥发性有机化合物中的应用和在加氢还原反应中的应用。
优选地，所述在处理挥发性有机化合物中的应用包括：使所述挥发性有机化合物与所述纳米复合材料接触进行催化氧化反应。
优选地，所述在加氢还原反应中的应用，包括在选自如下反应中的应用：对氯硝基苯加氢制造对氯苯胺的反应、硝基苯加氢制造苯胺的反应、硝基苯酚加氢制造氨基苯酚的反应、对硝基苯甲醚加氢制造对氨基苯甲醚的反应、苯酚加氢制造环己醇的反应、烯烃加氢的反应、芳烃加氢制造环己烷衍生物的反应、醛加氢制造醇的反应和酮加氢制造醇的反应。
附图说明
附图是用来帮助对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。
第一部分
图1-1是实施例1-1所制备的前躯体的X射线衍射(XRD)图。
图1-2是实施例1-1所制备的碳包覆镍纳米复合材料的磁性测试的照片。
图1-3是实施例1-1所制备的碳包覆镍纳米复合材料的透射电子显微镜(TEM)图。
图1-4是实施例1-1所制备的碳包覆镍纳米复合材料的XRD图。
图1-5A是实施例1-1所制备的碳包覆镍纳米复合材料的N 2吸附-脱附等温曲线图。
图1-5B是实施例1-1所制备的碳包覆镍纳米复合材料的孔分布曲线图。
图1-6是实施例1-2所制备的碳包覆镍纳米复合材料的TEM图。
图1-7是实施例1-2所制备的碳包覆镍纳米复合材料XRD图。
图1-8是实施例1-2所制备的碳包覆镍纳米复合材料的孔分布曲线图。
图1-9是实施例1-3所制备的碳包覆钴纳米复合材料的TEM图。
图1-10是实施例1-3所制备的碳包覆钴纳米复合材料XRD图。
图1-11是实施例1-3所制备的碳包覆钴纳米复合材料的孔分布曲线图。
图1-12是实施例1-4所制备的碳包覆镍纳米复合材料的TEM图。
图1-13是实施例1-5所制备的碳包覆镍纳米复合材料的TEM图。
图1-14是实施例1-6所制备的碳包覆镍和钴纳米复合材料的TEM图。
图1-15是实施例1-6所制备的碳包覆镍和钴纳米复合材料XRD图。
图1-16是实施例1-6所制备的碳包覆镍和钴纳米复合材料的孔分布曲线图。
图1-17是实施例1-7所制备的碳包覆镍纳米复合材料的TEM图。
图1-18是实施例1-7所制备的碳包覆镍纳米复合材料XRD图。
图1-19是实施例1-7所制备的碳包覆镍纳米复合材料的孔分布曲线图。
图1-20是实施例1-8所制备的碳包覆镍纳米复合材料的TEM图。
图1-21是实施例1-8所制备的碳包覆镍纳米复合材料XRD图。
图1-22是实施例1-9所制备的碳包覆镍纳米复合材料的TEM图。
图1-23是实施例1-9所制备的碳包覆镍纳米复合材料XRD图。
图1-24是实施例1-10所制备的碳包覆镍纳米复合材料的磁性测试的照片。
图1-25是实施例1-10所制备的碳包覆镍纳米复合材料的TEM图。
图1-26是实施例1-10所制备的碳包覆镍纳米复合材料XRD图。
图1-27是实施例1-10所制备的碳包覆镍纳米复合材料的孔分布曲线图。
图1-28是对比例1-4所制备的纳米复合材料的XRD图。
第二部分
图2-1是实施例2-1所制备的碳包覆镍纳米复合材料的磁性测试的照片。
图2-2是实施例2-1制备的碳包覆镍纳米复合材料的TEM图。
图2-3是实施例2-1制备的碳包覆镍纳米复合材料的XRD图。
图2-4A是实施例2-1制备的碳包覆镍纳米复合材料的N 2吸附-脱附等温曲线图。
图2-4B是实施例2-1制备的碳包覆镍纳米复合材料的孔分布曲线图。
图2-5是实施例2-2制备的碳包覆镍纳米复合材料的TEM图。
图2-6是实施例2-2制备的碳包覆镍纳米复合材料的XRD图。
图2-7是实施例2-2制备的碳包覆镍纳米复合材料的孔分布曲线图。
图2-8是实施例2-3制备的碳包覆钴纳米复合材料的TEM图。
图2-9是实施例2-3制备的碳包覆钴纳米复合材料的XRD图。
图2-10是实施例2-3制备的碳包覆钴纳米复合材料的孔分布曲线图。
图2-11是实施例2-1所制备的前躯体的XRD图。
图2-12是实施例2-4制备的碳包覆镍和钴纳米复合材料的TEM图。
图2-13是实施例2-4制备的碳包覆镍和钴纳米复合材料的XRD图。
图2-14是实施例2-4制备的碳包覆镍和钴纳米复合材料的孔分布曲线图。
图2-15是实施例2-5制备的碳包覆镍纳米复合材料的TEM图。
图2-16是实施例2-5制备的碳包覆镍纳米复合材料的XRD图。
图2-17是实施例2-6制备的碳包覆镍纳米复合材料的TEM图。
图2-18是实施例2-6制备的碳包覆镍纳米复合材料的XRD图。
图2-19是实施例2-7制备的碳包覆镍纳米复合材料的TEM图。
图2-20是实施例2-7制备的碳包覆镍纳米复合材料的XRD图。
图2-21是实施例2-8制备的碳包覆镍纳米复合材料的TEM图。
图2-22是实施例2-8制备的碳包覆镍纳米复合材料的XRD图。
图2-23是实施例2-8制备的碳包覆镍纳米复合材料的孔分布曲线图。
图2-24是实施例2-9制备的碳包覆镍纳米复合材料的TEM图。
图2-25是实施例2-9制备的碳包覆镍纳米复合材料的XRD图。
图2-26是实施例2-9制备的碳包覆镍纳米复合材料的孔分布曲线图。
图2-27是实施例2-10所制备的碳包覆镍纳米复合材料的磁性测试的照片。
图2-28是实施例2-10所制备的碳包覆镍纳米复合材料的TEM图。
图2-29是实施例2-10所制备的碳包覆镍纳米复合材料的XRD图。
图2-30是实施例2-10所制备的碳包覆镍纳米复合材料的孔分布曲线图。
第三部分
图3-1是实施例3-1制备的碳包覆镍纳米复合材料P2的XRD图。
图3-2A是实施例3-1制备的碳包覆镍纳米复合材料P2的N 2吸附-脱附等温曲线图。
图3-2B是实施例3-1制备的碳包覆镍纳米复合材料P2的孔径分布曲线图。
图3-3是实施例3-1制备的碳包覆镍纳米复合材料P2的扫描电子显微镜(SEM)和透射电子显微镜(TEM)图。
图3-4是实施例3-2制备的前驱体的热重-差热分析曲线(TG-DTA)图。
图3-5是实施例3-2制备的碳包覆镍纳米复合材料P4的XRD图。
图3-6是实施例3-2制备的碳包覆镍纳米复合材料P4的X射线光电子能谱(XPS)图。
图3-7A是实施例3-2制备的碳包覆镍纳米复合材料P4的N 2吸附-脱附等温曲线图。
图3-7B是实施例3-2制备的碳包覆镍纳米复合材料P4的孔径分布图。
具体实施方式
以下将结合附图通过具体的实施方式对本发明作出进一步的详细描述，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，但不以任何方式限制本发明。
本发明中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
本说明书所公开的数值点，不仅包括实施例中具体公开的数值点，还包括说明书中各数值范围的端点，这些数值点所任意组合的范围都应被视为本发明已公开或记载的范围。除非另有说明，本发明定义的数值范围均包括其端点值。
在本文中，措辞“包括”、“包含”为开放式表述，基本上等效 于短语“包括，但不限于”。
如在此使用的，除非上下文另外明确指出，否则单数形式的“一”、“一个”以及“该”包括复数指示物。因此，例如提及“一个事物”包括多于一个这样的事物，包括基本上如在此之前所述的所有实施方案以及变体并且参考实例和附图。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
术语
除非另外说明，本说明书中使用的术语应当理解为具有下面的含义。在此未直接定义的任何术语，应当被理解为具有与它们在本发明技术领域中通常所理解的相对应的含义。
在本文中，术语“包含碳包覆过渡金属颗粒的纳米复合材料”与“碳包覆过渡金属纳米复合材料”可以互换使用，指包含具有“核壳结构”的碳包覆过渡金属颗粒的纳米复合材料。
在本文中，术语“核壳结构”是指由石墨化碳材料包覆在过渡金属纳米颗粒的外表面上所形成的内核为过渡金属纳米颗粒、壳层(即外层)为石墨化碳层的复合结构。
在本文中，术语“石墨化碳层”是指在高分辨透射电镜下可明显观察到层状结构的碳结构，而非无定型结构，其层间距约为0.34nm。该石墨化碳层包覆过渡金属纳米颗粒后形成的复合材料一般呈球形或类球形。
在本文中，表述“掺杂氧和/或氮的石墨化碳层”是指所述石墨化碳层为“掺杂氧的石墨化碳层”或者“掺杂氧和氮的石墨化碳层”，一般地还会掺杂有少量的氢元素。
在本文中，所述“掺杂氧的石墨化碳层”中的“氧”是指氧元素，包括所述石墨化碳层中所含的以任何形式存在的氧元素。所述纳米复合材料的“氧含量”是指氧元素的含量，即以各种形式存在的氧元素的总含量。
在本文中，所述“掺杂氧和氮的石墨化碳层”中的“氧”是指氧元素、“氮”是指氮元素，包括所述石墨化碳层中所含的以任何形式存在的氧元素和氮元素。所述纳米复合材料的“氧含量”是指氧元素 的含量，即以各种形式存在的氧元素的总含量；同样，所述纳米复合材料的“氮含量”是指氮元素的含量，即以各种形式存在的氮元素的总含量。
在本文中，术语“介孔”是指孔径在2-50nm范围的孔。
在本文中，孔径小于2nm的孔定义为微孔，而孔径大于50nm的孔定义为大孔。
在本文中，术语“介孔分布峰”是指根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到的孔分布曲线上的介孔分布峰。
在本文中，术语“碳包覆率”用于反映过渡金属纳米颗粒被石墨化碳层有效包覆的比例，其可通过高分辨透射电镜(HRTEM)来观察。
在本文中，术语“碳包覆严密程度”用于反映过渡金属纳米颗粒被石墨化碳层与外部环境隔绝的比例，其可通过酸洗实验结果来表征。
在本文中，术语“酸处理”是指在碳包覆过渡金属纳米复合材料制备过程中，在高温热解步骤之后，用非氧化性强酸对高温热解所得的产物所进行的处理，该处理属于所述纳米复合材料制备过程的一个任选步骤，即，该处理如果存在的话，则构成所述制备过程的一部分。
在本文中，术语“酸洗”是指用硫酸水溶液对碳包覆过渡金属纳米复合材料进行处理，以测量其“酸洗损失率”的检测步骤，其不构成所述碳包覆过渡金属纳米复合材料的制备过程的一部分。
在本文中，术语“酸洗损失率”是指碳包覆过渡金属纳米复合材料经酸洗后过渡金属的损失比例，其用于反映石墨化碳层对过渡金属纳米颗粒的包覆的严密程度。如果石墨化碳层对过渡金属纳米颗粒的包覆不严密，则经酸洗后，内核中的过渡金属会被酸溶解而流失。酸洗损失率越大，表明石墨化碳层对过渡金属纳米颗粒的包覆的严密程度越低；反之，酸洗损失率越小，表明石墨化碳层对过渡金属纳米颗粒的包覆的严密程度越高。
在本文中，酸洗损失率≤10％的纳米复合材料定义为“严密包覆的纳米复合材料”。酸洗损失率≤10％表明该纳米复合材料中所含的碳包覆过渡金属颗粒具有严密包覆的核壳结构，即其中的过渡金属纳米颗粒被石墨化碳层严密包覆，而基本不与外界接触。
在第一方面，本发明提供一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或 氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料，即所述纳米复合材料在根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到的孔分布曲线上，具有至少一个介孔分布峰。
在一优选实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，不掺杂氢、氧以外的其他元素。
在另一优选实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，不掺杂氢、氧、氮以外的其他元素。
在优选的实施方式中，所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
在优选的实施方式中，所述纳米复合材料的酸洗损失率≤40％，例如可以为约10％-20％、约20％-30％或约30％-40％，优选≤30％，更优选≤10％。如上文所述，酸洗损失率反映了石墨化碳层对过渡金属内核的包覆的严密程度，酸洗损失率越小，表明包覆的严密程度越高。
在优选的实施方式中，所述纳米复合材料还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中。更优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
特别地，根据本发明的纳米复合材料中不含碳纳米管。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，且所述纳米复合材料在2-7nm的孔径范围和8-20nm的孔径范围内分别具有一个介孔分布峰；或者，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，且所述纳米复合材料在2-5nm的孔径范围和6-15nm的孔径范围内分别具有一个介孔分布峰，进一步优选地，所述纳米复合材料中孔径在2-5nm范围内的介孔体积占总孔体积的比例大于约5％，如约10％-30％。
在优选的实施方式中，所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，更优选大于约80％，进一步优选大于约90％，特别优选大于约95％，最优选为约100％。通过控制介孔体积占总孔体积的比例，使该复合材料具有丰富的介孔结构，从而获得更高的传质效率。
在优选的实施方式中，所述纳米复合材料的介孔体积为约 0.05-1.25cm 3/g。在一些具体实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层时，所述纳米复合材料的介孔体积可为约0.30-0.50cm 3/g。在另一些具体实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层时，所述纳米复合材料的介孔体积可为约0.10-0.30cm 3/g。
在优选的实施方式中，所述纳米复合材料的比表面积大于约140m 2/g，优选大于约200m 2/g。
在优选的实施方式中，以质量百分比计，所述纳米复合材料中，碳含量为约10.0％-60.0％，过渡金属含量为约30.0％-85.0％。在一些具体实施方式中，以质量百分比计，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层时，所述纳米复合材料的碳含量可为约15.0％-40.0％，过渡金属含量可为约50.0％-80.0％；或者，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层时，所述纳米复合材料的碳含量可为约30.0％-50.0％，过渡金属含量可为约30.0％-60.0％。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，并且以质量百分比计，所述纳米复合材料的氧含量小于约15.0％，优选为约1.0％-10.0％，更优选为约0.2％-5.0％；或者，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，并且以质量百分比计，所述纳米复合材料中氮和氧的总含量小于约15.0％，优选为约0.2％-12.0％，更优选为约0.5％-10.0％；进一步优选地，氮含量为约0.1-10％，特别优选为约1-5％。
在一些具体实施方式中，所述石墨化碳层还掺杂有氢，并且以质量百分比计，所述纳米复合材料的氢含量为约0.2-2％。
在具体实施方式中，根据本发明的纳米复合材料中的过渡金属元素以还原态(如零价态)存在，即不存在以氧化态(如氧化物)形式存在的过渡金属元素。
特别地，根据本发明的纳米复合材料中各组分的含量之和为100％。
在优选的实施方式中，所述石墨化碳层的厚度为约0.3-6.0nm，更优选为约0.3-3nm，特别优选为约1-3nm。
在优选的实施方式中，所述具有核壳结构的碳包覆过渡金属颗粒的粒径为约1-200nm，更优选为约3-100nm，进一步优选为约4-50nm。
在优选的实施方式中，所述过渡金属选自铁(Fe)、钴(Co)、镍(Ni)、 铜(Cu)和锌(Zn)中的一种或多种，更优选为铁、钴、镍和铜中的一种或多种，最优选为镍(Ni)。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，且所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构(fcc)和/或密排六方晶格结构(hcp)，即可以只存在面心立方晶格结构，也可以只存在密排立方晶格结构，还可以同时存在面心立方晶格结构和密排六方晶格结构。
不局限于具体理论，根据本发明第一方面的纳米复合材料被认为是一种由无定型碳基材和分散在其中的“被石墨化碳层严密包覆(基本不与外界接触)的过渡金属纳米颗粒”以及“可与外界接触的过渡金属纳米颗粒”构成的具有介孔结构的复合材料。所述纳米复合材料的掺杂氧和/或氮的石墨化碳层表面具有丰富的缺陷位，碳材料本身就具有催化活性，与过渡金属纳米颗粒协同发挥作用，使该纳米复合材料具有较佳的催化性能。
此外，根据本发明第一方面的纳米复合材料具有丰富的介孔结构，有利于反应物和产物的扩散，使该纳米复合材料的传质效率更高，从而具有更优异的催化性能。当所述纳米复合材料具有不同孔径范围的多级介孔结构时，可以使其表现出更独特的性能，可适用的应用范围也更广。
根据本发明第一方面的纳米复合材料在石墨化碳层中掺杂有氧和/或氮，氧含量可以通过在制备过程中额外引入含氧有机化合物，比如多元醇来调节，氮含量可以通过在制备过程中额外引入含氮有机化合物，比如六亚甲基四胺来调节。通过调节所述纳米复合材料中的氮、氧含量，可以调节碳层的催化性能，使其适用于催化不同的反应。
在第二方面，本发明提供了一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料的酸洗损失率≤10％，即为严密包覆的纳米复合材料。
在一优选实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，不掺杂氢、氧以外的其他元素。
在另一优选实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，不掺杂氢、氧、氮以外的其他元素。
在优选的实施方式中，所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。更优选地，所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
在优选的实施方式中，所述纳米复合材料还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中。更优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
特别地，根据本发明的纳米复合材料中不含碳纳米管。
在优选的实施方式中，所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，更优选大于约80％，进一步优选大于约90％，特别优选大于约95％，最优选为约100％。
在优选的实施方式中，所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g，在一些具体实施方式中，所述纳米复合材料的介孔体积可为约0.30-0.50cm 3/g。在另一些具体实施方式中，所述纳米复合材料的介孔体积可为约0.10-0.30cm 3/g。
在优选的实施方式中，所述纳米复合材料的比表面积大于约140m 2/g，优选大于约200m 2/g。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，且所述纳米复合材料在2-7nm的孔径范围和8-20nm的孔径范围内分别具有一个介孔分布峰；或者，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，且所述纳米复合材料在2-5nm的孔径范围和6-16nm的孔径范围内分别具有一个介孔分布峰，进一步优选地，所述纳米复合材料中孔径在2-5nm范围内的介孔体积占总孔体积的比例大于约5％，如约10％-30％。
在优选的实施方式中，以质量百分比计，所述纳米复合材料中，碳含量为约15.0％-60.0％，过渡金属含量为约30.0％-80.0％。在一些具体实施方式中，以质量百分比计，所述纳米复合材料的碳含量可为约30-60wt％，过渡金属含量可为约30-60wt％。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，并且以质量百分比计，所述纳米复合材料中的氧含量小于约15.0％，优选为约1.0％-10.0％，更优选为约0.2％-5.0％；或者，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，并且以 质量百分比计，所述纳米复合材料中氮和氧的总含量小于约15.0％，优选为约0.2％-12.0％，更优选为约0.5％-10.0％；进一步优选地，氮含量为约0.1-10％，特别优选为约1-5％。
在某些优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，并且以质量百分比计，所述纳米复合材料的氮含量为约2-8％。
在某些优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，并且以质量百分比计，所述纳米复合材料的氧含量为约3-9％。
在一些具体实施方式中，所述石墨化碳层还掺杂有氢，并且以质量百分比计，所述纳米复合材料的氢含量为约0.2-2％。
在具体实施方式中，根据本发明的纳米复合材料中的过渡金属元素以还原态(如零价态)存在，即不存在以氧化态(如氧化物)形式存在的过渡金属元素。
特别地，根据本发明的纳米复合材料中各组分的含量之和为100％。
在优选的实施方式中，所述石墨化碳层的厚度为约0.3-6.0nm，更优选为约0.3-3nm，特别优选为约1-3nm。
在优选的实施方式中，所述具有核壳结构的碳包覆过渡金属颗粒的粒径为约1-200nm，更优选为约3-100nm，进一步优选为约4-50nm。
在优选的实施方式中，所述过渡金属选自铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)和锌(Zn)中的一种或多种，更优选为铁、钴、镍和铜中的一种或多种，最优选为镍(Ni)。
在优选的实施方式中，所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，且所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构(fcc)和/或密排六方晶格结构(hcp)。
不局限于具体理论，根据本发明第二方面的纳米复合材料被认为是一种由无定型碳基材和分散在其中的“被石墨化碳层严密包覆(基本不与外界接触)的过渡金属纳米颗粒”构成的具有介孔结构的复合材料。这种严密包覆的纳米复合材料较非严密包覆的纳米复合材料而言，可以更好地保证内核过渡金属在应用中的损失率降低，从而更好地发挥该复合材料的作用。
本领域通常认为催化加氢反应的活性中心是过渡金属，不管催化 剂的具体结构如何，必须能使反应物与金属中心接触。但本发明的过渡金属纳米颗粒被石墨化碳层严密包覆的纳米复合材料，仍具有极佳的催化加氢还原有机化合物的能力。
此外，根据本发明第二方面的纳米复合材料具有丰富的介孔结构，有利于反应物和产物的扩散，使所述纳米复合材料的传质效率更高，从而具有更优异的催化性能。当所述纳米复合材料具有不同孔径范围的多级介孔结构时，可以使其表现出更独特的性能，可适用的应用范围也更广。
根据本发明第二方面的纳米复合材料在石墨化碳层中掺杂有氧和/或氮，氧含量可以通过在制备过程中额外引入含氧有机化合物，比如多元醇来调节，氮含量可以通过在制备过程中额外引入含氮有机化合物，比如六亚甲基四胺来调节。通过调节所述纳米复合材料中的氮、氧含量，可以调节碳层的催化性能，使其适用于催化不同的反应。
在第三方面，本发明提供了一种制备包含碳包覆过渡金属颗粒的纳米复合材料的方法，包括如下步骤：
i)将包含过渡金属源和多元有机羧酸的混合物与溶剂混合形成均相溶液；
ii)除去所述均相溶液中的溶剂，从而形成前驱体；
iii)在惰性保护气氛或还原气氛下将所述前驱体高温热解；以及
iv)任选地，用非氧化性强酸对步骤iii)的热解产物进行处理。
在优选的实施方式中，步骤i)所用的混合物中所述过渡金属源和多元有机羧酸的质量比为约1∶0.1-10，更优选约1∶0.5-5，特别优选约1∶0.8-3。
在优选的实施方式中，步骤i)所用的混合物进一步包含不同于所述多元有机羧酸的含氮有机化合物和/或含氧有机化合物。
在进一步优选的实施方式中，步骤i)所用的混合物中所述过渡金属源、所述多元有机羧酸和所述含氮有机化合物的质量比为约1∶0.1-100∶0.1-100，更优选为约1∶0.5-5∶0.5-5，特别优选为约1∶0.8-2∶1-2。
在进一步优选的实施方式中，所述含氮有机化合物选自尿素、三聚氰胺、二氰二胺、六亚甲基四胺和氨基酸中的一种或多种，所述含氧有机化合物选自多元醇和有机羧酸，如乳酸。
在某些优选实施方式中，步骤i)中所用的混合物还可进一步包含不 同于所述多元有机羧酸、含氮有机化合物和含氧有机化合物的其它有机化合物。任何可以补充产物中所需的碳源、同时不含其他掺杂原子的有机化合物均可使用，优选不具有挥发性的有机化合物。更优选地，所述混合物中该其它有机化合物与所述过渡金属源的质量比为约0-10∶1，进一步优选为约0-3∶1。
在优选的实施方式中，所述过渡金属选自铁、钴、镍、铜和锌中的一种或多种，更优选为铁、钴、镍和铜中的一种或多种，最优选为镍。
在优选的实施方式中，所述过渡金属源选自过渡金属的有机酸盐、碳酸盐、碱式碳酸盐、氧化物和氢氧化物中的一种或多种。
本发明对所述过渡金属有机酸盐没有特别的限制，只要能够与所述多元有机羧酸在溶剂中混合并形成均相溶液即可。例如，所述过渡金属有机酸盐包括但不限于所述过渡金属的不含杂原子的有机羧酸盐，如醋酸盐等。
本发明对于所述多元有机羧酸没有特别的限制，只要能与所述过渡金属有机酸盐在溶剂中混合并形成均相溶液即可。所述多元有机羧酸可以是含氮或不含氮的多元有机羧酸，在使用含氮多元有机羧酸的情况下相当于不含氮的多元有机羧酸与含氮有机化合物的结合。换而言之，当所用多元有机羧酸为含氮的多元有机羧酸时，可以不再额外添加含氮有机化合物，此类实施方式也在本发明的保护范围内。
在优选的实施方式中，所述多元有机羧酸选自柠檬酸、顺丁烯二酸、均苯三甲酸、对苯二甲酸、苹果酸、EDTA和吡啶二羧酸中的一种或多种。进一步优选地，所述吡啶二羧酸可以为2，3-吡啶二羧酸，2，4-吡啶二羧酸，2，5-吡啶二羧酸，2，6-吡啶二羧酸，3，4-吡啶二羧酸和/或3，5-吡啶二羧酸。
在某些优选实施方式中，步骤i)中所用的混合物包含过渡金属源和含氮的有机多元羧酸，任选地包含含氧有机化合物和/或其它有机化合物。
在特别优选的实施方式中，所述有机多元羧酸包括但不限于柠檬酸，所述含氮的有机多元羧酸包括但不限于乙二胺四乙酸(EDTA)，所述过渡金属源包括但不限于过渡金属的醋酸盐，所述含氮有机化合物包括但不限于六亚甲基四胺，所述含氧有机化合物包括但不限于有 机多元醇。
在优选的实施方式中，步骤i)所用的溶剂选自水、甲醇、乙醇、正丙醇和异丙醇中的一种或多种，更优选选自水、乙醇或其组合，最优选为水。
在优选的实施方式中，在步骤ii)中，可以通过例如蒸发来除去溶剂，例如在80-120℃下喷雾干燥，或在烘箱中干燥。
在本发明方法的步骤ii)中，除去溶剂后形成的前驱体可以是混合物，并且该混合物可以是水溶性的。
在优选的实施方式中，在步骤iii)中，所述惰性保护气氛为氮气或氩气，所述还原气氛为惰性气体与氢气的混合气体；所述高温热解过程包括升温段和恒温段，其中在升温段中以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，恒温段温度为约400-800℃。更优选地，升温段的升温速率为约0.5-10℃/min，进一步优选为约1-10℃/min，特别优选为约2.5-10℃/min，最优选约1-5℃/min；在恒温段保持恒温时间为约30-480min，进一步优选为约60-300min；恒温段温度为约500-800℃，进一步优选为约500-700℃。
在优选的实施方式中，步骤iv)中所用的非氧化性强酸包括但不限于氢氟酸、盐酸、硝酸和硫酸中的一种或两种以上的任意组合，优选盐酸和/或硫酸。
在进一步优选的实施方式中，步骤iv)的酸处理的条件为：在约30-100℃的温度下处理至少约1h，优选在约60-100℃的温度下处理约1-20h，更优选在约70-90℃的温度下处理约1-10h。
在具体实施方式中，根据本发明方法制备得到的纳米复合材料中的过渡金属元素以还原态(如零价态)存在，即不存在以氧化态(如氧化物)形式存在的过渡金属元素。
在某些优选实施方式中，根据本发明的制备纳米复合材料的方法包括如下步骤：
i)将过渡金属源、多元有机羧酸、及任选的含氮有机化合物、含氧有机化合物和其它有机化合物在选自水和乙醇的溶剂中混合形成均相溶液；
ii)蒸发除去溶剂得到含过渡金属的水溶性混合物；
iii)将所述水溶性混合物在惰性气氛或还原性气氛下高温热解；以 及
iv)任选地，将高温热解所得的产物用酸处理。
在进一步优选的实施方式中，所述蒸发溶剂的工艺和条件可以采用任意可行的现有技术，例如，在约80-120℃下喷雾干燥，或在烘箱中干燥。
在进一步优选的实施方式中，在步骤i)中将过渡金属源、不含氮的多元有机羧酸、含氮有机化合物、及任选的含氧有机化合物和其它有机化合物在溶剂中混合。
在进一步优选的实施方式中，在步骤i)中将过渡金属源、含氮的多元有机羧酸、及任选的含氧有机化合物和其它有机化合物在溶剂中混合。
与现有技术的方法相比，本发明的纳米复合材料制备方法简单高效，高温热解前驱体直接由过渡金属源与多元有机羧酸和任选的含氮有机化合物、含氧有机化合物及其它有机化合物在水性溶液中直接混合来制备，所得前驱体对过渡金属的原子利用率可达100％，克服了现有技术制备金属有机骨架结构前驱体需要使用高温高压反应釜自组装、大量浪费碳源前驱体、大量使用有机溶剂、以及提纯步骤繁琐等缺点。
本发明方法无需形成金属-有机骨架化合物，易于在制备过程中调节石墨化碳层中的掺杂元素含量，从而方便调节纳米复合材料的催化性能，以适用于不同催化反应。
此外，现有技术中制备具有严密包覆的石墨化碳层和过渡金属内核的纳米级核壳结构是很困难的，特别是在制备这种严密包覆的核壳结构的同时，还需要在复合材料中形成丰富的介孔结构。本发明方法不仅能实现这些目的，还能进一步在制造出具有严密包覆的核壳结构的同时，在复合材料中形成丰富的多级介孔结构。
在第四方面，本发明还提供了根据本发明方法制备得到的包含碳包覆过渡金属颗粒的纳米复合材料。
在具体实施方式中，根据本发明方法制备得到的纳米复合材料的碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒。优选地，所述碳包覆过渡金属颗粒呈球形或者类球形，其粒径为约1-200nm，优选为约3-100nm，更优选为约4-50nm。
在具体实施方式中，根据本发明方法制备得到的纳米复合材料中的过渡金属元素以还原态(如零价态)存在，即不存在以氧化态(如氧化物)形式存在的过渡金属元素。
在优选的实施方式中，根据本发明方法制备得到的纳米复合材料还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中；更优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
在优选的实施方式中，所述纳米复合材料具有至少一个介孔分布峰，优选具有两个或两个以上的介孔分布峰。
在优选的实施方式中，所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，更优选大于约80％，进一步优选大于约90％，特别优选大于约95％，最优选为约100％。
在优选的实施方式中，所述纳米复合材料的酸洗损失率≤40％，更优选≤30％，特别优选≤10％。
在优选的实施方式中，所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
在某些优选的实施方式中，所述纳米复合物材料具有如上文对根据本发明第一方面的纳米复合材料所限定的那些特征。
在某些优选的实施方式中，所述纳米复合物材料具有如上文对根据本发明第二方面的纳米复合材料所限定的那些特征。
通过透射电镜测试可以看出，根据本发明方法制得的纳米复合材料中不含碳纳米管。
根据本发明方法制备的纳米复合材料具有丰富的介孔结构，有利于反应物和产物的扩散，使该纳米复合材料的传质效率更高，从而具有更优异的催化性能。在一些实施方式中，单批次制造的此类复合材料在介孔范围内有两个分布峰；如将多批次制造的复合材料混合则在介孔范围内可以有更多的分布峰。当所述纳米复合材料具有不同孔径范围的多级介孔结构时，可以使其表现出更独特的性能，且多级介孔结构可适用的应用范围更广。
根据本发明方法制备的纳米复合材料在石墨化碳层中掺杂有氧和/或氮，氧含量可以通过在制备过程中额外引入含氧有机化合物，比如多元醇来调节，氮含量可以通过在制备过程中额外引入含氮有机化合 物，比如六亚甲基四胺来调节。通过调节所述纳米复合材料中的氮、氧含量，可以调节碳层的催化性能，使其适用于催化不同的反应。
根据本发明方法制备的纳米复合材料可广泛用于催化材料、吸波材料、信息存储材料、磁光材料、生物医学材料，以及润滑油添加剂等领域。尤其是，过渡金属为铁、钴、镍、或铜时，该复合材料可以用作对氯硝基苯加氢制造对氯苯胺、硝基苯加氢制造苯胺、硝基苯酚加氢制造氨基苯酚、对硝基苯甲醚加氢制造对氨基苯甲醚、苯酚加氢制造环己醇、烯烃加氢、芳烃加氢制造环己烷衍生物、醛加氢制造醇、酮加氢制造醇等反应的催化剂。
在第五方面，本发明还提供了根据本发明的纳米复合材料作为催化剂在处理挥发性有机化合物中的应用，包括：使所述挥发性有机化合物与所述纳米复合材料接触，进行催化氧化反应。
在优选的实施方式中，所述挥发性有机化合物为工业废气中含有的挥发性有机化合物。
在优选的实施方式中，所述挥发性有机化合物包括丁烷，且所述丁烷占所述工业废气的体积百分含量为约0.01％-2％。
在优选的实施方式中，所述催化氧化反应在约200-500℃的温度下进行，更优选在约300-400℃的温度下进行、特别优选在约350-400℃的温度下进行。
在进一步优选的实施方式中，所述催化氧化反应的反应空速为约2000-5000毫升工业废气/(小时·克所述催化剂)。
在优选的实施方式中，所述工业废气为正丁烷氧化制备顺酐产生的工业废气。
使用本发明的纳米复合材料作为催化剂，用于挥发性有机化合物的催化氧化反应，可降低反应的苛刻度。例如，在约350℃下可将顺酐生产工艺所产生的废气中含量为约0.01-2体积％的丁烷组分催化氧化成CO 2，消除率可以达90体积％以上，在约400℃下即可将丁烷组分完全催化氧化成CO 2。与现有技术相比，可降低反应温度，提高反应空速等，实现在较低温度下将化工生产工艺所产生的废气中的低浓度丁烷完全氧化，具有很好的工业应用前景。
在第六方面，本发明还提供了根据本发明的纳米复合材料作为催化剂在加氢还原反应中的应用。
在优选的实施方式中，所述加氢还原反应选自对氯硝基苯加氢制造对氯苯胺的反应、硝基苯加氢制造苯胺的反应、硝基苯酚加氢制造氨基苯酚的反应、对硝基苯甲醚加氢制造对氨基苯甲醚的反应、苯酚加氢制造环己醇的反应、烯烃加氢的反应、芳烃加氢制造环己烷衍生物的反应、醛加氢制造醇的反应和酮加氢制造醇的反应。
本发明的纳米复合材料通过石墨化碳层严密包覆过渡金属内核，保证了其在运输和使用过程中的安全性。此外，所述纳米复合材料的石墨化碳层具有极佳的催化有机化合物加氢还原反应的能力，从而有利于进一步提高该复合材料的催化性能。
在某些优选的实施方式中，本发明提供了以下各项的技术方案：
A1.一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。
A2.根据项目A1所述的纳米复合材料，其中所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
A3.根据项目A1或A2所述的纳米复合材料，其中所述多孔材料中介孔体积占总孔体积的比例大于约50％，优选大于约80％。
A4.根据项目A1至A3中任一项所述的纳米复合材料，其中所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g。
A5.根据项目A1至A4中任一项所述的纳米复合材料，其中所述纳米复合材料的酸洗损失率≤40％。
A6.根据项目A1至A5中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，碳含量为约10.0％-60.0％，过渡金属含量为约30.0％-85.0％；特别地，碳含量可为约15.0％-40.0％，过渡金属含量可为约50.0％-80.0％。
A7.根据项目A1至A6中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，氧含量小于约15.0％，优选为约0.2％-5.0％。
A8.根据项目A1至A7中任一项所述的纳米复合材料，其中所述石墨化碳层的厚度为约0.3-6nm，优选为约0.3-3nm。
A9.根据项目A1至A8中任一项所述的纳米复合材料，其中所述 核壳结构的粒径为约1-200nm，优选为约3-100nm，更优选为约4-50nm。
A10.根据项目A1至A9中任一项所述的纳米复合材料，其中所述过渡金属为选自铁、钴、镍、铜和锌中的一种或多种。
B1.一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料的酸洗损失率≤10％。
B2.根据项目B1所述的纳米复合材料，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。
B3.根据项目B1所述的纳米复合材料，其中所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
B4.根据项目B1至B3中任一项所述的纳米复合材料，其中所述多孔材料中介孔体积占总孔体积的比例大于约50％，优选大于约80％。
B5.根据项目B1至B4中任一项所述的纳米复合材料，其中所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g。
B6.根据项目B1至B5中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料的碳含量为约15％-60％，过渡金属含量为约30％-80％，特别地，碳含量可为约30％-60％，过渡金属含量可为约30％-60％。
B7.根据项目B1至B6中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，氧含量小于约15.0％，优选为约1.0％-10.0％。
B8.根据项目B1至B7中任一项所述的纳米复合材料，其中所述石墨化碳层的厚度为约0.3-6.0nm，优选为约0.3-3nm。
B9.根据项目B1至B8中任一项所述的纳米复合材料，其中所述核壳结构的粒径为约1-200nm，优选为约3-100nm，更优选为约4-50nm。
B10.根据项目B1至B9中任一项所述的纳米复合材料，其中所述过渡金属选自铁、钴、镍、铜和锌中的一种或多种，优选为镍。
C1.一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料的酸洗损失率≤10％。
C2.根据项目C1所述的纳米复合材料，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。
C3.根据项目C2所述的纳米复合材料，其中所述纳米复合材料为具有两个或两个以上介孔分布峰的多孔材料。
C4.根据项目C1至C3中任一项所述的纳米复合材料，其中所述多孔材料中介孔体积占总孔体积的比例大于约50％，优选大于约80％。
C5.根据项目C1至C4中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中的碳含量为约15-60wt％，过渡金属含量为约30-80wt％。
C6.根据项目C1至C5中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中的氮和氧的总含量小于约15％。
C7.根据项目C1至C6中任一项所述的纳米复合材料，其中所述石墨化碳层的厚度为约0.3-6nm，优选为约0.3-3nm。
C8.根据项目C1至C7中任一项所述的纳米复合材料，其中所述核壳结构的粒径为约1-200nm，优选为约3-100nm，优选为约4-50nm。
C9.根据项目C1至C8中任一项所述的纳米复合材料，其中所述过渡金属选自铁、钴、镍、铜和锌中的一种或多种，优选为镍。
C10.根据项目C1至C9中任一项所述的纳米复合材料，其中所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
D1.一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料。
D2.根据项目D1所述的纳米复合材料，其中所述纳米复合材料具有两个或两个以上的介孔分布峰。
D3.根据项目D1或D2所述的纳米复合材料，其中所述多孔材料中介孔体积占总孔体积的比例大于约50％，优选大于约80％。
D4.根据项目D1至D3中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，碳含量为约10.0％-60.0％，过渡金属含量为约30.0％-85.0％；特别地，碳含量可为约30.0％-50.0％，过渡金属含量可为约30.0％-60.0％。
D5.根据项目D1至D4中任一项所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，氮和氧的总含量小于约15.0％，优选为约0.2％-12.0％，更优选为约0.5％-10.0％。
D6.根据项目D1至D5中任一项所述的纳米复合材料，其中以质量百分比计，氮含量小于约15％，优选为约0.1-10％，更优选为约1-5％。
D7.根据项目D1至D6中任一项所述的纳米复合材料，其中所述纳米复合材料的酸洗损失率≤40％。
D8.根据项目D1至D7中任一项所述的纳米复合材料，其中所述石墨化碳层的厚度为约0.3-6.0nm，优选为约0.3-3nm。
D9.根据项目D1至D8中任一项所述的纳米复合材料，其中所述核壳结构的粒径为约1-200nm，优选为约3-100nm，更优选为约4-50nm。
D10.根据项目D1至D9中任一项所述的纳米复合材料，其中所述过渡金属为选自铁、钴、镍、铜和锌中的一种或多种。
D11.根据项目D1至D10中任一项所述的纳米复合材料，其中所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
E1、一种制备碳包覆过渡金属纳米复合材料的方法，包括如下步骤：
i)将含过渡金属盐和多元有机羧酸的混合物与溶剂混合形成均相溶液；
ii)除去所述均相溶液中的溶剂，从而形成前驱体；及
iii)在惰性保护气氛或还原气氛下将所述前驱体高温热解。
E2、根据项目E1所述的方法，其中所述过渡金属为铁、钴、镍、铜中的一种或多种。
E3、根据项目E1或E2所述的方法，其中所述过渡金属盐为过渡金属的有机酸盐、碳酸盐、碱式碳酸盐中的一种或多种；优选所述过渡金属的有机酸盐为所述过渡金属的不含杂原子的有机羧酸盐，例如醋酸盐。
E4、根据项目E1至E3中任一项所述的方法，其中所述多元有机羧酸为柠檬酸、顺丁烯二酸、均苯三甲酸、对苯二甲酸、苹果酸、EDTA、吡啶二羧酸的一种或多种。
E5、根据项目E1至E4中任一项所述的方法，其中所述过渡金属盐和多元有机羧酸的质量比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.8-3。
E6、根据项目E1至E5中任一项所述的方法，其中所述溶剂选自水、乙醇或其混合物。
E7、根据项目E1至E6中任一项所述的方法，其中在所述步骤iii)中，所述惰性保护气氛为氮气或氩气，所述高温热解以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，所述恒温段温度为约400-800℃；优选地，所述升温速率为约1-10℃/min，在恒温段保持恒温时间为60-480min，所述恒温段温度为约500-800℃。
E8、根据项目E1至E6中任一项所述的方法，其中所述还原气氛为惰性气体与氢气的混合气体，所述高温热解以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，所述恒温段温度为约400-800℃；优选地，所述升温速率为约1-10℃/min，在恒温段保持恒温时间为约60-480min，所述恒温段温度为约500-800℃。
E9、根据项目E1至E8中任一项所述的方法，进一步包括在所述步骤iii)之后对热解产物用非氧化性强酸处理的步骤。
E10、按照项目E1至E9中任一项所述的方法制备得到的碳包覆过渡金属纳米复合材料。
E11、根据项目E10所述的纳米复合材料，其中所述纳米复合材料具有至少一个介孔分布峰，优选具有两个或两个以上的介孔分布峰。
E12、根据项目E10或E11所述的纳米复合材料，其中所述纳米复合材料中，介孔体积占总孔体积的比例大于约50％，优选大于约80％。
E13、根据项目E10至E12中任一项所述的纳米复合材料，其中所述纳米复合材料的酸洗损失率≤40％，优选≤30％，更优选≤10％。
E14、根据项目E10至E13中任一项所述的纳米复合材料，其中所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
F1、一种制备碳包覆过渡金属纳米复合材料的方法，包括如下步骤：
i)将包含过渡金属盐、多元有机羧酸和含氮有机化合物的混合物与溶剂混合，形成均相溶液；
ii)除去所述均相溶液中的溶剂，从而形成前驱体；及
iii)在惰性保护气氛或还原气氛下，将所述前驱体高温热解。
F2、根据项目F1所述的方法，其中所述过渡金属为选自铁、钴、镍、铜中的一种或多种。
F3、根据项目F1或F2所述的方法，其中所述过渡金属盐为所述过渡金属的有机酸盐、碳酸盐、碱式碳酸盐中的一种或多种；优选所述过渡金属的有机酸盐为所述过渡金属的不含杂原子的有机羧酸盐，例如醋酸盐。
F4、根据项目F1至F3中任一项所述的方法，其中所述多元有机羧酸为选自柠檬酸、顺丁烯二酸、均苯三甲酸、对苯二甲酸、苹果酸、EDTA、吡啶二羧酸中的一种或多种。
F5、根据项目F1至F4中任一项所述的方法，其中所述含氮有机化合物为选自尿素、三聚氰胺、二氰二胺、六亚甲基四胺、氨基酸中的一种或多种。
F6、根据项目F1至F5中任一项所述的方法，其中所述过渡金属盐、所述多元有机羧酸、所述含氮有机化合物的质量比为约1∶0.1-100∶0.1-100，优选为约1∶0.5-5∶0.5-5，更优选约1∶0.8-2∶1-2。
F7、根据项目F1至F6中任一项所述的方法，其中所述溶剂选自水、乙醇及其混合物。
F8、根据项目F1至F7中任一项所述的方法，其中在所述步骤iii)中，所述惰性保护气氛为氮气或氩气，所述高温热解以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，所述恒温段温度为约400-800℃；优选地，所述升温速率为约1-10℃/min，在恒温段保持恒温时间为约60-480min，所述恒温段温度为约500-800℃。
F9、根据项目F1至F7中任一项所述的方法，其中所述还原气氛为惰性气体与氢气的混合气体，所述高温热解以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，所述恒温段温度为约400-800℃；优选地，所述升温速率为约1-10℃/min，所述恒温段温度为约500-800℃。
F10、根据项目F1至F9中任一项所述的方法，进一步包括在所述步骤iii)之后对热解产物用非氧化性强酸处理的步骤。
F11、按照项目F1-F10中任一项所述的方法制备得到的碳包覆过 渡金属纳米复合材料。
F12、根据项目F11所述的纳米复合材料，其中所述纳米复合材料具有至少一个介孔分布峰，优选具有两个或两个以上的介孔分布峰。
F13、根据项目F11或F12所述的纳米复合材料，其中所述纳米复合材料中，介孔体积占总孔体积的比例大于约50％，优选大于约80％。
F14、根据项目F11至F13中任一项所述的纳米复合材料，其中所述纳米复合材料的酸洗损失率≤40％，优选≤30％，更优选≤10％。
F15、根据项目F11至F14中任一项所述的纳米复合材料，其中所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
G1、一种对氯硝基苯加氢制造对氯苯胺的方法，包括在催化剂存在下使对氯硝基苯加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
G2、根据项目G1所述的方法，包括将所述催化剂与对氯硝基苯在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
G3、根据项目G1或G2所述的方法，其中加氢反应的温度为约60℃-120℃，氢气压力为约0.5MPa-2MPa。
H1、一种硝基苯加氢制造苯胺的方法，包括在催化剂存在下使硝基苯加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
H2、根据项目H1所述的方法，包括将所述催化剂与硝基苯在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
H3、根据项目H1或H2所述的方法，其中加氢反应的温度为约60℃-120℃，氢气压力为约0.5MPa-2MPa。
11、一种硝基苯酚加氢制造氨基苯酚的方法，包括在催化剂存在下使硝基苯酚加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
12、根据项目11所述的方法，包括将所述催化剂与硝基苯酚在溶 剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
13、根据项目11或12所述的方法，其中加氢反应的温度为约50℃-120℃，氢气压力为约0.5MPa-2MPa。
J1、一种对硝基苯甲醚加氢制造对氨基苯甲醚的方法，包括在催化剂存在下使对硝基苯甲醚加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
J2、根据项目J1所述的方法，包括将所述催化剂与对硝基苯甲醚在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
J3、根据项目J1或J2所述的方法，其中加氢反应的温度为约50℃-120℃，氢气压力为约0.5MPa-2MPa。
K1、一种苯酚加氢制造环己醇的方法，包括在催化剂存在下使苯酚加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
K2、根据项目K1所述的方法，包括将所述催化剂与苯酚类化合物在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
K3、根据项目K1或K2所述的方法，其中加氢反应的温度为约150℃-250℃，氢气压力为约3MPa-6MPa。
L1、一种烯烃加氢的方法，包括在催化剂存在下使烯烃加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D111、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
L2、根据项目L1所述的方法，包括将所述催化剂与所述烯烃在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
L3、根据项目L1或L2所述的方法，其中加氢反应的温度为约100℃-130℃，氢气压力为约1MPa-3MPa。
M1、一种芳烃加氢制造环己烷衍生物的方法，包括在催化剂存在下使芳烃加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述 催化剂。
M2、根据项目M1所述的方法，包括将所述催化剂与所述芳烃在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
M3、根据项目M1或M2所述的方法，其中加氢反应的温度为约200℃-300℃，氢气压力为约3MPa-6MPa。
N1、一种醛加氢制造醇的方法，包括在催化剂存在下使所述醛加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
N2、根据项目N1所述的方法，包括将所述催化剂与所述醛在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
N3、根据项目N1或N2所述的方法，其中加氢反应的温度为约80℃-180℃，氢气压力为约2MPa-5MPa。
O1、一种酮加氢制造醇的方法，包括在催化剂存在下使所述酮加氢还原的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
O2、根据项目O1所述的方法，包括将所述催化剂与所述酮在溶剂中混合，而后进行加氢还原的步骤，其中所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
O3、根据项目O1或O2所述的方法，其中加氢反应的温度为约100℃-200℃，氢气压力为约3MPa-6MPa。
P1、一种处理挥发性有机物的方法，包括在催化剂存在下使所述挥发性有机物催化氧化的步骤，其中以项目A1-A10、B1-B10、C1-C10、D1-D11、E10-E14和F11-F15中任一项所述的纳米复合材料作为所述催化剂。
P2、根据项目P1所述的方法，其中所述挥发性有机化合物为工业废气、特别是正丁烷氧化制备顺酐产生的工业废气中所含的挥发性有机化合物。
P3、根据项目P2所述的方法，其中所述挥发性有机化合物包括丁烷，且丁烷在所述工业废气中的体积百分含量为约0.01-2％。
P4、根据项目P2或P3所述的方法，其中所述催化氧化反应的温 度为约200-500℃，优选约350-400℃，反应空速为约2000-5000毫升工业废气/(小时·克所述催化剂)。
Q1一种通过催化加氢还原有机化合物的方法，其特征在于，采用具有核壳结构的催化剂，采用氢气为还原剂，对有机化合物进行催化加氢还原；所述核壳结构的壳层为石墨化碳层，内核为过渡金属；所述的内核被石墨化碳层严密包覆。
Q2、根据项目Q1所述的方法，其特征在于，所述的有机化合物为含有以下基团之一或其任意组合的有机化合物：硝基、羰基和碳碳双键。
Q3、根据项目Q1或Q2所述的方法，其特征在于，所述催化剂的孔分布图中，在介孔范围内有大于一个的分布峰(比如两个分布峰)。
Q4、根据项目Q1至Q3中任一项所述的方法，其特征在于，所述过渡金属为铁、钴、镍、铜和锌中的一种或其任意的组合。
Q5、一种通过催化加氢还原有机化合物的方法，其特征在于，采用具有核壳结构的催化剂，采用氢气为还原剂，对有机化合物进行催化加氢还原；所述核壳结构的壳层为石墨化碳层，内核为过渡金属；所述催化剂的孔分布图中，介孔范围内有大于一个的分布峰。
Q6、根据项目Q5所述的方法，其特征在于，所述的有机化合物为含有以下基团之一或其任意组合的有机化合物：硝基、羰基和碳碳双键。
Q7、根据项目Q5或Q6所述的方法，其特征在于，所述催化剂的孔分布图中，介孔范围内有两个分布峰。
Q8、根据项目Q5至Q7中任一项所述的方法，其特征在于，所述过渡金属为铁、钴、镍、铜和锌中的一种或其任意的组合。
Q9、一种通过催化加氢将硝基苯还原为苯胺的方法，其特征在于，采用项目Q1至Q8中任一项所述的方法对硝基苯进行催化加氢还原。
Q10、一种通过催化加氢将卤代硝基苯还原为卤代苯胺的方法，其特征在于，采用项目Q1至Q8中任一项所述的方法对卤代硝基苯进行催化加氢还原。
Q11、一种通过催化加氢将硝基苯酚还原为氨基苯酚的方法，其特征在于，采用项目Q1至Q8中任一项所述的方法对硝基苯酚进行催化加氢还原。
Q12、一种通过催化加氢还原硝基苯甲醚为氨基苯甲醚的方法，其特征在于，采用项目Q1至Q8中任一项所述的方法对硝基苯甲醚进行催化加氢还原。
Q13、一种碳与过渡金属的复合材料，其特征在于，具有核壳结构，所述核壳结构的壳层为石墨化碳层，内核为过渡金属；所述复合材料的孔分布图中，介孔范围内有大于一个的分布峰。
Q14、根据项目Q13所述的复合材料，其特征在于，所述复合材料的孔分布图中，介孔范围内有两个分布峰(比如在1-7nm以及8-16nm出现两个分布峰)。
Q15、根据项目Q13或Q14所述的复合材料，其特征在于，所述过渡金属的粒径在1nm至200nm中任意两个整数点形成的范围之间(比如1、5、10、15、20、25、30、40、50、60、70、80、90、100、110、120、130、140、150、160、170、180、190、200中任意两点所形成的范围)。
Q16、根据项目Q13至Q15中任一项所述的复合材料，其特征在于，所述过渡金属为铁、钴、镍、铜和锌中的一种或其任意的组合。
Q17、根据项目Q13至Q16中任一项所述的复合材料在催化加氢还原有机化合物中的应用。
Q18、根据项目Q17所述的应用，其特征在于，所述的有机化合物为含有以下基团之一或其任意组合的有机化合物：硝基、羰基和碳碳双键。
下面将通过实施例来对本发明做进一步说明，但是本发明并不因此而受到任何限制。
试剂、仪器与测试
如无特殊说明，本申请中所采用的试剂均为分析纯，所用试剂均为市售可得，例如购自西格玛奥德里奇(Sigma-Aldrich)。
本申请中，所用XRD衍射仪的型号为XRD-6000型X射线粉末衍射仪(日本岛津)。XRD测试条件为：Cu靶，Kα射线(波长λ＝0.154nm)，管电压为40kV，管电流为200mA，扫描速度为10°(2θ)/min。
本申请中，过渡金属粒子的平均粒径由XRD图分峰后，采用谢乐公式：D＝k γ/(B cos θ)计算得到。其中k为Scherrer常数，k＝0.89； B为半高宽；θ为衍射角，单位弧度(rad)；γ为x射线波长，0.154054nm。
本申请中，通过扫描电镜(SEM)表征材料的表面形貌。所采用的扫描电镜的型号为Hitachi S-4800冷场扫描发射电镜，扫描电镜的测试条件为：将粉末样品通过导电胶固定在样品台观察，加速电压为5kV。
本申请中，所用高分辨透射电镜(HRTEM)的型号为JEM-2100(HRTEM)(日本电子株式会社)。高分辨透射电镜的测试条件为：加速电压为200kV。
本申请中，所用X射线光电子能谱分析仪(XPS)为VG Scientifc公司生产的配备有Avantage V5.926软件的ESCALab220i-XL型射线电子能谱仪。X射线光电子能谱分析测试条件为：激发源为单色化A1KαX射线，功率为330W，分析测试时基础真空为3×10 -9mbar。另外，电子结合能用C1s峰(284.6eV)校正，后期分峰处理软件为XPSPEAK。
本申请中，对于碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层的纳米复合材料，其碳(C)、氢(H)、氧(O)三种元素的分析在Elementar Micro Cube元素分析仪上进行。具体操作方法和条件如下：样品在锡杯中称量1-2mg，放入自动进样盘，通过球阀进入燃烧管燃烧，燃烧温度为1000℃(为了去除进样时大气干扰，采用氦气吹扫)，然后用还原铜对燃烧后的气体进行还原，形成二氧化碳和水。混合气体通过两根解吸柱进行分离，依次进TCD检测器检测。氧元素的分析是利用高温分解，在碳催化剂的作用下，将样品中的氧转化为CO，然后采用TCD检测CO。由于该复合材料中仅含有碳、氢、氧和金属元素，因此由碳、氢、氧三种元素的总含量即可得到金属元素的总含量。
本申请中，对于碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层的纳米复合材料，其碳(C)、氢(H)、氧(O)、氮(N)四种元素的分析也在Elementar Micro Cube元素分析仪上进行。具体操作方法和条件如下：样品在锡杯中称量1-2mg，放入自动进样盘，通过球阀进入燃烧管燃烧，燃烧温度为1000℃(为了去除进样时大气干扰，采用氦气吹扫)，然后用还原铜对燃烧后的气体进行还原，形成氮气、二氧化碳和水。混合气体通过三根解吸柱进行分离，依次进TCD检测器检测。氧元素的分析是利用高温分解，在碳催化剂的作用下，将样品中的氧转化为CO，然后采用TCD检测CO。由于该复合材料中仅含有碳、氢、氧、氮和金属元素，因此由碳、氢、氧、氮四种元素的总含量即可得到金 属元素的总含量。
本申请中，不同金属元素之间的比例由X射线荧光光谱分析仪(XRF)测定，由已知的碳、氢、氧和氮(如果存在的话)元素的总含量，算出不同金属元素在复合材料中的含量。本申请中所用X射线荧光光谱分析仪(XRF)的型号为Rigaku 3013X射线荧光光谱仪。X射线荧光光谱分析测试条件为：扫描时间为100s，气氛为空气。
本申请中，样品的孔结构性质由Quantachrome AS-6B型分析仪测定，比表面积和孔体积由Brunauer-Emmett-Taller(BET)方法得到，孔分布曲线根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到。
本申请中，气体的组成由在线气相色谱分析得到，色谱型号为Agilent GC 7890B，精确度为10 -6。测试气体从进样口通入色谱，经色谱柱分离，各个色谱峰经过积分计算出各气体组分百分比。
本申请中，所述“酸洗损失率”按以下方式测量和计算：
按20mL硫酸水溶液(1mol/L)投加1g样品的比例，在90℃下对样品处理8h，然后用去离子水洗涤至中性，干燥后称重、分析。按下式计算酸洗损失率：
酸洗损失率＝[1-(酸洗后复合材料中过渡金属的质量分数×酸洗后复合材料的质量)÷(待酸洗复合材料中过渡金属的质量分数×待酸洗复合材料的质量)]×100％。
制备实施例及对比例
第一部分
实施例1-1
称取10g醋酸镍和10g柠檬酸，加入30mL去离子水中，在70℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至650℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-2
称取10g醋酸镍和20g柠檬酸，加入50mL去离子水中，在80℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量150mL/min，并以5℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-3
称取10g醋酸钴和30g柠檬酸，加入50mL去离子水中，在80℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量150mL/min，并以5℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆钴纳米复合材料。
实施例1-4
称取10g醋酸镍，10g柠檬酸和3g顺丁烯二酸，加入50mL去离子水中，在60℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以3℃/min的速率升温至550℃，恒温8h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-5
称取10g醋酸镍，7g柠檬酸和5g季戊四醇，加入150mL去离子水中，在60℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以6℃/min的速率升温至600℃，恒温1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-6
称取5g醋酸镍，5g醋酸钴和16.83g柠檬酸，加入到含有30mL去离子水的烧杯中，在80℃下搅拌得到均相溶液，并继续加热蒸干后得到前躯体。
将前躯体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入流量为150mL/min的氮气，并以5℃/min的速率升温至500℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍钴纳米复合材 料。
实施例1-7
称取10g醋酸镍和20g乙二胺四乙酸，加入150mL去离子水中，在60℃下搅拌得到混合溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以4℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-8
称取10g醋酸镍和10g对苯二甲酸，加入30mL去离子水中，在70℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至650℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-9
称取10g醋酸镍和8g吡啶二羧酸，加入150mL去离子水中，在60℃下搅拌得到混合溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以4℃/min的速率升温至600℃，然后通入流量30mL/min的氢气，恒温2h后，关闭氢气，停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例1-10
重复实施例1-1的方法，不同之处是在实施例1-1之后增加酸处理步骤，即将2g实施例1-1所得的材料加入40mL硫酸水溶液(1mol/L)中，在90℃下处理8h。然后用去离子水洗涤至中性，得到严密保覆的碳包覆镍纳米复合材料。
对比例1-1
按文献RSC Advances，2017，7，1531-1539中公开的方法制备碳包 覆纳米镍纳米复合材料。
称取1g六水氯化镍溶解于58mL N，N-二甲基甲酰胺(DMF)，称取2g对苯二甲酸溶解于15mL N，N-二甲基甲酰胺(DMF)中。然后，将氯化镍的DMF溶液缓慢滴加到对苯二甲酸的DMF溶液中，并在室温下搅拌1h。将混合溶液转移到高压釜中，在120℃下反应16h，冷却后得到绿色沉淀。用DMF洗涤3次，最后在70℃干燥，将固体研磨后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量40mL/min，并以10℃/min的速率升温至600℃，恒温1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
对比例1-2
重复实施例1-7的方法，不同之处仅在于将20g乙二胺四乙酸用20g乙二胺四乙酸二钠代替。
对比例1-3
重复实施例1-1的方法，不同之处仅在于将10g醋酸镍用10g硝酸镍代替。
对比例1-4
将10g醋酸镍固体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入流量为150mL/min的氮气，并以5℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到样品材料。
所得材料的表征
实施例1-1至1-10制备的材料中所含元素的质量百分含量列于表1-1中。
表1-1 实施例所得材料的元素含量
Figure PCTCN2018097303-appb-000001
对实施例1-1至1-10和对比例1-1至1-4制备的材料进行酸洗，酸洗损失率列于表1-2中。
表1-2 实施例与对比例所得材料的酸洗损失率
实施例编号 酸洗损失率(％)
实施例1-1 36.2
实施例1-2 13.2
实施例1-3 9.5
实施例1-4 9.5
实施例1-5 28.6
实施例1-6 23.1
实施例1-7 12.4
实施例1-8 29.4
实施例1-9 25.6
实施例1-10 0.56
对比例1-1 92
对比例1-2 100
对比例1-3 100
对比例1-4 100
结合表1-1和表1-2的数据可以看出，本发明实施例1-1至1-9制备的碳包覆过渡金属纳米复合材料中，碳对过渡金属的包覆效果较好，即大部分金属被严密包覆在碳层内。
对实施例1-1至1-9的纳米复合材料进行X射线光电子能谱(XPS)测试，表明复合材料中Ni价态为0价，且复合纳米材料中的O不存在金属-氧(M-O)键，只存在羧基氧、羰基氧和羟基氧，充分证明了这种核壳结构有效地将高活性的Ni纳米粒子与空气隔绝，核壳结构完整，因而更适于苛刻反应条件下的使用。
图1-1是实施例1-1所制备的前躯体的XRD图，说明该前躯体为无定形材料；图1-2为实施例1-1所制备的碳包覆镍纳米复合材料的磁性测试的照片，用磁铁吸引后，碳包覆镍纳米复合材料的悬浮液迅速变澄清，表明该复合材料具有强磁性；图1-3为实施例1-1所制备的碳包覆镍纳米复合材料的TEM图，可看出，该材料为包含碳包覆金属颗粒的复合材料，在镍纳米颗粒的外层包裹着具有一定石墨化程度的碳 层，形成完整的核壳结构。图1-4是实施例1-1所制备的碳包覆镍纳米复合材料的XRD图，从中可看出，在该材料的衍射图中存在对应于石墨碳的衍射峰(2θ角为26°)和对应于面心立方结构的镍(fcc-Ni)的衍射峰(2θ角为44.5°、51.7°和76.4°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为4.7nm。BET测试表明，该材料的比表面积为146m 2/g，孔体积为0.37cm 3/g，其中介孔体积为0.365cm 3/g，占总孔体积的98.6％。图1-5A和图1-5B分别为该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线，可以看出，该复合材料在3.77nm和10.26nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为36.2％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-6是实施例1-2制备的碳包覆镍纳米复合材料的TEM图。从图1-6可以看出，该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-7)存在对应于石墨碳的衍射峰(2θ角为26°)和对应于fcc-Ni的衍射峰(44.5°、51.9°和76.2°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为34.5nm。BET测试表明，该材料的比表面积为137m 2/g，孔体积为0.343cm 3/g，其中介孔体积为0.323cm 3/g，占总孔体积的94％。图1-8是实施例1-2所制备的碳包覆镍纳米复合材料的孔分布曲线图。从图1-8中可以看出，该材料的BJH孔径分布曲线中在3.85nm和11.53nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为13.2％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-9是实施例1-3所制备的碳包覆钴纳米复合材料的TEM图。从图1-9中可以看出，该材料含有以金属钴纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-10)存在对应于石墨碳的衍射峰(2θ角为26°)和对应于fcc-Co的衍射峰(44.3°、51.4°和75.9°)，说明该材料包括具有一定石墨化程度的碳和具有面心立方结构的钴。由谢乐公式计算得到该碳包覆钴纳米粒子的平均粒径为24nm。BET测试表明，该材料的比表面积为192m 2/g，孔体积为0.398cm 3/g，其中介孔体积为0.394cm 3/g，占总孔体积的99％。图 1-11是实施例1-3所制备的碳包覆钴纳米复合材料的孔分布曲线图。从图1-11中可以看出，该材料的BJH孔径分布曲线中在3.38nm和8.98nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为9.5％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-12是实施例1-4所制备的碳包覆镍纳米复合材料的TEM图。从图1-12中可以看出，该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。经过酸洗实验，该材料的酸洗损失率为9.5％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-13是实施例1-5所制备的碳包覆镍纳米复合材料的TEM图。从图1-13中可以看出，该材料形成了以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。经过酸洗实验，该材料的酸洗损失率为28.6％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-14是实施例1-6所制备的碳包覆镍钴纳米复合材料的TEM图。从图1-14中可以看出，该材料含有以金属镍或钴纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-15)存在对应于石墨碳的衍射峰(2θ角为25.6°)和对应于fcc-Ni和fcc-Co的衍射峰(44.3°、51.7°和76.0°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍和钴。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为39nm。BET测试表明，该材料的比表面积为159m 2/g，孔体积为0.208cm 3/g，其中介孔体积为0.196cm 3/g，占总孔体积的94％。图1-16是实施例1-6所制备的碳包覆镍钴纳米复合材料的孔分布曲线图。从图1-16中可以看出，该材料的BJH孔径分布曲线中在3.25nm和8.94nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为23.1％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-17是实施例1-7所制备的碳包覆镍纳米复合材料的TEM图。从图1-17中可以看出，该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-18)存在对应于石墨碳的衍射峰(2θ角为25.6°)、对应于fcc-Ni的衍射峰 (44.4°、51.8°和76.4°)和对应于密排六方结构的镍(hcp-Ni)的衍射峰(2θ角为41.9°、44.7°、47.5°和62.6°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构和密排六方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为7.2nm。BET测试表明，该材料的比表面积为228m 2/g，孔体积为0.293cm 3/g，其中介孔体积为0.293cm 3/g，占总孔体积的100％。图1-19是实施例1-7所制备的碳包覆镍纳米复合材料的孔分布曲线图。从图1-19中可以看出，该材料的BJH孔径分布曲线中在3.97nm和6.39nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为12.4％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-20是实施例1-8所制备的碳包覆镍纳米复合材料的TEM图。从图1-20中可以看出，该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-21)存在对应于石墨碳的衍射峰(2θ角为25.8°)和对应于fcc-Ni的衍射峰(44.6°、51.8°和76.4°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为8.4nm。经过酸洗实验，该材料的酸洗损失率为29.4％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-22是实施例1-9所制备的碳包覆镍纳米复合材料的TEM图。从图1-22中可以看出，该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图1-23)存在对应于石墨碳的衍射峰(2θ角为25.9°)和对应于fcc-Ni的衍射峰(44.4°、51.7°和76.3°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为7.5nm。经过酸洗实验，该材料的酸洗损失率为25.6％。在前述方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图1-24是实施例1-10所制备的碳包覆镍纳米复合材料的磁性测试的照片，经磁铁吸引后，含碳包覆镍纳米复合材料的悬浮液迅速变清，表明所制备的碳包覆材料具有强磁性。图1-25是该纳米复合材料的TEM图，由图中可看出，该材料含有以金属镍纳米颗粒为核，以石墨化碳层为壳的核壳结构。该复合材料的X射线衍射谱图如图1-26所示，从中可看出，在该材料的衍射图中存在对应于石墨碳的衍射峰(2θ角 为25.7°)和对应于fcc-Ni的衍射峰(44.5°、51.9°和76.2°)。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为4.2nm。BET测试结果表明，该材料的比表面积为176m 2/g，孔体积为0.381cm 3/g，其中介孔体积为0.376cm 3/g，占总孔体积的98.7％。图1-27所示是实施例1-10所制备的碳包覆镍纳米复合材料的孔分布曲线图。从图1-27中可以看出，该材料的BJH孔径分布曲线中在3.80nm和10.47nm处存在两个介孔分布峰。
对比例1-1制备的碳包覆镍纳米复合材料经过上述表征测试，表明该材料的XRD衍射图中存在对应于石墨碳的衍射峰(2θ角为26°)和对应于fcc-Ni的衍射峰(44.5°、51.9°和76.2°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。BET测试表明，该材料的比表面积为159m 2/g，孔体积为0.208cm 3/g，其中＞2nm的孔体积为0.05cm 3/g，占总孔体积的24％。在该材料的BJH孔径分布曲线中仅在0.68nm处存在1个微孔分布峰。经过酸洗实验，该材料的酸洗损失率为92％。
图1-28为对比例1-4制备的样品材料的XRD图，从中可看出，在该材料的衍射图中存在对应于fcc-Ni的衍射峰(44.2°、51.6°和76.2°)。经元素分析仪和X射线荧光光谱分析仪(XRF)测定，该材料中所含元素的质量百分含量为：碳1.34％，氢0.32％，氧0.18％，镍98.16％。
比较实施例1-1至1-10和对比例1-1至1-3可以看出，本发明的方法更加简单高效，高温热解前驱体直接由过渡金属盐与多元有机羧酸在溶剂(可为水)中直接反应制备，前驱体对原料中过渡金属的原子利用率可达100％，克服了现有技术制备金属有机骨架结构前驱体需要使用高温高压反应釜自组装、大量浪费碳源前驱体、大量使用有机溶剂、提纯步骤繁琐等缺点；并且不需要高分子助剂，简化了反应步骤。
进一步地，本发明方法能够制备严密包覆的纳米复合材料，使得该材料能在更苛刻的条件下使用。更进一步地，本发明方法能够制备严密包覆的纳米复合材料，并使其具有丰富的介孔结构，特别是多级介孔结构，从而适合在更多的领域中应用。
第二部分
实施例2-1
称取10g醋酸镍、10g柠檬酸和20g六亚甲基四胺，加入30mL去离子水中，在70℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至650℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-2
称取10g醋酸镍，20g柠檬酸和20g六亚甲基四胺，加入100mL去离子水中，在80℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量150mL/min，并以5℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-3
称取10g醋酸钴、10g柠檬酸和20g六亚甲基四胺，将它们加入到含有150mL去离子水的烧杯中，在60℃下搅拌得到均相溶液，并继续加热蒸干得到前躯体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至700℃，恒温1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆钴的纳米复合材料。
实施例2-4
称取10g醋酸镍、10g醋酸钴、20g柠檬酸和10g六亚甲基四胺，将它们加入到含有150mL去离子水的烧杯中，在60℃搅拌形成均相溶液后继续加热蒸干得到固体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以4℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍钴的纳米复合材料。
实施例2-5
称取10g醋酸镍、10g柠檬酸和20g二氰二胺，加入150mL去离子水中，在60℃下搅拌得到均相溶液，并继续加热蒸干，将固体研磨后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至700℃，恒温1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-6
称取10g醋酸镍、10g柠檬酸、20g尿素和3g顺丁烯二酸，加入50mL去离子水中，在60℃下搅拌得到均相溶液，并继续加热蒸干，将固体研磨后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以3℃/min的速率升温至550℃，恒温3h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-7
称取10g醋酸镍、20g对苯二甲酸和20g六亚甲基四胺，加入100mL去离子水中，在80℃下搅拌得到均相溶液，并继续加热蒸干，将固体研磨后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量80mL/min，并以8℃/min的速率升温至800℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-8
称取10g醋酸镍、7g柠檬酸，10g三聚氰胺和5g季戊四醇，加入150mL去离子水中，在60℃下搅拌得到均相溶液，并继续加热蒸干后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以6℃/min的速率升温至600℃，恒温1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-9
称取20g醋酸镍和10g乙二胺四乙酸，加入150mL去离子水中，在60℃搅拌形成均相溶液后继续加热蒸干，将固体研磨后得到前驱体。
将前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以4℃/min的速率升温至600℃，恒温2h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料。
实施例2-10
重复实施例2-1的方法，不同之处是在实施例2-1后增加酸处理步骤，即将2g实施例2-1所得的材料加入100mL 10wt％的盐酸中，在回流温度下处理12h。然后用去离子水洗涤至中性，120℃烘干，得到严密保覆的碳包覆镍纳米复合材料。
对比例2-1
Ni-MOF材料的制备：称取3.09g硝酸镍、2.8g对苯二甲酸和0.95g三乙烯二胺，加入到120mL二甲基甲酰胺中，在120℃下反应8h，然后密封，于120℃静置40h。过滤后用二甲基甲酰胺和甲醇洗涤，真空干燥得到Ni-MOF材料。
氮掺杂碳包覆镍(Ni@C-N)纳米材料的合成：将得到的Ni-MOF置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以4℃/min的速率升温至200℃，恒温2h，然后升温到500℃，恒温8h，停止加热。在氮气气氛下冷却至室温，得到Ni@C-N纳米材料。
对比例2-2
重复实施例2-1的方法，不同之处仅在于将10g醋酸镍替换成10g硝酸镍。
对比例2-3
重复实施例2-9的方法，不同之处仅在于将10g乙二胺四乙酸替换成10g乙二胺四乙酸二钠。
所得材料的表征
实施例2-1至2-11制备的材料中所含元素的质量百分含量列于表2-1中。
表2-1 实施例所得材料的元素含量
Figure PCTCN2018097303-appb-000002
对实施例2-1至2-11和对比例2-1至2-3制备的材料进行酸洗，酸洗损失率列于表2-2中。
表2-2 实施例和对比例所得材料的酸洗损失率
实施例编号 酸洗损失率(％)
实施例2-1 14
实施例2-2 9.3
实施例2-3 31.2
实施例2-4 38.4
实施例2-5 31.2
实施例2-6 25.4
实施例2-7 16.7
实施例2-8 39.8
实施例2-9 21.7
实施例2-10 0.34
对比例2-1 64.2
对比例2-2 78.2
对比例2-3 100
结合表2-1和表2-2的数据可以看出，本发明实施例2-1至2-11制备的碳包覆过渡金属纳米复合材料中，碳对过渡金属的包覆效果较好，即大部分金属被严密包覆在碳层内。
图2-1是实施例2-1制备的氧氮掺杂碳包覆镍纳米复合材料的磁性测试的照片，经磁铁吸引后，含氧氮掺杂碳包覆镍纳米复合材料的悬浮液迅速变澄清，表明该复合材料具有强磁性。图2-2是实施例2-1制备的氧氮掺杂碳包覆镍纳米复合材料的TEM图。从图2-2中可以看出，该复合材料包含碳包覆金属镍颗粒，该颗粒在镍纳米颗粒的外层包裹着具有一定石墨化程度的碳层，形成完整的核壳结构。图2-3是实施例2-1制备的氧氮掺杂碳包覆镍纳米复合材料的XRD图。从图2-3中可以看出，在该材料的衍射图中存在对应于石墨碳的衍射峰(2θ角为25.96°)和对应于面心立方结构的镍(fcc-Ni)的衍射峰(2θ角为44.38°、51.83°和76.42°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为6.3nm。BET测试表明，该材料的比表面积为114m 2/g，孔体积 为0.181cm 3/g，其中介孔体积为0.173cm 3/g，占总孔体积的95.6％。图2-4A和图2-4B分别为该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线，可以看出，该复合材料在3.75nm和10.03nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为14％。
图2-5是实施例2-2制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图(图2-6)中存在对应于石墨碳的衍射峰(2θ角为25.8°)和对应于fcc-Ni的衍射峰(2θ角为44.4°、51.9°和76.5°)以及对应于密排立方结构的镍(hcp-Ni)的衍射峰(2θ角为41.9°、44.4°、47.5°和62.41°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构和密排立方结构存在的镍。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为31.4nm。BET测试表明，该材料的比表面积为126m 2/g，孔体积为0.213cm 3/g，其中介孔体积为0.207cm 3/g，占总孔体积的97.1％。通过测定该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线(图2-7)，发现该复合材料在3.83nm和11.16nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为9.3％。
图2-8是实施例2-3制备的碳包覆钴纳米复合材料的TEM图，表明该材料含有以金属钴纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图(图2-9)中存在对应于钴的衍射峰(2θ角为44.42°)，说明该材料中存在单质钴。由谢乐公式计算得到该碳包覆钴纳米粒子的平均粒径为17.5nm。BET测试表明，该材料的比表面积为140m 2/g，孔体积为0.158cm 3/g，其中介孔体积为0.158cm 3/g，占总孔体积的100％。通过测定该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线(图2-10)，发现该复合材料在3.77nm和13.32nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为31.2％。
图2-11是实施例2-4所制备的前躯体的XRD图，说明合成的前躯体材料为无定形材料。图2-12是实施例2-4制备的碳包覆镍钴纳米复合材料的TEM图，表明该材料含有以金属镍或钴纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图2-13)存在对应于fcc-Ni和钴的衍射峰(2θ角为44.5°、51.7°和76.2°)，说明该材料包括具有一定石墨化程度的碳、以面心立方结构存在的镍和/或钴。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为24.4nm。 该材料的比表面积为182m 2/g，孔体积为0.256cm 3/g，其中介孔体积为0.256cm 3/g，占总孔体积的100％。通过测定该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线(图2-14)，发现该复合材料在3.7nm和6.34nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为38.4％。
图2-15是实施例2-5制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图2-16)存在对应于石墨碳的衍射峰(2θ角为25.8°)、对应于fcc-Ni的衍射峰(44.4°、51.9°和76.2°)和对应于hcp-Ni的衍射峰(2θ角为42.1°、44.4°、47.42°和62.63°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构和密排立方结构存在的镍。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为7.6nm。经过酸洗实验，该材料的酸洗损失率为31.2％。
图2-17是实施例2-6制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图2-18)存在对应于fcc-Ni的衍射峰(44.45°、51.8°和76.3°)和对应于hcp-Ni的衍射峰(2θ角为41.6°、44.4°、47.6°和62.6°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构和密排六方结构存在的镍。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为28.4nm。经过酸洗实验，该材料的酸洗损失率为25.4％。
图2-19是实施例2-7制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图(图2-20)中，存在对应于石墨碳的衍射峰(2θ角为26.04°)和对应于fcc-Ni的衍射峰(44.6°、51.8°和76.3°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为4.7nm。经过酸洗实验，该材料的酸洗损失率为16.7％。
图2-21是实施例2-8制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图2-22)存在对应于fcc-Ni的衍射峰(44.4°、51.9°和76.3°)和对应于hcp-Ni的衍射峰(2θ角为41.7°、 44.4°、47.5°和62.6°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构和密排六方结构存在的镍。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为32.4nm。BET测试表明，该材料的比表面积为228m 2/g，孔体积为0.293cm 3/g，其中介孔体积为0.289cm 3/g，占总孔体积的98.6％。通过测定该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线(图2-23)，发现该复合材料在3.75nm处存在一个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为39.8％。
图2-24是实施例2-9制备的碳包覆镍纳米复合材料的TEM图，表明该材料含有以金属镍纳米颗粒为核，具有一定石墨化程度的碳为壳的核壳结构。在该材料的XRD衍射图中(图2-25)存在对应于石墨碳的衍射峰(2θ角为25.9°)和对应于fcc-Ni的衍射峰(44.5°、51.7°和76.3°)，说明该材料包括具有一定石墨化程度的碳和以面心立方结构存在的镍。由谢乐公式计算得到该碳包覆纳米粒子的平均粒径为7.6nm。BET测试表明，该材料的比表面积为232m 2/g，孔体积为0.313cm 3/g，其中介孔体积为0.313cm 3/g，占总孔体积的100％。通过测定该材料的N 2吸附-脱附等温曲线及BJH孔径分布曲线(图2-26)，发现该复合材料在4.02nm和6.30nm处存在两个介孔分布峰。经过酸洗实验，该材料的酸洗损失率为21.7％。
图2-27是实施例2-10所制备的碳包覆镍纳米纳米复合材料的磁性测试的照片，经磁铁吸引后，含碳包覆镍纳米复合材料的悬浮液迅速变清，表明该材料具有强磁性。图2-28是该材料的TEM图，从中可以看出，该材料为含有碳包覆金属核壳结构的纳米复合材料，在镍纳米颗粒的外层包裹着具有一定石墨化程度的碳层，形成完整的核壳结构。该碳包覆镍纳米复合材料的X射线衍射谱图如图2-29所示，从中可以看出，在该材料的衍射图中存在对应于石墨碳的衍射峰(2θ角为25.97°)和对应于fcc Ni的衍射峰(2θ角为44.47°、51.34°和76.26°)。由谢乐公式计算得到该碳包覆镍纳米粒子的平均粒径为8.1nm。BET测试表明，该材料的比表面积为200m 2/g，孔体积为0.204cm 3/g，其中介孔体积为0.0201cm 3/g，占总孔体积的98.6％。图2-30为该材料的BJH孔径分布曲线，从中可以看出，所述复合材料在3.79nm和10.01nm处存在两个介孔分布峰。
对比例2-1制备的碳包覆镍纳米复合材料经过上述表征测试，表明 该材料形成了以金属镍纳米颗粒为核，碳为壳的核壳结构，粒径为28.2nm。在该材料的XRD衍射图中存在对应于fcc-Ni的衍射峰(44.45°、51.32°和76.16°)，说明该材料中镍以面心立方结构存在。经过酸洗实验，该材料的酸洗损失率为64.2％。
比较实施例2-1至2-11和对比例2-1至2-3可以看出，本发明的方法更加简单高效，高温热解前驱体直接由过渡金属盐与多元有机羧酸和含氮化合物在溶剂中直接反应制备，前驱体对原料中过渡金属的原子利用率可达100％，克服了现有技术制备金属有机骨架结构前驱体需要使用高温高压反应釜自组装、大量浪费碳源前驱体、大量使用有机溶剂、提纯步骤繁琐等缺点；并且不需要高分子助剂，简化了反应步骤。
第三部分
实施例3-1
称取2.92g(10mmol)乙二胺四乙酸、1.53g(5mmol)1，3-丙二胺四乙酸和1.85g(20mmol)氢氧化镍，加入120mL去离子水中，在80℃下搅拌得到均相溶液，并继续加热蒸干，将固体研磨后得到前驱体。
将得到的前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量80mL/min，并以2.5℃/min的速率升温至725℃，恒温3.5h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料，编号P1。
将得到的碳包覆镍纳米复合材料P1加入50mL 0.5mol/L的H 2SO 4溶液中，在90℃下搅拌并回流6h，随后将溶液进行抽滤，并用去离子水洗至中性。然后，将粉末置于100℃的烘箱中干燥2h，得到碳包覆镍纳米复合材料，编号P2。
实施例3-2
称取10mmol NiCO 3和10mmol柠檬酸，加入150mL去离子水中，在70℃下搅拌得到均相溶液，并继续加热蒸干，将固体研磨后得到前驱体。
将得到的前驱体置于瓷舟内，然后将瓷舟置于管式炉的恒温区，通入氮气，流量100mL/min，并以5℃/min的速率升温至450℃，恒温 1h后停止加热。在氮气气氛下冷却至室温，得到碳包覆镍纳米复合材料P3。
将得到的碳包覆镍纳米复合材料P3加入60mL 1mol/L的HCl溶液中，在85℃下搅拌并回流4h，随后将溶液进行抽滤，并用去离子水洗至中性。然后，将粉末置于100℃的烘箱中干燥2h，得到碳包覆镍纳米复合材料P4。
所得材料的表征
图3-1是实施例3-1中所得材料P2的XRD图。图3-1中只存在碳材料的衍射峰以及hcp-Ni和fcc-Ni的衍射峰，hcp-Ni在42°和62°的衍射峰近乎消失。图3-2A是实施例3-1中所得材料P2的N 2吸附-脱附等温曲线图，图3-2B是实施例3-1中所得材料P2的孔径分布曲线图。图3-2B显示材料P2的孔径分布在3.7nm处和10.0nm处出现了两个分布峰。材料P2测得的比表面积为253m 2/g，孔体积为0.481cm 3/g，其中介孔体积占总孔体积的比例为99.3％。图3-3是材料P2的SEM和TEM图。从图3-3(a)可以看到该材料整体为无规则块状。从图3-3(b)可以看出镍纳米颗粒均匀分散在碳基材中。从图3-3(c)可以看出明显的石墨壳层与金属内核，直接证明了纳米颗粒的核壳结构。元素分析仪测定材料P2的碳含量为46.91wt％，氢含量为0.42wt％，氮含量为1.54wt％，氧含量为1.83wt％，归一化后镍含量为49.30wt％。按上文“试剂、仪器与测试”部分记载的酸洗损失率测量方法测量，实施例3-1中所得材料P1的酸洗损失率为40％，材料P2的酸洗损失率小于2％，在该测量方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
图3-4是实施例3-2的前驱体材料的热重-差热分析曲线(TG-DTA)图。从图3-4中可以看出，该前驱体在升温过程中存在两个明显的吸热峰，其中在366℃的吸热峰对应于前驱体高温热解碳化及Ni 2+还原成Ni单质的过程，并且在400℃之后前驱体的质量相对稳定。图3-5是实施例3-2中所得材料P4的XRD图。从图3-5中可以看出碳材料的衍射峰以及fcc-Ni的衍射峰。根据谢乐公式计算，镍纳米颗粒的平均粒径为8.6nm。图3-6是实施例3-2中所得材料P4的XPS图，从中可以明显看出C、O、Ni的电子结合能峰。图3-7A是实施例3-2中所得材料 P4的N 2吸附-脱附等温曲线图，图3-7B是实施例3-2中所得材料P4的孔径分布图。从图3-7A中可以看出材料P4在p/p 0＝0.4-1.0之间出现明显的滞后环。从图3-7B中可以看出，材料P4的孔径分布在3.5nm处和6.9nm处出现了两个分布峰。材料P4的比表面积为301m 2/g，孔体积为0.453cm 3/g，其中介孔体积占总孔体积的比例为100％。元素分析仪测定材料P4的碳含量为39.80wt％，氢含量为1.01wt％，氧含量为2.50wt％，归一化后镍含量为56.69wt％。按上文“试剂、仪器与测试”部分记载的酸洗损失率测量方法测量，实施例3-2中所得材料P3的酸洗损失率为43％，材料P4的酸洗损失率小于1％。在该测量方法的基础上，继续增加酸洗时间，酸洗损失率基本保持不变。
应用实施例
实施例4-1
将第一部分制备实施例和对比例中所制备的材料和市售氧化亚镍(NiO)(分析纯，批号：20160803，国药集团化学试剂公司)分别作为催化剂用于工业正丁烷氧化制备顺酐生产工艺所产生的废气中丁烷的完全催化消除实验。进行相应催化剂的丁烷消除率评价，在相同条件下，丁烷消除率越高，说明催化剂活性越高。具体评价方法为：
将收集的含丁烷的顺酐生产工艺废气送入装载有催化剂的固定床反应器中与该催化剂接触并进行催化氧化反应，得到的反应产物进行气相色谱分析，并计算丁烷的消除率：
丁烷消除率＝100％-反应产物中丁烷体积/顺酐生产工艺废气中丁烷体积×100％。
所述顺酐生产工艺废气含约1体积％丁烷，其余为空气以及极少量的一氧化碳和二氧化碳，反应空速为5000毫升工业废气/(小时·克催化剂)，评价时间为5小时，具体反应温度和丁烷消除率数据见表4-1。
表4-1 实施例4-1的反应温度和丁烷消除率数据
Figure PCTCN2018097303-appb-000003
由表4-1可以看出，本发明实施例1-1至1-3、1-6和1-8制备的纳 米复合材料在400℃以下即可完全催化氧化丁烷成CO 2，其中实施例1-3所得的碳包覆钴纳米复合材料和实施例1-6所得的碳包覆镍钴纳米复合材料在350℃下即可使含1体积％丁烷的顺酐生产工艺废气中的丁烷消除率达到100％。可见，本发明的纳米复合材料，特别是未经酸处理步骤的纳米复合材料用作催化氧化催化剂时，可表现出良好的低温活性，这对于通过催化燃烧彻底去除工业废气中的挥发性有机化合物具有重要意义。石墨化碳层在反应条件下起到了分隔稳定金属活性中心的作用，有效阻止了活性中心的聚集失活。本发明提供的纳米复合材料应用于顺酐生产工艺废气处理时可以大幅降低反应温度，降低能耗。
实施例4-2
将第二部分制备实施例及对比例1-4中制备的纳米复合材料和市售氧化亚镍(NiO)(分析纯，批号：20160803，国药集团化学试剂公司)分别作为催化剂用于工业正丁烷氧化制备顺酐生产工艺所产生的废气中丁烷的完全催化消除实验。进行相应催化剂的丁烷消除率评价，具体评价方法为：
将收集的含丁烷的顺酐生产工艺废气送入装载有催化剂的固定床反应器中与该催化剂接触并进行催化氧化反应，得到的反应产物进行气相色谱分析，并计算丁烷的消除率：
丁烷消除率＝100％-反应产物中丁烷体积/顺酐生产工艺废气中丁烷体积×100％。
所述顺酐生产工艺废气含约1体积％丁烷，其余为空气以及极少量的一氧化碳和二氧化碳，反应空速为5000毫升工业废气/(小时·克催化剂)，评价时间为5小时，具体反应温度和丁烷消除率数据见表4-2。
表4-2 实施例4-2的反应温度和丁烷消除率数据
Figure PCTCN2018097303-appb-000004
* 实施例2-1所得材料经酸处理后得到的材料，酸处理的条件为：称取2.0g制备实施例2-1所得的纳米碳复合材料，用1M的硫酸80mL在90℃下洗涤8h，然后用去离子水洗涤至中性，120℃烘干。
由表4-2可以看出，本发明实施例2-1至2-4制备的纳米复合材料在350℃下即可使含1体积％丁烷的顺酐生产工艺废气中的丁烷消除率 达到100％，所需温度明显低于对比例1-4的复合材料和市售氧化亚镍。可见，本发明的纳米复合材料，特别是未经酸处理步骤的纳米复合材料用作催化氧化催化剂时，可表现出良好的低温活性，这对于通过催化燃烧彻底去除工业废气中的挥发性有机化合物具有重要意义。石墨化碳层在反应条件下起到了分隔稳定金属活性中心的作用，有效阻止了活性中心的聚集失活。本发明提供的纳米复合材料应用于顺酐生产工艺废气处理时可以大幅降低反应温度，保持催化剂的稳定性，降低能耗。
实施例4-3
将实施例1-1制备的纳米复合材料作为催化剂用于硝基苯加氢制备苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2.7mmol硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。硝基苯的转化率为100％，苯胺的选择性为99.9％。
实施例4-4
将实施例1-10制备的纳米复合材料作为催化剂用于硝基苯加氢制备苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2.7mmol硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。硝基苯的转化率为100％，苯胺的选择性为99.9％。
实施例4-5
将实施例1-1制备的纳米复合材料作为催化剂用于对氯硝基苯加氢制备对氯苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、3mmol对氯硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为0.5MPa， 搅拌升温，升温至120℃，反应0.5小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对氯硝基苯的转化率为100％，对氯苯胺的选择性为99.5％。
实施例4-6
将实施例1-10制备的纳米复合材料作为催化剂用于对氯硝基苯加氢制备对氯苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2mmol对氯硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对氯硝基苯的转化率为100％，对氯苯胺的选择性为99.9％。
实施例4-7
将实施例2-1制备的纳米复合材料作为催化剂用于硝基苯加氢制备苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2.7mmol硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。硝基苯的转化率为100％，苯胺的选择性为99.9％。
实施例4-8
将实施例2-1制备的纳米复合材料作为催化剂用于对氯硝基苯加氢制备对氯苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、4.2mmol对氯硝基苯，50mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为0.5MPa，搅拌升温，升温至120℃，反应0.5小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对氯硝基苯的转化率为100％，对氯苯胺的选择性为99.2％。
实施例4-9
将实施例1-1制备的纳米复合材料作为催化剂用于苯酚加氢制备环己醇的反应，具体的实验步骤为：
将0.1g复合材料、5.5mmol苯酚，50mL水加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至250℃，反应6小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯酚的转化率为100％，环己醇的选择性为97.8％。
实施例4-10
将实施例1-10制备的纳米复合材料作为催化剂用于苯酚加氢制备环己醇的反应，具体的实验步骤为：
将0.2g复合材料、7mmol苯酚，50mL水加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯酚的转化率为100％，环己醇的选择性为99.8％。
实施例4-11
将实施例1-1制备的纳米复合材料作为催化剂用于丙酮加氢制备异丙醇的反应，具体的实验步骤为：
将0.1g复合材料、34mmol丙酮，100mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为6MPa，搅拌升温，升温至100℃，反应12小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丙酮的转化率为100％，异丙醇的选择性为97.3％。
实施例4-12
将实施例1-10制备的纳米复合材料作为催化剂用于丙酮加氢制备异丙醇的反应，具体的实验步骤为：
将0.2g复合材料、11.6mmol丙酮，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时，停止加热。降至室温，排压，开反应釜取产物进行气相色谱分析。丙酮的转化率为96.4％，异丙醇的选择性为99.9％。
实施例4-13
将实施例1-1制备的纳米复合材料作为催化剂用于对硝基苯酚加氢制备对氨基苯酚的反应，具体的实验步骤为：
将0.1g复合材料、3.5mmol对硝基苯酚，50mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为0.5MPa，搅拌升温，升温至120℃，反应1小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯酚的转化率为100％，对氨基苯酚的选择性为99.1％。
实施例4-14
将实施例1-10制备的纳米复合材料作为催化剂用于对硝基苯酚加氢制备对氨基苯酚的反应，具体的实验步骤为：
将0.2g复合材料、4.8mmol对硝基苯酚，50mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯酚的转化率为100％，对氨基苯酚的选择性为99.8％。
实施例4-15
将实施例1-1制备的纳米复合材料作为催化剂用于对硝基苯甲醚加氢制备对氨基苯甲醚的反应，具体的实验步骤为：
将0.1g复合材料、3.2mmol对硝基苯甲醚，50mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为0.5MPa，搅拌升温，升温至120℃，反应0.5小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯甲醚的转化率为100％，对氨基苯甲醚的选择性为99.2％。
实施例4-16
将实施例1-10制备的纳米复合材料作为催化剂用于对硝基苯甲醚加氢制备对氨基苯甲醚的反应，具体的实验步骤为：
将0.2g复合材料、4.5mmol对硝基苯甲醚，50mL乙醇加入反应 釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1MPa，搅拌升温，升温至80℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯甲醚的转化率为100％，对氨基苯甲醚的选择性为99.7％。
实施例4-17
将实施例1-1制备的纳米复合材料作为催化剂用于烯烃加氢的反应，具体的实验步骤为：
将0.1g复合材料、19mmol苯乙烯，100mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至100℃，反应3小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯乙烯的转化率为100％，乙苯的选择性为98.4％。
实施例4-18
将实施例1-10制备的纳米复合材料作为催化剂用于烯烃加氢的反应，具体的实验步骤为：
将0.2g复合材料、6.4mmol苯乙烯，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1.5MPa，搅拌升温，升温至120℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯乙烯的转化率为100％，乙苯的选择性为99.9％。
实施例4-19
将实施例1-1制备的纳米复合材料作为催化剂用于芳烃加氢制造环己烷衍生物的反应，具体的实验步骤为：
将0.1g复合材料、20mmol甲苯，100mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为6MPa，搅拌升温，升温至200℃，反应10小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。甲苯的转化率为98.3％，甲基环己烷的选择性为97.9％。
实施例4-20
将实施例1-10制备的纳米复合材料作为催化剂用于芳烃加氢制造环己烷衍生物的反应，具体的实验步骤为：
将0.2g复合材料、7.2mmol甲苯，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至200℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。甲苯的转化率为95.3％，甲基环己烷的选择性为99.6％。
实施例4-21
将实施例1-1制备的纳米复合材料作为催化剂用于醛类加氢制造醇类的反应，具体的实验步骤为：
将0.1g复合材料、28mmol丁醛，100mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为5MPa，搅拌升温，升温至80℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丁醛的转化率为100％，正丁醇的选择性为99.6％。
实施例4-22
将实施例1-10制备的纳米复合材料作为催化剂用于醛类加氢制造醇类的反应，具体的实验步骤为：
将0.2g复合材料、9.2mmol丁醛，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丁醛的转化率为97.5％，正丁醇的选择性为99.9％。
实施例4-23
将实施例2-10制备的纳米复合材料作为催化剂用于硝基苯加氢制备苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2.7mmol硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌 升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。硝基苯的转化率为100％，苯胺的选择性为99.9％。
实施例4-24
将实施例2-10制备的纳米复合材料作为催化剂用于对氯硝基苯加氢制备对氯苯胺的反应，具体的实验步骤为：
将0.1g纳米复合材料、2.1mmol对氯硝基苯，30mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对氯硝基苯的转化率为100％，对氯苯胺的选择性为99.9％。
实施例4-25
将实施例2-1制备的纳米复合材料作为催化剂用于醛类加氢制造醇类的反应，具体的实验步骤为：
将0.1g复合材料、4.6mmol丁醛，30mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丁醛的转化率为99.1％，正丁醇的选择性为99.4％。
实施例4-26
将实施例2-10制备的纳米复合材料作为催化剂用于醛类加氢制造醇类的反应，具体的实验步骤为：
将0.2g复合材料、9.2mmol丁醛，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丁醛的转化率为100％，正丁醇的选择性为99.4％。
实施例4-27
将实施例2-1制备的纳米复合材料作为催化剂用于芳烃加氢制造环己烷衍生物的反应，具体的实验步骤为：
将0.1g复合材料、3.6mmol甲苯，30mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至200℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。甲苯的转化率为99.4％，甲基环己烷的选择性为99.6％。
实施例4-28
将实施例2-10制备的纳米复合材料作为催化剂用于芳烃加氢制造环己烷衍生物的反应，具体的实验步骤为：
将0.2g复合材料、7.2mmol甲苯，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至200℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。甲苯的转化率为95.5％，甲基环己烷的选择性为99.3％。
实施例4-29
将实施例2-1制备的纳米复合材料作为催化剂用于苯酚加氢制造环己醇的反应，具体的实验步骤为：
将0.1g复合材料、3.5mmol苯酚，30mL水加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时，停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯酚的转化率为100％，环己醇的选择性为99.8％。
实施例4-30
将实施例2-10制备的纳米复合材料作为催化剂用于苯酚加氢制造环己醇的反应，具体的实验步骤为：
将0.2g复合材料、7mmol苯酚，50mL水加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯酚的转化率为100％，环己醇的选择性为99.6％。
实施例4-31
将实施例2-1制备的纳米复合材料作为催化剂用于对硝基苯酚加氢制造对氨基苯酚的反应，具体的实验步骤为：
将0.1g复合材料、2.4mmol对硝基苯酚，30mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯酚的转化率为100％，对氨基苯酚的选择性为99.9％。
实施例4-32
将实施例2-10制备的纳米复合材料作为催化剂用于对硝基苯酚加氢制造对氨基苯酚的反应，具体的实验步骤为：
将0.2g复合材料、4.8mmol对硝基苯酚，50mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1MPa，搅拌升温，升温至60℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯酚的转化率为100％，对氨基苯酚的选择性为99.8％。
实施例4-33
将实施例2-1制备的纳米复合材料作为催化剂用于对硝基苯甲醚加氢制造对氨基苯甲醚的反应，具体的实验步骤为：
将0.1g复合材料、2.2mmol对硝基苯甲醚，30mL乙醇加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1MPa，搅拌升温，升温至100℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯甲醚的转化率为100％，对氨基苯甲醚的选择性为99.9％。
实施例4-34
将实施例2-10制备的纳米复合材料作为催化剂用于对硝基苯甲醚加氢制造对氨基苯甲醚的反应，具体的实验步骤为：
将0.2g复合材料、4.5mmol对硝基苯甲醚，50mL乙醇加入反应 釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1.5MPa，搅拌升温，升温至80℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对硝基苯甲醚的转化率为100％，对氨基苯甲醚的选择性为99.9％。
实施例4-35
将实施例2-1制备的纳米复合材料作为催化剂用于酮类加氢制造醇类的反应，具体的实验步骤为：
将0.1g复合材料、5.8mmol丙酮，30mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丙酮的转化率为99.1％，异丙醇的选择性为99.9％。
实施例4-36
将实施例2-10制备的纳米复合材料作为催化剂用于酮类加氢制造醇类的反应，具体的实验步骤为：
将0.2g复合材料、11.6mmol丙酮，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为3MPa，搅拌升温，升温至150℃，反应8小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。丙酮的转化率为97.9％，异丙醇的选择性为99.5％。
实施例4-37
将实施例2-1制备的纳米复合材料作为催化剂用于烯烃加氢反应，具体的实验步骤为：
将0.1g复合材料、3.2mmol苯乙烯，30mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1.5MPa，搅拌升温，升温至120℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯乙烯的转化率为100％，乙苯的选择性为99.8％。
实施例4-38
将实施例2-10制备的纳米复合材料作为催化剂用于烯烃加氢反应，具体的实验步骤为：
将0.2g复合材料、6.4mmol苯乙烯，50mL环己烷加入反应釜中，通H 2置换反应釜3次后，通H 2使反应釜内压力为1.5MPa，搅拌升温，升温至120℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。苯乙烯的转化率为100％，乙苯的选择性为99.6％。
实施例4-39
将实施例3-1制备的纳米复合材料P2作为催化剂用于对氯硝基苯加氢制备对氯苯胺的反应，具体的实验步骤为：
将3g复合材料、10g对氯硝基苯，200mL无水乙醇加入反应釜中，通H 2置换反应釜3次，通H 2使反应釜内压力为2MPa，搅拌升温，升温至120℃，反应2小时。停止加热，降至室温，排压，开反应釜取产物进行气相色谱分析。对氯硝基苯的转化率为100％，对氯苯胺的选择性为98.5％。
在上文的说明书中，已经参照特定的实施方式描述了本发明的构思。然而，本领域技术人员可以理解，在不脱离所附的权利要求中限定的本发明范围的情况下可以做出各种修改和变更。因此，说明书和附图应认为是说明性的，而不是限制性的，并且所有这类修改和变更应当涵盖在本发明的范围之内。

Claims (27)

  1. 一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料，优选为具有两个或两个以上介孔分布峰的多孔材料。
  2. 根据权利要求1所述的纳米复合材料，其中所述纳米复合材料的酸洗损失率≤40％，优选≤30％，更优选≤10％。
  3. 一种包含碳包覆过渡金属颗粒的纳米复合材料，所述碳包覆过渡金属颗粒具有核壳结构，壳层为掺杂氧和/或氮的石墨化碳层，内核为过渡金属纳米颗粒，其中所述纳米复合材料的酸洗损失率≤10％。
  4. 根据权利要求3所述的纳米复合材料，其中所述纳米复合材料为具有至少一个介孔分布峰的多孔材料，优选为具有两个或两个以上介孔分布峰的多孔材料。
  5. 根据权利要求1-4中任一项所述的纳米复合材料，还包含无定型碳基材，所述碳包覆过渡金属颗粒分散在所述无定型碳基材中；优选地，所述纳米复合材料由无定型碳基材和分散在其中的所述碳包覆过渡金属颗粒组成。
  6. 根据权利要求1-5中任一项所述的纳米复合材料，其中所述纳米复合材料的介孔体积占总孔体积的比例大于约50％，优选大于约80％，更优选大于约90％，特别优选大于约95％；优选地，所述纳米复合材料的介孔体积为约0.05-1.25cm 3/g。
  7. 根据权利要求1或2所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，碳含量为约10.0％-60.0％，过渡金属含量为约30.0％-85.0％。
  8. 根据权利要求3或4所述的纳米复合材料，其中以质量百分比计，所述纳米复合材料中，碳含量为约15.0％-60.0％，过渡金属含量为约30.0％-80.0％。
  9. 根据权利要求1-8中任一项所述的纳米复合材料，其中所述碳包覆过渡金属颗粒的壳层为掺杂氧的石墨化碳层，并且以质量百分比计，所述纳米复合材料中的氧含量小于约15.0％，优选为约1.0％-10.0％，更优选为约0.2％-5.0％；或者，所述碳包覆过渡金属颗粒的壳层为掺杂 氧和氮的石墨化碳层，并且以质量百分比计，所述纳米复合材料中氮和氧的总含量小于约15.0％，优选为约0.2％-12.0％，更优选为约0.5％-10.0％，其中氮含量优选为约0.1-10％，更优选为约1-5％。
  10. 根据权利要求1-9中任一项所述的纳米复合材料，其中所述石墨化碳层的厚度为约0.3-6nm，优选为约0.3-3nm。
  11. 根据权利要求1-10中任一项所述的纳米复合材料，其中所述核壳结构的粒径为约1-200nm，优选为约3-100nm，更优选为约4-50nm。
  12. 根据权利要求1-11中任一项所述的纳米复合材料，其中所述过渡金属选自铁、钴、镍、铜和锌中的一种或多种。
  13. 根据权利要求1-12中任一项所述的纳米复合材料，其中所述碳包覆过渡金属颗粒的壳层为掺杂氧和氮的石墨化碳层，且所述过渡金属纳米颗粒的晶格结构为面心立方晶格结构和/或密排六方晶格结构。
  14. 一种制备包含碳包覆过渡金属颗粒的纳米复合材料的方法，包括如下步骤：
    i)将包含过渡金属源和多元有机羧酸的混合物与溶剂混合形成均相溶液；
    ii)除去所述均相溶液中的溶剂，从而形成前驱体；
    iii)在惰性保护气氛或还原气氛下将所述前驱体高温热解；以及
    iv)任选地，用非氧化性强酸对步骤iii)的热解产物进行处理。
  15. 根据权利要求14所述的方法，其中步骤i)中所用的所述混合物进一步包含不同于所述多元有机羧酸的含氮有机化合物和/或含氧有机化合物，以及任选的其它有机化合物。
  16. 根据权利要求15所述的方法，其中所述含氮有机化合物选自尿素、三聚氰胺、二氰二胺、六亚甲基四胺和氨基酸中的一种或多种，所述含氧有机化合物选自多元醇和有机羧酸，如乳酸。
  17. 根据权利要求14-16中任一项所述的方法，其中所述过渡金属选自铁、钴、镍、铜和锌中的一种或多种。
  18. 根据权利要求14-17中任一项所述的方法，其中所述过渡金属源选自过渡金属的有机酸盐、碳酸盐、碱式碳酸盐、氧化物和氢氧化物中的一种或多种；优选地，所述过渡金属的有机酸盐为所述过渡金属的不含杂原子的有机羧酸盐，例如醋酸盐。
  19. 根据权利要求14-18中任一项所述的方法，其中所述多元有机羧酸选自柠檬酸、顺丁烯二酸、均苯三甲酸、对苯二甲酸、苹果酸、EDTA和吡啶二羧酸中的一种或多种。
  20. 根据权利要求14所述的方法，其中过渡金属源和多元有机羧酸的质量比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.8-3。
  21. 根据权利要求15或16所述的方法，其中过渡金属源、多元有机羧酸和含氮有机化合物的质量比为约1∶0.1-100∶0.1-100，优选为约1∶0.5-5∶0.5-5，更优选为约1∶0.8-2∶1-2。
  22. 根据权利要求14-21中任一项所述的方法，其中步骤i)所用的溶剂选自水、甲醇、乙醇、正丙醇和异丙醇中的一种或多种，优选选自水、乙醇或其组合，最优选为水。
  23. 根据权利要求14-22中任一项所述的方法，其中在步骤iii)中，所述惰性保护气氛为氮气或氩气，所述还原气氛为惰性气体与氢气的混合气体；所述高温热解以约0.5-30℃/min速率升温至恒温段，在恒温段保持恒温时间为约20-600min，恒温段温度为约400-800℃；优选地，升温速率为约1-10℃/min，在恒温段保持恒温时间为约60-480min，恒温段温度为约500-800℃。
  24. 根据权利要求14-23中任一项所述的方法，其中步骤iv)中所用的非氧化性强酸选自氢氟酸、盐酸、硝酸和硫酸中的一种或多种，优选盐酸和/或硫酸。
  25. 按照权利要求14-24中任一项所述方法制备得到的包含碳包覆过渡金属颗粒的纳米复合材料。
  26. 根据权利要求1-13和25中任一项所述的纳米复合材料作为催化剂在处理挥发性有机化合物中的应用，包括：使所述挥发性有机化合物与所述纳米复合材料接触进行催化氧化反应。
  27. 根据权利要求1-13和25中任一项所述的纳米复合材料作为催化剂在加氢还原反应中的应用，优选地所述加氢还原反应选自对氯硝基苯加氢制造对氯苯胺的反应、硝基苯加氢制造苯胺的反应、硝基苯酚加氢制造氨基苯酚的反应、对硝基苯甲醚加氢制造对氨基苯甲醚的反应、苯酚加氢制造环己醇的反应、烯烃加氢的反应、芳烃加氢制造环己烷衍生物的反应、醛加氢制造醇的反应和酮加氢制造醇的反应。
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