CN111468126A - Carbon-coated transition metal nanocomposite containing alkali metal, and preparation method and application thereof - Google Patents
Carbon-coated transition metal nanocomposite containing alkali metal, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111468126A CN111468126A CN201910063359.6A CN201910063359A CN111468126A CN 111468126 A CN111468126 A CN 111468126A CN 201910063359 A CN201910063359 A CN 201910063359A CN 111468126 A CN111468126 A CN 111468126A
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- Prior art keywords
- nanocomposite
- alkali metal
- transition metal
- carbon
- constant temperature
- Prior art date
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 101
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 74
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 70
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- 150000003624 transition metals Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
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- 125000004429 atom Chemical group 0.000 claims description 4
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- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052730 francium Inorganic materials 0.000 claims description 3
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
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Images
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
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Abstract
The invention provides an alkali metal-containing carbon-coated transition metal nanocomposite and a preparation method and application thereof. The alkali metal of the shell layer of the nano composite material and the transition metal of the inner core act synergistically, so that the catalytic performance is improved. The nano composite material has good repeatability, high activity and high selectivity when being used as a catalyst, and can be applied to various catalytic reactions, such as catalytic oxidation reaction, catalytic hydrogenation reaction and the like.
Description
Technical Field
The invention relates to the field of carbon-coated metal composite materials, in particular to a carbon-coated transition metal nanocomposite containing alkali metal, and a preparation method and application thereof.
Background
It has been found that nanocarbon catalysts, such as carbon fibers, nanodiamonds, carbon nanotubes, and (oxidized) graphene, are catalytically active for a series of reactions, such as catalytic direct dehydrogenation, oxidative dehydrogenation, halogenation, hydroxylation, alkylation of hydrocarbons, and liquid-phase oxidation and condensation reactions of aldehydes and ketones. The active sites of the nanocarbon catalyst are mainly structural defects and heteroatom functional groups of the carbon material, so in order to improve the catalytic activity of the nanocarbon catalyst, the number of the structural defects and the number of the heteroatom functional groups need to be increased, but the stability of the material is reduced.
Transition metal nano materials are widely concerned due to excellent optical, electrical, magnetic and catalytic properties, but because of high activity of transition metal nano particles, the transition metal nano particles are easy to agglomerate or be oxidized and even spontaneously combust in the air, and the properties and the application of the materials are greatly influenced. Transition metal nanomaterials have high catalytic activity but poor stability, while nanocarbon materials have good chemical stability but need further improvement in catalytic activity, and if the two are combined in a proper manner, a new synergistic effect may be generated, so that they exhibit new unique properties.
At present, relevant documents for coating transition metals by carbon materials are reported, but various problems still exist in the prior materials in practical application, such as harsh manufacturing conditions, complex process, low coating rate, and not tight coating, the prior materials need to be treated by nitric acid when oxygen-containing groups are introduced, the carbon coating layer is easy to damage, adverse effects are caused to metal cores, and the like, and the prior materials cannot be suitable for industrial production and application. For example, a method of pyrolyzing a metal-organic framework compound (MOF) as a precursor, which requires a crystalline solid Material (MOF) having a periodic structure to be prepared in a solvent at high temperature and high pressure, generally has strict conditions for preparing MOFs, requires expensive ligands, and is difficult to mass-produce; in addition, the composite material prepared by the method has an imprecise coating of the metal particles. Also, for example, CN 105032424a is a catalyst for selective hydrogenation of aromatic nitro compounds, the method for coating metal particles in this document is pechini method (sol-gel method), which also requires preparation of solid coordination polymers in solvents, similar to MOF method, and the method also produces composite materials with tight coating of metal particles.
The mesoporous material generally has a large specific surface area and a relatively regular pore channel structure, so that the mesoporous material can play a better role in separation, adsorption and catalytic reaction of macromolecules and can be a microreactor for limited-domain catalysis. Due to the characteristics of high hydrothermal stability, strong hydrophobicity, organophilic property and the like, the mesoporous carbon material has unique advantages in reactions such as hydrogenation, oxidation, decomposition and the like. If the mesoporous structure can be manufactured in the carbon-coated transition metal material, the mass transfer efficiency can be obviously improved, and the service performance can be improved. At present, the preparation methods of mesoporous carbon materials mainly comprise a catalytic activation method, an organogel carbonization method and a template method, but the preparation processes of the methods are still too complex.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a carbon-coated transition metal nanocomposite containing alkali metal, a preparation method and application thereof. Furthermore, the nano composite material of the invention also has abundant mesoporous structure. The invention also provides application of the material in treating Volatile Organic Compounds (VOCs) and application in catalytic hydrogenation reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides an alkali metal-containing carbon-coated transition metal nanocomposite, which includes a core-shell structure having a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing an alkali metal and oxygen, and the inner core is a transition metal nanoparticle.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having two or more mesopore distribution peaks.
According to one embodiment of the present invention, the proportion of the mesopore volume in the mesoporous material is greater than 50%, preferably greater than 80%, of the total pore volume.
According to an embodiment of the present invention, wherein the alkali metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 3 at%, in atomic percent; the carbon content is 80at percent to 95at percent, preferably 84at percent to 92at percent; the content of the transition metal is 0.1at percent to 10at percent, preferably 1at percent to 8at percent; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr), and the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn).
The second aspect of the present invention also provides a method for preparing the above nanocomposite, comprising:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with the solution containing alkali metal, and then drying;
and (3) placing the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated transition metal nanocomposite containing the alkali metal.
According to an embodiment of the present invention, wherein the transition metal salt is selected from one or more of organic acid salt, carbonate and basic carbonate of transition metal, the organic acid salt of transition metal is preferably organic carboxylate of transition metal without heteroatom, more preferably acetate of transition metal without heteroatom, wherein the heteroatom refers to metal atom other than the transition metal.
According to one embodiment of the invention, wherein the polybasic organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA) and dipicolinic acid.
According to an embodiment of the present invention, the mass ratio of the transition metal salt to the polybasic organic carboxylic acid is 1:0.1 to 10, preferably 1:0.5 to 5, and more preferably 1:0.8 to 3.
According to one embodiment of the invention, wherein the solvent is water and/or ethanol.
According to an embodiment of the present invention, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of inert gas and hydrogen.
According to one embodiment of the invention, the solution containing alkali metal is a solution containing salt and/or alkali of alkali metal, and the mass ratio of the salt and/or alkali of alkali metal to the product after primary pyrolysis is 1: 2-100.
According to one embodiment of the invention, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-500 ℃, and preferably 100-400 ℃; the constant temperature time is 20min to 600min, preferably 30min to 300 min; the inert atmosphere is nitrogen or argon.
A third aspect of the present invention provides the use of the above nanocomposite as a catalyst in the treatment of volatile organic compounds, comprising:
contacting the volatile organic compound with the nanocomposite to perform a catalytic oxidation reaction.
According to an embodiment of the present invention, wherein the volatile organic compound is a volatile organic compound contained in the industrial waste gas.
According to one embodiment of the present invention, the volatile organic compound comprises butane, and the content of the butane in the industrial waste gas is 0.01-2% by volume.
According to one embodiment of the present invention, wherein the catalytic oxidation reaction is carried out at a temperature of 200 ℃ to 500 ℃, preferably at a temperature of 300 ℃ to 400 ℃.
According to one embodiment of the invention, the reaction space velocity of the catalytic oxidation reaction is 2000-5000 ml industrial waste gas/(hour-g of the catalyst).
According to one embodiment of the present invention, the industrial waste gas is industrial waste gas generated by preparing maleic anhydride through n-butane oxidation.
A fourth aspect of the present invention provides the use of the above nanocomposite as a catalyst in a hydrogenation reduction reaction.
According to one embodiment of the invention, the method comprises the step of catalyzing olefin compounds to carry out hydrogenation reduction reaction by using the catalyst under a hydrogen atmosphere.
According to one embodiment of the invention, wherein the olefinic compound is an alkene or a cycloalkene, preferably styrene or cyclohexene.
According to one embodiment of the invention, wherein the catalyst represents 1% to 50%, preferably 5% to 30% of the mass of the olefinic compound.
According to one embodiment of the present invention, the temperature of the hydrogenation reduction reaction is 100 ℃ to 130 ℃, and the pressure of the hydrogen is 1MPa to 3 MPa.
According to an embodiment of the present invention, the olefin compound and the catalyst are mixed in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is one or more selected from the group consisting of alcohols, ethers, alkanes and water.
The invention has the beneficial effects that:
the carbon-coated transition metal nanocomposite disclosed by the invention has the advantages that the carbon material has catalytic activity and can play a role in cooperation with the alkali metal of the shell and the transition metal of the core, so that the catalytic performance is improved. Furthermore, the nano composite material of the invention also has rich mesopores, especially can have a multi-stage mesopore structure, and is favorable for better playing a role in more applications, especially the applications in the field of catalysis.
The transition metal nano-particles of the nano-composite material have high carbon coating rate and adjustable content of doped oxygen, and oxygen elements are not required to be introduced by means of nitric acid treatment and the like, so that the electronic characteristics of the graphitized carbon layer can be adjusted, and the nano-composite material is suitable for catalyzing different reactions.
The nano composite material contains the graphitized carbon layer of alkali metal, the ferromagnetic metal inner core coated by the graphitized carbon layer and rich pore structures, so that the magnetic separation function and the adsorption function are better combined, and the nano composite material is particularly suitable for the field of adsorption separation. The nano composite material can be used as a catalyst for various organic reactions, is favorable for improving the efficiency of catalytic reactions, particularly has excellent catalytic effect and selectivity for catalytic hydrogenation reactions, and has good industrial application prospect. In one illustrative application of the present invention, the nanocomposite of the present invention exhibits good low temperature activity when used as a catalytic oxidation catalyst, which is of great significance for the complete removal of volatile organic compounds from industrial waste gases by catalytic combustion. In another exemplary application of the invention, the nanocomposite of the invention, as a catalyst, exhibits good repeatability, high activity and high selectivity in the catalytic reduction of olefinic compounds to paraffinic compounds, not only the conversion rate of reactants is substantially 100%, but also the product selectivity can reach more than 99%, and simultaneously the catalytic reaction rate is increased.
The carbon-coated transition metal nanocomposite containing the alkali metal is not self-ignited in air, can be stored in air for a long time like common commodities, and does not influence the service performance of the nanocomposite in reactions such as catalytic oxidation, catalytic hydrogenation and the like.
Drawings
In order that the embodiments of the invention may be more readily understood, reference should now be made to the following detailed description taken in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, various components are not necessarily drawn to scale and are provided for illustrative purposes only. In fact, the dimensions of the various elements may be arbitrarily expanded or reduced for clarity of discussion.
FIG. 1 is a photograph showing the magnetic properties of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 1;
FIG. 2 is a TEM image of an alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 1;
FIG. 3 is an XRD pattern of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 1;
FIGS. 4a and 4b show N of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 1, respectively2Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 5 is a TEM image of an alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 2;
FIG. 6 is an XRD pattern of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 2;
FIGS. 7a and 7b show N of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 2, respectively2Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 8 is a TEM image of an alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 3;
FIG. 9 is an XRD pattern of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 3;
FIG. 10 shows the BJH pore size distribution curve of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 3;
FIG. 11 is a TEM image of an alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 4;
FIG. 12 is an XRD pattern of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 4;
FIG. 13 shows the BJH pore size distribution curve of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 4;
FIG. 14 is a TEM image of an alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 5;
FIG. 15 is an XRD pattern of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 5;
FIG. 16 shows the BJH pore size distribution curve of the alkali metal-containing carbon-coated transition metal nanocomposite prepared in example 5;
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The numerical ranges of the invention include the numbers defining the range. The phrase "comprising" is used herein as an open-ended term substantially equivalent to the word "including, but not limited to," and the phrase "comprising" has a corresponding meaning. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a thing" includes more than one such thing, including all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings. Any terms not directly defined herein should be understood to have meanings associated with them as commonly understood in the art of the present invention. The following terms as used throughout this specification should be understood to have the following meanings unless otherwise indicated.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Term(s) for
The term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is about 0.34 nm. The composite material formed after the graphitized carbon layer is coated with the transition metal nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The terms "alkali metal" and "oxygen" in the "graphitized carbon layer containing alkali metal and oxygen" refer to alkali metal elements and oxygen elements, wherein the "alkali metal content" of the nanocomposite refers to the content of the alkali metal elements, and the "oxygen content" refers to the content of the oxygen elements, and specifically means that the alkali metal elements and the oxygen elements exist in various forms in the graphitized carbon layer formed in the preparation process of the carbon-coated nanocomposite, the "alkali metal content" is the total content of all forms of alkali metal elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkali metal content" and "oxygen content" were determined by XPS method.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "olefinic compound" refers to a group of hydrocarbon compounds having a structure in which C ═ C bonds (carbon-carbon double bonds) are present in the molecule.
The term "TOF" is defined herein as the amount of a reactant converted per unit time by a single active metal atom, and TOF measures the rate at which a catalyst catalyzes a reaction and indicates the intrinsic activity of the catalyst.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are Cu target, K α ray (the wavelength lambda is 0.154nm), tube voltage is 40kV, tube current is 200mA, and scanning speed is 10 degrees (2 theta)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV.
The X-ray photoelectron spectrum analyzer (XPS) is an ESCA L ab220i-X L type electron spectrum analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromized A1K α X-rays, the power is 330W, and the basic vacuum is 3 × 10 during analysis and test-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6eV), and the late peak processing software was XPSPEAK.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
In the invention, the composition of the gas is obtained by on-line gas chromatography analysis, and the chromatographic type is as follows: agilent GC7890B, accuracy 10-6. And introducing test gas into the chromatogram from the sample inlet, separating by using a chromatographic column, and calculating the percentage of each gas component by integrating each chromatographic peak.
In the invention, after the average particle diameter of the metal nanoparticles is divided into peaks by an XRD (X-ray diffraction) pattern, the average particle diameter is calculated according to the Sherle formula: d ═ k γ/(B cos θ) was calculated. Wherein k is Scherrer constant, k is 0.89; b is half-height width; theta is the diffraction angle, unit radian; gamma is the x-ray wavelength, 0.154054 nm.
The invention provides an alkali metal-containing carbon-coated transition metal nanocomposite, which comprises a core-shell structure with a shell layer and a core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the core is transition metal nanoparticles.
The nanocomposite of the present invention is a composite material composed of a "graphitized carbon layer containing an alkali metal and oxygen", a "transition metal nanoparticle tightly coated with (not in contact with) the graphitized carbon layer", and a "transition metal nanoparticle in contact with and confined to the outside". The surface of the graphitized carbon layer containing oxygen of the nano composite material has rich defect sites, the carbon material has catalytic activity, and the transition metal coated in the graphitized carbon layer has a penetrating effect, so that the electronic state of the alkali metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nano composite material has better catalytic performance.
In some embodiments, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. As known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play better roles in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the batch-produced composite has two distribution peaks in the mesoporous range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the nanocomposite of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively.
In some embodiments, the proportion of mesopore volume in the composite material to the total pore volume is greater than 50%, preferably greater than 80%, according to the nanocomposite material of the present invention. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous volume thereof may be 0.05cm3/g～1.25cm3Per g, also may be 0.30cm3/g～0.50cm3/g。
The nanocomposites according to the invention, in some embodiments, have specific surface areas generally greater than 140m2/g, may be greater than 200m2/g。
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
According to the nanocomposite of the invention, in some embodiments, the carbon layer of the composite is doped with an oxygen element and not with a nitrogen element.
According to the nanocomposite material of the invention, in some embodiments, the carbon layer of the composite material is doped with only oxygen, and is not doped with other elements than hydrogen and oxygen.
The nanocomposite according to the present invention, in some embodiments, has an element content, as determined by XPS method, in atomic percent: alkali metal content 0.1 at% to 3 at%, preferably 0.2 at% to 3 at%; the carbon content is 80 at% to 95 at%, preferably 84 at% to 92 at%; the content of transition metal is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to the nanocomposite material of the present invention, the graphitized carbon layer is doped with oxygen. The oxygen content can be adjusted by additionally introducing an oxygen-containing compound, such as a polyol, during the manufacturing process. The catalytic performance of the graphitized carbon layer can be adjusted by adjusting the oxygen content in the nano composite material, so that the graphitized carbon layer is suitable for catalyzing different reactions. In some embodiments, the oxygen content in the nanocomposite is less than 15.0%, preferably 5% to 12%, by mass.
According to the nanocomposite of the invention, in some embodiments, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm. The particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, and more preferably 4nm to 50 nm.
According to the nanocomposite of the invention, in some embodiments, the one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr) and the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn), preferably one or more of iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with a solution containing the alkali metal, and then carrying out drying treatment; wherein the contacting mode comprises the step of immersing the product after the primary pyrolysis in the alkali metal solution, or the step of placing the product after the primary pyrolysis in the alkali metal solution and stirring. The time for dipping or stirring is not suitable to be too long or too short, preferably between 10min and 300min, the temperature is preferably between 0 ℃ and 100 ℃, and the contact reaction is preferably carried out under the condition of stirring. According to the invention, the product of the primary pyrolysis may or may not be filtered after being contacted with the alkali metal-containing solution, and the obtained product is dried. And (3) placing the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated transition metal nanocomposite containing the alkali metal.
Specifically, the precursor is a water-soluble mixture, which means that a transition metal salt and a polybasic organic carboxylic acid are dissolved in a solvent such as water and/or ethanol to form a homogeneous solution, and then the solvent is directly removed to obtain the precursor containing the transition metal. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be by any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
In some embodiments, the transition metal salt is selected from one or more of organic acid salts, carbonates, and basic carbonates of transition metals, preferably organic acid salts of transition metals that do not contain heteroatoms, more preferably acetates of transition metals that do not contain heteroatoms, where the heteroatoms refer to metal atoms other than the transition metals.
In some embodiments, the poly-organic carboxylic acid includes, but is not limited to, one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid.
In some embodiments, the mass ratio of the transition metal salt to the polybasic organic carboxylic acid is 1: 0.1-10, preferably 1: 0.5-5, and more preferably 1: 0.8-3.
In some embodiments, the method further comprises mixing the transition metal salt, the polybasic organic carboxylic acid and other organic compounds except the two in a solvent such as water, ethanol and the like to form a homogeneous solution, and removing the solvent to obtain the transition metal-containing water-soluble mixture. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the transition metal salt, the poly-organic carboxylic acid and the other organic compound is 1:0.5 to 10:0 to 10, preferably 1:1 to 3:0 to 3.
In some embodiments, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodiments, the alkali metal-containing solution is an alkali metal salt and/or base-containing solution, such as a potassium bicarbonate solution, a potassium hydroxide solution, a sodium carbonate solution, and the like. The mass ratio of the alkali metal salt and/or alkali to the product after primary pyrolysis is 1: 2-100, preferably 1: 2-50, and more preferably 1: 2-20. When the alkali metal-containing salt or alkali is excessive, the core-shell structure of the carbon-coated transition metal is easily broken during the secondary pyrolysis, for example, when the transition metal is nickel, the nickel of the core is exposed to air to be spontaneously ignited.
According to one embodiment of the invention, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-500 ℃, and preferably 100-400 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
The invention also provides the application of the composite material as a catalyst in treating volatile organic compounds, wherein industrial waste gas often contains Volatile Organic Compounds (VOCs), the VOCs generally refer to organic compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of less than 250 ℃ at normal pressure, and the common organic compounds comprise alkanes, aromatic hydrocarbons, ether alcohols, halogenated hydrocarbons and the like. In chemical and petrochemical industries, the generation and emission of VOCs are the most important, and the VOCs are easy to be encountered in life (formaldehyde and the like are generated during decoration). For example, in the production of maleic anhydride from commercial n-butane, the above-mentioned VOCs are produced when the oxygen in the raw material and air is not converted to 100% into the product over the catalyst. VOCs are one of the main causes of photochemical smog, are used as important pollutants for controlling the air quality together with nitrogen oxides, inhalable particles and the like, and have high toxicity, carcinogenic hazards and the like, so that catalytic oxidation materials with excellent performance are urgently needed for treatment.
The method comprises the step of contacting the catalyst with gaseous volatile organic compounds to perform catalytic oxidation reaction, wherein the volatile organic compounds comprise butane, and the butane accounts for 0.01-2% of the industrial waste gas by volume.
In some embodiments, the temperature of the catalytic oxidation reaction is from 200 ℃ to 500 ℃, preferably from 300 ℃ to 400 ℃. The reaction space velocity is 2000-5000 ml industrial waste gas/(hour-g of the catalyst). The composite material of the invention is used as a catalyst to catalyze and oxidize butane components with the content of 0.01-2 volume percent in waste gas generated in a maleic anhydride production process into CO at 350 ℃ under the condition of reducing reaction severity, for example2The elimination rate can reach more than 90 percent by volume, and the butane component can be completely catalyzed and oxidized into CO at 400 DEG C2. Compared with the prior art, the method has the advantages of reducing the reaction temperature, increasing the airspeed and the like, and can obtain good reaction effect.
The invention also provides the application of the nano composite material as a catalyst for catalytic hydrogenation reaction.
In some embodiments, the catalyst is used to catalyze the hydrogenation reduction reaction of olefinic compounds under a hydrogen atmosphere. Wherein the olefinic compound is an alkene or a cycloalkene, preferably styrene or cyclohexene.
In some embodiments, the catalyst comprises 1% to 50%, preferably 5% to 30% of the olefinic compound mass.
In some embodiments, the temperature of the hydrogenation reduction reaction is 100 ℃ to 130 ℃, and the pressure of the hydrogen is 1MPa to 3 MPa.
In some embodiments, the olefin compound and the catalyst are mixed in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is one or more selected from alcohols, ethers, alkanes and water. Such as water, ethanol, tetrahydrofuran, cyclohexane, and the like.
By using the nano composite material as a catalyst to catalyze olefin to carry out catalytic hydrogenation reaction, the reaction conversion rate can basically reach 100%, the product selectivity can basically reach more than 99%, and good repeatability, high activity and high selectivity are represented.
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
Example 1
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30m L of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) 2g of the material obtained in step (2) were weighed, 4ml of an aqueous solution containing 0.1538g of potassium hydrogencarbonate was added, and after stirring at room temperature for 24 hours, the product was dried at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 400 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite containing potassium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 84.9 at%, the nickel content was 6.34 at%, the oxygen content was 8.36 at%, and the potassium content was 0.4 at%.
As shown in fig. 1, the nanocomposite was placed in water as a suspension, a magnet was placed on the outside of the container, and after a period of time the nanocomposite was attracted to one side of the magnet, which was seen to be magnetic. The TEM image of the nanocomposite is shown in fig. 2, and it can be seen that a graphitized carbon layer is wrapped on the outer layer of the nickel nanoparticle to form a complete core-shell structure. The X-ray diffraction pattern of this nanocomposite is shown in FIG. 3, and the XRD pattern of this material shows diffraction peaks (2. theta. angle 25.9 ℃) of graphite carbon and diffraction peaks (2. theta. angles 44.5 °, 51.7 ° and 76.4 ℃) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 5.2nm by the scherrer equation.
The BET test shows that the specific surface area of the nano composite material is 151m2Per g, pore volume 0.365cm3Per g, wherein>The mesoporous volume of 2nm is 0.365cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 4a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 4b, which is a BJH pore size distribution curve of the nanocomposite, and it can be seen that the composite has two mesopore distribution peaks at 3.77nm and 12.19 nm.
Example 2
(1) 10g of nickel acetate and 20g of citric acid were weighed into a beaker containing 50m L of deionized water, stirred at 80 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (2) placing the solid obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 15M L1M potassium hydroxide (KOH) aqueous solution, stirring for 24h at room temperature, filtering, and drying the product at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite containing potassium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: 91.55 at% of carbon, 1.86 at% of nickel, 6.41 at% of oxygen and 0.18 at% of potassium.
From the TEM image (fig. 5) of this material it can be seen that: the outer layer of the nickel nano-particles is wrapped with a graphitized carbon layer to form a complete core-shell structure. Fig. 6 shows an X-ray diffraction pattern of the nanocomposite material in which XRD patterns showed the presence of diffraction peaks corresponding to carbon (2 θ angle of 25.9 °) and fcc Ni (2 θ angles of 44.5 °, 51.7 ° and 76.4 °), and the average particle diameter of the carbon-coated nickel nanoparticles was 31.3nm as calculated from scherrer's equation.
The BET test shows that the specific surface area of the material is 168m2Per g, pore volume 0.342cm3Per g, wherein>Pore volume of 0.32cm at 2nm3(ii) in terms of/g, 93.6% of the total pore volume. FIGS. 7a and 7b show N of the nanocomposite, respectively2According to the adsorption-desorption isotherm and the BJH pore size distribution curve, two mesoporous distribution peaks exist at 3.38nm and 8.94nm of the composite material.
Example 3
(1) Weighing 10g of nickel acetate and 10g of terephthalic acid, adding the nickel acetate and the terephthalic acid into 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (3) placing the solid precursor in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the material containing the carbon-coated nickel.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of L aqueous solution containing 0.2765g of sodium carbonate, soaking at room temperature for 24h, and drying the product at 120 ℃.
(4) And (3) placing the material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nano composite material containing sodium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content is 82.27 at%; the nickel content was 4.34 at%, the oxygen content was 11.69 at%, and the sodium content was 1.7 at%.
FIG. 8 TEM image of the nanocomposite, it can be seen that: the carbon-coated nickel-based composite material comprises a core-shell structure of carbon-coated nickel, a graphitized carbon layer is used as a shell, and nano metal nickel is used as a core. Fig. 9 is an XRD pattern of the nanocomposite, which shows the presence of diffraction peaks corresponding to carbon (2 theta angle of 25.9 °) and fcc Ni (2 theta angles of 44.5 °, 51.7 ° and 76.4 °). The average particle size of the carbon-coated nickel nanoparticles was calculated to be 27.6nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 164m2Per g, pore volume 0.33cm3Per g, wherein>Pore volume of 0.33cm at 2nm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 10 shows N of the nanocomposite2The adsorption-desorption isotherm and the BJH pore size distribution curve show that two mesoporous distribution peaks exist at 4.01nm and 18.9nm of the BJH pore size distribution curve of the material.
Example 4
(1) Weighing 10g of cobalt acetate and 30g of citric acid, adding the mixture into a beaker containing 50m L of deionized water, stirring the mixture at 80 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) placing the solid obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated cobalt material.
(3) Weighing 2g of the carbon-coated cobalt material obtained in the step (2), adding 4m of L aqueous solution containing 0.408g of sodium carbonate, soaking at room temperature for 24h, and drying the product at 120 ℃.
(4) And (3) placing the material obtained in the step (3) into a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 300 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the sodium-containing carbon-coated cobalt nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content is 88.93 at%; the cobalt content was 1.24 at%; the oxygen content is 7.03 at%; the sodium content was 2.8 at%.
Fig. 11 is a TEM image of the nanocomposite, which shows that the nanocomposite contains a core-shell structure of carbon-coated cobalt, with a graphitized carbon layer as a shell and nano-metallic cobalt as a core. Fig. 12 is an XRD pattern of the nanocomposite material, in which diffraction peaks corresponding to fcc Co (2 θ angles of 44.5 °, 51.7 °, and 76.4 °) are present in the diffraction pattern of the material. The average particle size of the carbon-coated cobalt nanoparticles is calculated to be 17.5nm by the Sherle formula.
The BET test shows that the specific surface area of the material is 183m2Per g, pore volume 0.37cm3Per g, wherein>Pore volume of 0.37cm at 2nm3(ii) in terms of/g, representing 100% of the total pore volume. Fig. 13 shows the BJH pore size distribution curve of the nanocomposite, and it can be seen that there are two mesopore distribution peaks at 3.03nm and 8.17nm in the BJH pore size distribution curve of the nanocomposite.
Example 5
(1) 5g of nickel acetate, 5g of cobalt acetate and 16.83g of citric acid were weighed into a beaker containing 30m L of deionized water, stirred at 80 ℃ to obtain a homogeneous solution, and continuously heated to dryness to obtain a solid precursor.
(2) And (2) placing the powder obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the material mixed with carbon-coated nickel and carbon-coated cobalt.
(3) 2g of the material obtained in step (2) were weighed, 4m of L aqueous solution containing 0.2213g of sodium nitrate was added, and the mixture was immersed at room temperature for 12 hours, and then the product was dried at 120 ℃.
(4) And (3) placing the material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 400 ℃ at the speed of 8 ℃/min, keeping the temperature for 0.5h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated nickel and/or cobalt nano composite material mixed with sodium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content is 89.71 at%; the cobalt content was 2.12 at%; the nickel content was 1.62 at%; the oxygen content was 5.74 at%; the sodium content was 0.81 at%.
Fig. 14 is a TEM image of the material, and it can be seen from the figure that the material contains a core-shell structure with a graphitized carbon layer as a shell and a nano-metallic nickel and/or a nano-metallic cobalt as a core. Fig. 15 is an XRD pattern of the nanocomposite material, in which diffraction peaks corresponding to carbon (2 θ angle of 25.9 °) and fcc Ni and/or Co (2 θ angles of 44.5 °, 51.7 ° and 76.4 °) were present. The average particle size of the nanoparticles was calculated to be 18.5nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 172m2Per g, pore volume 0.192cm3Per g, wherein>Pore volume at 2nm of 0.189cm3In terms of/g, 98.4% of the total pore volume. Fig. 16 shows the BJH pore size distribution curve of the nanocomposite, which has two mesopore distribution peaks at 3.40nm and 10.22 nm.
Comparative example 1
The same as example 1, except that 1.5g of potassium bicarbonate was added in step (3), and the resulting carbon-coated nickel composite material was impregnated and calcined at 400 ℃ to make it flammable in air.
Comparative example 2
The same as example 1, except that steps (3) and (4) were not performed, the carbon-coated nickel nanocomposite material containing no alkali metal was obtained.
Test example 1
The nanocomposite prepared in examples 1-5 and comparative example 2 was used as a catalyst in a complete catalytic elimination experiment of butane in exhaust gas generated in a production process for preparing maleic anhydride by industrial n-butane oxidation, and the butane elimination rate of the catalytic material was evaluated, wherein under the same conditions, the higher the butane elimination rate, the higher the catalyst activity. The specific evaluation method comprises the following steps:
sending the collected butane-containing maleic anhydride production process waste gas into a fixed bed reactor loaded with a composite material to contact with the composite material serving as a catalyst for catalytic oxidation reaction, carrying out gas chromatography analysis on the obtained reaction product, and calculating the butane elimination rate, wherein the butane elimination rate is 100 percent, and the butane volume in the reaction product/the butane volume in the maleic anhydride production process waste gas is × 100 percent.
The waste gas of the maleic anhydride production process contains about 1 volume percent of butane, the balance of air and a very small amount of carbon monoxide and carbon dioxide, the reaction space velocity is 5000 milliliters of industrial waste gas/(hour-gram catalyst), the evaluation time is 5 hours, and the specific reaction temperature and the butane elimination rate data are shown in Table 1.
TABLE 1
As can be seen from Table 1, the alkali metal-containing carbon-coated transition metal nanocomposite prepared by the method of the present invention can completely catalyze the oxidation of butane to CO at 400 ℃2. When the catalyst is used as a catalytic oxidation catalyst, the catalyst shows good low-temperature activity, and has important significance for completely removing volatile organic compounds in industrial waste gas through catalytic combustion. The graphitized carbon layer plays a role in separating and stabilizing the active center of the metal under the reaction condition, and effectively prevents the aggregation and inactivation of the active center. When the catalytic material provided by the invention is applied to the treatment of the waste gas in the maleic anhydride production process, the reaction temperature can be greatly reduced, the energy consumption is reduced, and the catalytic efficiency is further improved after the alkali metal is added, for example, the butane in the waste gas in the maleic anhydride production process containing 1 volume percent of butane in the carbon-coated transition metal composite material with the preferred composition is eliminated at 340 DEG CThe rate can reach 100%.
Test example 2
The nanocomposite prepared in example 1 is used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 1.96g of styrene and 100m of L g of cyclohexane were placed in a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2And (3) controlling the pressure in the reaction kettle to be 3.0MPa, stirring and heating, heating to the preset reaction temperature of 100 ℃, stopping heating after continuously reacting for 3 hours, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out a product ethylbenzene for chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion-amount of reacted reaction mass/amount of added reaction × 100%
The selectivity is × 100% based on the mass of the target product/mass of the reaction product
After analysis, the conversion rate of the obtained styrene is 100%, and the selectivity of the obtained ethylbenzene is 99.0%.
When the reaction proceeded for 300s, a sample was taken and subjected to chromatography to calculate the conversion of the reactant, and TOF of the catalyst was 9.96 × 10, which was obtained by the formula TOF (amount of reacted reactant substance)/(amount of catalytically active metal substance 300s)-3s-1。
Test example 3
The nanocomposite prepared in example 2 is used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 0.33g of styrene and 30m of L m of cyclohexane were added to a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 120 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product ethylbenzene is taken out for chromatographic analysis, and the conversion rate of reactants, the product selectivity and the TOF are respectively calculated by the formula shown in the test example 2, so that the conversion rate of styrene is 100 percent, the selectivity of ethylbenzene is 99.7 percent, and the TOF is 10.1 × 10-3s-1。
Test example 4
The nanocomposite prepared in example 3 is used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.50g of styrene and 50m of L water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 1MPa, stirring and heating, heating to 130 deg.C, continuously making reaction for 1 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product ethyl benzene to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by means of the formula shown in test example 2 to obtain styrene conversion rate of 100%, ethyl benzene selectivity of 99.2% and TOF of 8.62 × 10-3s-1。
Test example 5
The nanocomposite prepared in example 4 was used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps were:
adding 0.1g of nano composite material, 0.50g of styrene and 30m of L water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 2MPa, stirring and heating, heating to a preset reaction temperature of 110 deg.C, continuously reacting for 2 hr, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, taking out product ethylbenzene and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using formula shown in test example 2 to obtain styrene conversion rate of 100%, ethylbenzene selectivity of 99.3% and TOF of 9.41 × 10-3s-1。
Test example 6
The nanocomposite prepared in example 5 was used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps were:
0.1g of the nanocomposite, 0.33g of styrene and 30m of L m of cyclohexane were added to a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to 120 ℃ of the preset reaction temperature, and the reaction is continued for 2 hoursStopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, taking out product ethylbenzene, performing chromatographic analysis, and calculating reactant conversion rate, product selectivity and TOF by the formula shown in test example 2 to obtain styrene conversion rate of 100%, ethylbenzene selectivity of 99.2%, and TOF of 9.27 × 10-3s-1。
Test example 7
The nanocomposite prepared in example 1 is used as a catalyst for olefin compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of cyclohexene and 30m of L m of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 120 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product cyclohexane is taken out for chromatographic analysis, and the conversion rate of the reactant, the product selectivity and the TOF are respectively calculated by the formula shown in the test example 2, so that the conversion rate of cyclohexene is 100 percent, the selectivity of cyclohexane is 99.5 percent, and the TOF is 9.60 × 10-3s-1。
Test example 8
The nanocomposite prepared in the comparative example 2 is used as a catalyst for olefin hydrogenation reduction reaction, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 1.96g of styrene and 100m of L g of cyclohexane were placed in a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is controlled to be 3.0MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction is continued for 3 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product ethylbenzene is taken out for chromatographic analysis, and the conversion rate of reactants, the product selectivity and the TOF are respectively calculated by the formula shown in the test example 2, so that the conversion rate of styrene is 100 percent, the selectivity of ethylbenzene is 98.4 percent, and the TOF is 5.15 × 10-3s-1。
From the above test examples 2-8, it can be seen that the nanocomposite of the present invention has a good catalytic effect when used as a catalyst for catalytic hydrogenation of an olefin compound, wherein compared with a catalyst containing no alkali metal, the nanocomposite containing carbon-coated transition metal of the present invention has high conversion rate and product selectivity for catalytic reaction, and has a higher catalytic reaction rate and better catalytic performance.
It is noted that although various embodiments of the present invention are disclosed herein, many adaptations and modifications may be made within the scope of the present invention in accordance with the common general knowledge of those skilled in the art. Such variations include the substitution of known equivalents for any aspect of the invention to achieve the same result in substantially the same way. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (25)
1. A carbon-coated transition metal nanocomposite containing alkali metal comprises a core-shell structure having a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the inner core is transition metal nanoparticles.
2. The nanocomposite of claim 1, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
3. Nanocomposite according to claim 2, wherein the mesoporous material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
4. The nanocomposite as claimed in claim 1, wherein the alkali metal content is 0.1 at% to 3 at%, the carbon content is 80 at% to 95 at%, the transition metal content is 0.1 at% to 10 at%, and the oxygen content is 1 at% to 15 at%, in terms of atomic percentage.
5. The nanocomposite of any of claims 1-4, wherein the alkali metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, and francium, and the transition metal is selected from one or more of iron, cobalt, nickel, copper, and zinc.
6. A method of preparing a nanocomposite material as claimed in any one of claims 1 to 5, comprising:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with a solution containing the alkali metal, and then drying;
and (3) placing the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated transition metal nanocomposite containing the alkali metal.
7. The production method according to claim 6, wherein the transition metal salt is selected from one or more of organic acid salts, carbonates, and hydroxycarbonates of transition metals, preferably organic acid salts of transition metals containing no hetero atom, more preferably acetates of transition metals containing no hetero atom, wherein the hetero atom means a metal atom other than the transition metals.
8. The production method according to claim 6, wherein the polyvalent organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid, and dipicolinic acid.
9. The production method according to claim 6, wherein the mass ratio of the transition metal salt to the polyvalent organic carboxylic acid is 1:0.1 to 10, preferably 1:0.5 to 5, and more preferably 1:0.8 to 3.
10. The production method according to claim 6, wherein the solvent is water and/or ethanol.
11. The production method according to claim 6, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of inert gas and hydrogen.
12. The preparation method according to claim 6, wherein the solution containing the alkali metal is a solution containing a salt and/or an alkali of the alkali metal, and the mass ratio of the salt and/or the alkali of the alkali metal to the product after the primary pyrolysis is 1: 2-100.
13. The production method according to claim 6, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-500 ℃, and preferably 100-400 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
14. Use of a nanocomposite according to any one of claims 1 to 5 as a catalyst in the treatment of volatile organic compounds, comprising:
contacting the volatile organic compound with the nanocomposite to perform a catalytic oxidation reaction.
15. Use according to claim 14, wherein the volatile organic compounds are volatile organic compounds contained in industrial waste gases.
16. The use according to claim 15, wherein the volatile organic compound comprises butane, and the content of the butane in the industrial waste gas is 0.01-2% by volume.
17. Use according to claim 16, wherein the catalytic oxidation reaction is carried out at a temperature of from 200 ℃ to 500 ℃, preferably from 300 ℃ to 400 ℃.
18. The use according to claim 17, wherein the reaction space velocity of the catalytic oxidation reaction is 2000-5000 ml industrial waste gas/(hr-g of the catalyst).
19. The use according to any one of claims 14 to 18, wherein the industrial waste gas is industrial waste gas generated in preparation of maleic anhydride through n-butane oxidation.
20. Use of the nanocomposite according to any one of claims 1 to 5 as a catalyst in a hydrogenation reduction reaction.
21. The use of claim 20, which comprises catalyzing the olefin-based compound with the catalyst in a hydrogen atmosphere for a hydrogenation reduction reaction.
22. Use according to claim 21, wherein the olefinic compound is an alkene or a cycloalkene, preferably styrene or cyclohexene.
23. Use according to claim 21, wherein the catalyst represents 1-50%, preferably 5-30% of the olefinic compound mass.
24. The use according to claim 21, wherein the temperature of the hydrogenation reduction reaction is between 100 ℃ and 130 ℃ and the pressure of the hydrogen is between 1MPa and 3 MPa.
25. The use according to claim 21, wherein the olefinic compound and the catalyst are mixed in a solvent and subjected to a hydrogenation reduction reaction, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water.
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