CN112705234A - Oxygen-doped carbon-based nickel carbide nano composite material and preparation method and application thereof - Google Patents

Oxygen-doped carbon-based nickel carbide nano composite material and preparation method and application thereof Download PDF

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CN112705234A
CN112705234A CN201911018112.9A CN201911018112A CN112705234A CN 112705234 A CN112705234 A CN 112705234A CN 201911018112 A CN201911018112 A CN 201911018112A CN 112705234 A CN112705234 A CN 112705234A
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nickel
oxygen
acid
composite material
nanocomposite
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CN112705234B (en
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吴耿煌
荣峻峰
达志坚
林伟国
谢婧新
纪洪波
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
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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
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention provides an oxygen-doped carbon-based nickel carbide nano composite material and a preparation method and application thereof, the nano composite material comprises an oxygen-doped carbon substrate and nickel carbide nano particles loaded on the carbon substrate, and a peak exists in a binding energy range of 287 eV-290 eV in a C1s X-ray photoelectron energy spectrogram of the nano composite material. The nano composite material adopts a method of pyrolyzing a metal salt precursor, obtains the nano composite material containing carbon matrix doped with rich oxygen and nickel carbide nano particles loaded on the carbon matrix through strictly and accurately controlling reaction conditions, and has good application prospects in catalytic hydrogenation reaction, electrocatalytic reaction and the like.

Description

Oxygen-doped carbon-based nickel carbide nano composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of transition metal carbide composite materials, in particular to an oxygen-doped carbon-based nickel carbide nano composite material and a preparation method and application thereof.
Background
Transition metal carbides are interstitial compounds produced by the insertion of carbon atoms into a transition metal lattice, having the properties of covalent solids, ionic crystals and transition metals.
Transition metal carbides have many excellent properties, including high hardness, high melting point, high electrical conductivity, and have found wide attention among researchers because of their applications in the fields of supercapacitors, catalysis, and electrocatalysis.
Nickel carbide is a typical transition metal carbide, and the main synthesis methods include vapor deposition, mechanical alloying, and liquid phase methods. Such as Sarr et al (J.Phys.chem.C., 2014,118 (40)), 23385-23392, by atomic deposition using nickel acetylacetonate as the nickel source and ethanol as the reducing agent to deposit a nickel carbide film at 300 ℃. Ghosh et al (Journal of Alloys and Compounds,2009,479(1-2):193- "200) prepared nickel carbide nanoparticles by means of mechanical ball milling in an inert atmosphere. Leng et al (Journal of nanoscience and nanotechnology,2006,6(1): 221-.
The preparation of the carbide nano material by the vapor deposition method has high energy consumption and low efficiency, and is not beneficial to mass preparation. The particle size of the nano particles is not easy to control by adopting a mechanical ball milling method; the liquid phase method requires the use of a large amount of organic solvents, which causes pollution, and the cost of metal organic precursors adopted by part of the liquid phase methods is high.
In addition, the surface charge density of nickel carbide, which is applied in the electrocatalytic direction, has a significant influence on the catalytic performance. In the field of carbon catalysis, the regulation and control of the oxygen-containing functional group of the carbon substrate is a means for effectively controlling the electrophilic performance of the carbon material. The prior preparation method is difficult to regulate and control the heteroatom doping of the composite material.
In conclusion, a method for preparing small-size carbon-based nickel carbide nanoparticles doped with rich oxygen atoms in a green, simple and low-cost manner is still lacking in the prior art, and is one of the difficulties in the field.
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 present invention has a main object to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide an oxygen-doped nickel carbide-based nanocomposite, which is prepared by pyrolyzing a metal salt precursor, and has good application prospects in catalytic hydrogenation or electrocatalytic reactions, and a method for preparing the same, and applications thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the present invention provides an oxygen-doped carbon-based nickel carbide nanocomposite, which comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, wherein the nanocomposite has a C1s X-ray photoelectron energy spectrum with a peak in a binding energy range from 287eV to 290 eV.
According to one embodiment of the present invention, the carbon content is 15% to 50%, the oxygen content is 4% to 20%, the hydrogen content is 1% to 4%, and the nickel content is 35% to 75% based on the total mass of the nanocomposite. Preferably, the carbon content is 20-35%, the oxygen content is 6-12%, the hydrogen content is 1-3%, and the nickel content is 40-70%.
According to one embodiment of the invention, the nickel carbide nanoparticles have an average particle size of 12nm to 30nm, preferably 15nm to 25 nm.
Another aspect of the present invention provides a method for preparing the oxygen-doped carbon-based nickel carbide nanocomposite, comprising the following steps: mixing a nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt to prepare a precursor; pyrolyzing the precursor in inert atmosphere to obtain a nano composite material; wherein the pyrolysis temperature is 310-340 ℃, and preferably 315-340 ℃.
According to one embodiment of the present invention, the step of preparing the precursor comprises: putting a nickel source, nitrogen-free organic carboxylic acid and alkali metal salt into a solvent, heating and stirring to form a homogeneous solution, and removing the solvent to obtain a precursor; or putting a nickel source and nitrogen-free organic carboxylic acid into a solvent, heating and stirring to form a homogeneous solution, and mixing the solid obtained after the solvent is removed with alkali metal salt to obtain the precursor.
According to one embodiment of the invention, the alkali metal salt is selected from one or more of sodium chloride, potassium sulfate, sodium carbonate and potassium carbonate.
According to one embodiment of the present invention, the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, nickel hydroxycarbonate and nickel acetate, and the nitrogen-free organic acid carboxylic acid is selected from one or more of citric acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid and trimesic acid.
According to one embodiment of the present invention, the molar ratio of the nickel source to the carboxyl group and the alkali metal salt in the organic carboxylic acid is 1 (2-8) to (0.1-20), preferably 1 (3-6) to (1-10).
According to one embodiment of the invention, the temperature of the heating and stirring is from 30 ℃ to 150 ℃, preferably from 70 ℃ to 120 ℃.
According to one embodiment of the invention, the solvent is selected from one or more of water, alcohols and N, N-dimethylformamide.
According to one embodiment of the invention, pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.2 ℃/min to 10 ℃/min, the temperature of the constant temperature section is 310 ℃ to 340 ℃, and the constant temperature time is 10min to 600 min. Preferably, the heating rate is 0.5 ℃/min to 1.5 ℃/min, the temperature of the constant temperature section is 315 ℃ to 340 ℃, and the constant temperature time is 20min to 300 min.
According to an embodiment of the invention, the method further comprises treating the pyrolyzed product with water washing.
The third aspect of the invention provides the application of the oxygen-doped carbon-based nickel carbide nano composite material as a catalyst in catalytic hydrogenation reaction or electrocatalytic reaction.
According to one embodiment of the present invention, the reaction substrate in the catalytic hydrogenation reaction is an organic substance containing a reducible group.
According to one embodiment of the invention, in the catalytic hydrogenation reaction, the mass ratio of the catalyst to the reaction substrate is 1: 0.1-500, the reaction temperature is 30-250 ℃, and the hydrogen pressure is 0.5-5 MPa. Preferably, the mass ratio of the catalyst to the reaction substrate is 1: 0.1-100, the reaction temperature is 50-200 ℃, and the hydrogen pressure is 1-3 MPa.
According to the technical scheme, the oxygen-doped carbon-based nickel carbide nano composite material and the preparation method and application thereof have the advantages and positive effects that:
according to the oxygen-doped carbon-based nickel carbide nano composite material, a method for pyrolyzing a metal salt precursor is adopted, and reaction conditions are strictly controlled, so that the composite material containing the oxygen-doped carbon substrate and the nickel carbide nano particles loaded on the carbon substrate is obtained, the central electron density of the nickel carbide is influenced by an oxygen-containing functional group, the catalytic performance of the material can be regulated and controlled, the performance of the material is further improved, and the oxygen-doped carbon-based nickel carbide nano composite material has a good application prospect in catalytic hydrogenation reaction, electrocatalytic reaction and the like; the preparation method of the nano composite material is environment-friendly, simple in process and low in cost, the utilization rate of nickel in the preparation process of the precursor can reach 100%, no heavy metal-containing wastewater is generated, and the preparation method is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction pattern of the nanocomposite prepared in example 1;
FIG. 2 is a C1s X-ray photoelectron spectrum of the nanocomposite prepared in example 1;
FIG. 3 is a transmission electron microscope photograph at different magnifications of the nanocomposite prepared in example 1;
FIG. 4 is an X-ray diffraction pattern of the nanocomposite prepared in example 2;
FIG. 5 is a C1s X-ray photoelectron spectrum of the nanocomposite prepared in example 2.
FIG. 6 is an X-ray diffraction pattern of the nanocomposite prepared in example 3.
Fig. 7 is an X-ray diffraction pattern of the nanocomposite prepared in comparative example 1.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application 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.
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 term "oxygen" doped with oxygen in the present invention refers to oxygen element, wherein the "oxygen content" of the nanocomposite refers to the content of oxygen element, specifically, oxygen element exists in various forms in the formed carbon layer during the preparation process of the nanocomposite, and the "oxygen content" is the total content of all forms of oxygen element.
One aspect of the present invention provides an oxygen-doped carbon-based nickel carbide nanocomposite, which comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, wherein the nanocomposite has a C1s X-ray photoelectron energy spectrum with a peak in a binding energy range from 287eV to 290 eV.
According to the present invention, nickel carbide, a typical type of transition metal carbide, has many excellent properties including high hardness, high melting point, and high electrical conductivity. The nanocomposite material of the invention obtains a nickel carbide-containing nanocomposite material through a specific preparation method and reaction conditions, and specifically, the nanocomposite material comprises a carbon matrix doped with oxygen and nickel carbide nanoparticles loaded on the carbon matrix. The inventors of the present invention have found that such an oxygen-doped carbon matrix may act synergistically with nickel carbide nanoparticles supported thereon. As the carbon substrate has carboxyl groups, a spectrum peak exists at the position where the binding energy is 287 eV-290 eV in a C1s X-ray photoelectron energy spectrogram, which is different from the spectrum peak of the existing carbon-coated nickel carbide material, and the fact that the composite material obtained by the special preparation method has a microstructure which is substantially different from other materials is shown. In addition, the oxygen-containing functional group influences the central electron density of the nickel carbide, and the catalytic performance of the nickel carbide can be further regulated and controlled, so that the performance of the material is optimized. The material has wide application prospect in the fields of catalysis, supercapacitors and the like.
In some embodiments, the carbon content is 15% to 50%, the oxygen content is 4% to 20%, the hydrogen content is 1% to 4%, and the nickel content is 35% to 75% based on the total mass of the nanocomposite. Preferably, the carbon content is 20-35%, the oxygen content is 6-12%, the hydrogen content is 1-3%, and the nickel content is 40-70%.
In some embodiments, the nickel carbide nanoparticles have an average particle size of 12nm to 30nm, preferably 15nm to 25 nm.
Another aspect of the present invention provides a method for preparing the oxygen-doped carbon-based nickel carbide nanocomposite, comprising the following steps:
mixing a nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt to prepare a precursor;
pyrolyzing the precursor in inert atmosphere to obtain a nano composite material; wherein the pyrolysis temperature is 310-340 ℃.
In the early studies according to the present invention, the inventors found that a carbon-coated nickel nanocomposite material can be obtained by a precursor pyrolysis method, for example, patent CN 109309213a discloses a carbon-coated nickel nanocomposite material and a preparation method thereof, wherein the precursor constant temperature section temperature is 425 ℃ to 800 ℃. In fact, the temperature range for the preparation of carbon-coated nickel nanoparticles by the prior art pyrogenic process is also generally carried out at the aforementioned temperatures. However, the inventor finds that the green, simple and low-cost preparation of the novel nickel carbide nano composite material with controllable doping elements can be realized by strictly controlling the reaction conditions, the reaction raw materials and the proportion thereof. Compared with the prior art, the method disclosed by the invention does not need to use an organic solvent and a surfactant, and does not need to introduce combustible reducing gases such as hydrogen in the pyrolysis process, so that the preparation of the nickel carbide breaks through the defects of high energy consumption, complex process and the like of the traditional method, the possibility is brought to industrial large-scale production, and the method has important significance.
In some embodiments, the step of preparing the precursor comprises: putting a nickel source, nitrogen-free organic carboxylic acid and alkali metal salt into a solvent, heating and stirring to form a homogeneous solution, and removing the solvent to obtain a precursor; or putting a nickel source and nitrogen-free organic carboxylic acid into a solvent, heating and stirring to form a homogeneous solution, and mixing the solid obtained after the solvent is removed with alkali metal salt to obtain the precursor. Specifically, the solvent may be removed by evaporation of the solvent, and the temperature and process may be any available technique, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven. In some embodiments, the solvent is selected from one or more of water, alcohols, and N, N-dimethylformamide, preferably water.
In some embodiments, the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, nickel hydroxycarbonate, and nickel acetate, and the nitrogen-free organic acid carboxylic acid is selected from one or more of citric acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid, and trimesic acid.
In some embodiments, the alkali metal salt is selected from one or more of sodium chloride, potassium sulfate, sodium carbonate, and potassium carbonate. As can be seen by those skilled in the art, the preparation of nickel carbide is relatively difficult, and the reaction conditions, especially the reaction temperature, required in general are relatively strict and need to be precisely controlled to obtain the nickel carbide. However, the inventors of the present invention have found that by adding a certain amount of alkali metal salt as a stabilizer, it is more advantageous to form a stable nickel carbide phase, and a nickel carbide composite material can be formed within a relatively wide reaction temperature range.
In some embodiments, the molar ratio of the carboxyl group in the nickel source and the organic carboxylic acid to the alkali metal salt is 1 (2-8): 0.1-20), preferably 1 (3-6): 1-10.
In some embodiments, the temperature of the heating and stirring is from 30 ℃ to 150 ℃, preferably from 70 ℃ to 120 ℃.
In some embodiments, the pyrolysis process of the present invention specifically comprises: heating the precursor to a constant temperature section in an inert atmosphere, such as nitrogen or argon, and keeping the constant temperature in the constant temperature section; wherein the heating rate is 0.2 ℃/min to 10 ℃/min, the temperature of the constant temperature section is 310 ℃ to 340 ℃, and the constant temperature time is 10min to 600 min. Preferably, the heating rate is 0.5 ℃/min to 1.5 ℃/min, the temperature of the constant temperature section is 315 ℃ to 340 ℃, and the constant temperature time is 20min to 300 min. As mentioned above, by strictly controlling these reaction conditions, the nanocomposite material of the present invention can be obtained better.
In some embodiments, the method further comprises treating the pyrolyzed product with a water wash. So as to remove soluble substances possibly contained in the obtained product, and then filtering and drying the product to obtain the nano composite material of the invention.
The third aspect of the invention provides the application of the oxygen-doped carbon-based nickel carbide nano composite material as a catalyst in catalytic hydrogenation reaction or electrocatalytic reaction.
Taking catalytic hydrogenation reaction as an example, the nanocomposite material of the invention is applied to catalytic hydrogenation reaction, and a reaction substrate is an organic matter containing reducible groups. Alternatively, the reaction substrate includes, but is not limited to, styrene, benzaldehyde, aromatic nitro compounds, and the like.
In some embodiments, in the catalytic hydrogenation reaction, the mass ratio of the catalyst to the reaction substrate is 1: 0.1-100, the reaction temperature can be 30-250 ℃, and the hydrogen pressure is controlled at 0.5-5 MPa. Preferably, the mass ratio of the catalyst to the reaction substrate is 1: 0.1-100, the reaction temperature can be 50-200 ℃, and the hydrogen pressure is controlled at 1-3 MPa.
The nano composite material prepared by the method has the advantages of simple preparation process and low cost, the utilization rate of nickel in the precursor preparation process can reach 100%, no heavy metal-containing wastewater is generated, and compared with the existing preparation method of the nickel carbide composite material, the preparation method is more suitable for large-scale industrial production.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, all reagents used in the invention are analytically pure.
Instrumentation and testing
Elements on the surface of the material were detected by an X-ray photoelectron spectroscopy (XPS). The adopted X-ray photoelectron spectrum analyzer is an ESCALB 220i-XL type ray photoelectron spectrum analyzer which is manufactured by VG scientific company and is provided with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test-9mbar。
The information such as the composition of the material, the structure or the form of the internal atoms or molecules of the material and the like is obtained through XRD. The XRD diffractometer adopted is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and XRD test conditions are as follows: the Cu target was irradiated with K α rays (wavelength λ is 0.154nm), tube voltage was 40kV, tube current was 200mA, and scanning speed was 10 ° (2 θ)/min.
The surface morphology of the material was characterized by High Resolution Transmission Electron Microscopy (HRTEM). The type of the adopted high-resolution transmission electron microscope is JEM-2100 (Japanese electronic Co., Ltd.), and the testing conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV. The particle size of the nanoparticles in the sample is measured by an electron microscope picture.
The analysis of three elements of carbon (C), hydrogen (H) and oxygen (O) was performed on an Elementar Micro Cube element analyzer. The specific operation method and conditions are as follows: weighing 1-2mg of sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (for removing atmospheric interference during sample feeding, helium gas is adopted for blowing), and then reducing the combusted gas by using reduced copper, carbon dioxide and water. And separating the mixed gas through a desorption column, and sequentially detecting the mixed gas in a TCD detector. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
The content of the metal elements is the normalized result of the material after the content of carbon, hydrogen and oxygen is removed.
Example 1
This example illustrates the preparation of an oxygen-doped nickel carbide-based nanocomposite material according to the present invention.
1) 10.51g (50mmol) of citric acid monohydrate, 4.64g (50mmol) of nickel hydroxide and 5.84g (100mmol) of sodium chloride are weighed and added into 150mL of deionized water, the mixture is stirred at 110 ℃ to obtain a uniform solution, the uniform solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
2) Placing 7g of the 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 at a flow rate of 100mL/min, heating to 330 ℃ at a speed of 1 ℃/min, keeping the temperature for 150min, stopping heating, and cooling to room temperature under the nitrogen atmosphere.
3) Transferring the composite material in the porcelain boat obtained in the step 2) to a flask, adding 50mL of deionized water, stirring at 60 ℃ for 20min, then performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nano composite material.
Material characterization:
FIG. 1 is an X-ray diffraction pattern of the nanocomposite prepared in example 1. As can be seen from fig. 1, the diffraction peaks at 2 θ of 39.3 °, 41.6 °, 44.7 °, 58.6 °, 71.2 °, and 78.1 ° correspond to the diffraction peaks of a typical nickel carbide material. The average particle size of the nickel carbide nanoparticles was 21.4nm, calculated according to the scherrer equation. The content of C in the nano material measured by an element analyzer is 25.94%, the content of H is 2.06%, the content of O is 10.18%, and the content of Ni after normalization is 61.82%. It can be seen that the composite material is doped with a large amount of oxygen. FIG. 2 is a C1s X-ray photoelectron spectrum of the nanocomposite prepared in example 1. After the spectrogram is subjected to peak fitting, the oxygen-containing functional groups on the carbon substrate are mainly hydroxyl functional groups and carboxyl functional groups, wherein a clear peak exists at the position where the binding energy is 287-290 eV. FIG. 3 is a transmission electron microscope image at different magnifications of the nanocomposite material prepared in example 1. It can be seen from fig. 3(a) that nickel carbide is highly densely dispersed on the support carbon; from fig. 3(b), the lattice fringes of the nickel carbide nanoparticles and the morphology of the carrier carbon can be seen.
Example 2
This example illustrates the preparation of an oxygen-doped nickel carbide-based nanocomposite material according to the present invention.
1) 10.51g (50mmol) of citric acid monohydrate, 4.64g (50mmol) of nickel hydroxide and 11.69g (200mmol) of sodium chloride are weighed and added into 150mL of deionized water, the mixture is stirred at 110 ℃ to obtain a uniform solution, the uniform solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
2) Putting 8g of the precursor in the step 1) into a porcelain boat, then putting the porcelain boat into a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100mL/min, heating to 330 ℃ at a speed of 1.5 ℃/min, keeping the temperature for 150min, stopping heating, and cooling to room temperature under a nitrogen atmosphere.
3) Transferring the composite material in the porcelain boat obtained in the step 2) to a flask, adding 50mL of deionized water, stirring at 60 ℃ for 20min, then performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nano composite material.
Material characterization:
fig. 4 is an XRD pattern of the nanocomposite prepared in example 2. Similarly to example 1, the diffraction peak of nickel carbide was also present in fig. 4. The average particle size of the nickel carbide nanoparticles was also 21.1nm, calculated according to the scherrer equation. The content of C in the nano material measured by an element analyzer is 24.07%, the content of H is 1.68%, the content of O is 7.92%, and the content of Ni after normalization is 66.32%. FIG. 5 is a C1s X-ray photoelectron spectrum of the nanocomposite prepared in example 2. After the spectrogram is subjected to peak-splitting fitting, the oxygen-containing functional groups on the carbon substrate are mainly hydroxyl functional groups and carboxyl functional groups, and a clear peak exists at the position where the binding energy is 287-290 eV.
Example 3
1) 10.51g (50mmol) of citric acid monohydrate, 4.64g (50mmol) of nickel hydroxide and 5.84g (100mmol) of sodium chloride are weighed and added into 150mL of deionized water, the mixture is stirred at 110 ℃ to obtain a uniform solution, the uniform solution is continuously heated and evaporated to dryness, and the solid is ground to obtain a precursor.
2) Placing 7g of the 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 at a flow rate of 100mL/min, heating to 340 ℃ at a speed of 1 ℃/min, keeping the temperature for 150min, stopping heating, and cooling to room temperature under a nitrogen atmosphere.
3) Transferring the composite material in the porcelain boat obtained in the step 2) to a flask, adding 50mL of deionized water, stirring at 60 ℃ for 20min, then performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nano composite material.
Fig. 6 is an XRD pattern of the nanocomposite prepared in example 3. Similar to fig. 4, the diffraction peaks of nickel carbide are also present in fig. 6. The average particle size of the nickel carbide nanoparticles was 21.1nm, calculated according to the scherrer equation.
Comparative example 1
A nanocomposite was prepared using the method of example 1, except that no sodium chloride was added to the precursor.
Material characterization: FIG. 7 shows the Nami prepared in comparative example 1X-ray diffraction spectrum of the rice composite material. From the figure, only the diffraction peak corresponding to face centered cubic (fcc) Ni and the diffraction peak of NiO were observed, and no corresponding Ni was observed3Diffraction peak of C.
Therefore, the alkali metal salt can be used as a stabilizer to promote the generation of nickel carbide, and when no alkali metal salt exists in the precursor, the carbon-based nickel carbide nano composite material cannot be prepared.
Application example 1
The application example is used for illustrating that the oxygen-doped carbon-based nickel carbide nano composite material provided by the invention is used as a catalyst for catalyzing the hydrogenation reaction of styrene.
100mg of the nanocomposite material of example 1, 208mg of styrene and 30mL of absolute ethanol were added to a reaction vessel, and H was introduced2After 4 times of replacement, the pressure in the reaction kettle is maintained at 1.0MPa, and the air inlet valve is closed. Stirring, heating to 120 ℃, timing, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, taking out the product, and performing chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion rate-reacted mass of reaction substance/addition of reaction substance. times.100%
The selectivity is the mass of the target product/mass of the reaction product x 100%
After analysis, 100% conversion of styrene and 100% selectivity to ethylbenzene were obtained.
Therefore, the composite material of the invention has quite good catalytic activity in hydrogenation reaction.
In conclusion, the oxygen-doped carbon-based nickel carbide nano composite material is obtained by adopting the method for pyrolyzing the metal salt precursor and controlling the specific reaction conditions, compared with the traditional preparation process of the nickel carbide composite material, the method has the advantages of greenness, simplicity, low cost and the like, and the obtained material has good application prospects in catalytic hydrogenation reaction, electrocatalysis reaction and the like.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims (15)

1. An oxygen-doped nickel carbide-based nanocomposite material, comprising an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, wherein the nanocomposite material has a C1s X-ray photoelectron spectroscopy spectrum with a peak in a binding energy range of 287eV to 290 eV.
2. The nanocomposite as claimed in claim 1, wherein the carbon content is 15 to 50%, the oxygen content is 4 to 20%, the hydrogen content is 1 to 4%, and the nickel content is 35 to 75% based on the total mass of the nanocomposite.
3. The nanocomposite as recited in claim 1, wherein the nickel carbide nanoparticles have an average particle size of 12nm to 30 nm.
4. A preparation method of the oxygen-doped carbon-based nickel carbide nanocomposite material as claimed in any one of claims 1 to 3, comprising the following steps:
mixing a nickel source, a nitrogen-free organic carboxylic acid and an alkali metal salt to prepare a precursor;
pyrolyzing the precursor under inert atmosphere to obtain the nano composite material;
wherein the pyrolysis temperature is 310-340 ℃.
5. The production method according to claim 4, wherein the step of preparing the precursor includes:
placing the nickel source, the nitrogen-free organic carboxylic acid and the alkali metal salt in a solvent, heating and stirring to form a homogeneous solution, and removing the solvent to obtain the precursor; or
And (3) placing the nickel source and the nitrogen-free organic carboxylic acid in a solvent, heating and stirring to form a homogeneous solution, and mixing the solid obtained after the solvent is removed and the alkali metal salt to obtain the precursor.
6. The method according to claim 4, wherein the alkali metal salt is one or more selected from the group consisting of sodium chloride, potassium sulfate, sodium carbonate, and potassium carbonate.
7. The production method according to claim 4, wherein the nickel source is one or more selected from the group consisting of nickel hydroxide, nickel carbonate, basic nickel carbonate and nickel acetate, and the nitrogen-free organic acid carboxylic acid is one or more selected from the group consisting of citric acid, maleic acid, fumaric acid, succinic acid, tartaric acid, malic acid, gluconic acid and trimesic acid.
8. The method according to claim 4, wherein the molar ratio of the nickel source to the carboxyl group and the alkali metal salt in the organic carboxylic acid is 1 (2-8) to (0.1-20).
9. The method according to claim 4, wherein the temperature of the heating and stirring is 30 to 150 ℃.
10. The method according to claim 4, wherein the solvent is one or more selected from the group consisting of water, alcohols, and N, N-dimethylformamide.
11. The method of claim 4, wherein the pyrolyzing comprises: heating the precursor to a constant temperature section under inert atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.2-10 ℃/min, the temperature of the constant temperature section is 310-340 ℃, and the constant temperature time is 10-600 min.
12. The method of claim 4, further comprising treating the pyrolyzed product with water washing.
13. The use of the oxygen-doped carbon-based nickel carbide nanocomposite as claimed in any one of claims 1 to 3 as a catalyst in catalytic hydrogenation reactions or electrocatalytic reactions.
14. The use according to claim 13, wherein the substrate of the catalytic hydrogenation reaction is an organic substance containing a reducible group.
15. The application of the catalyst according to claim 14, wherein in the catalytic hydrogenation reaction, the mass ratio of the catalyst to the reaction substrate is 1: 0.1-500, the reaction temperature is 30-250 ℃, and the hydrogen pressure is 0.5-5 MPa.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116020079A (en) * 2021-10-27 2023-04-28 中国石油化工股份有限公司 Catalytic hydrodechlorination process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669347A (en) * 2015-12-31 2016-06-15 浙江工业大学 Method for reducing content of unsaturated hydrocarbons in linear alkylbenzene
CN109304476A (en) * 2017-07-28 2019-02-05 中国石油化工股份有限公司 Carbon coating transition metal nanocomposite and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669347A (en) * 2015-12-31 2016-06-15 浙江工业大学 Method for reducing content of unsaturated hydrocarbons in linear alkylbenzene
CN109304476A (en) * 2017-07-28 2019-02-05 中国石油化工股份有限公司 Carbon coating transition metal nanocomposite and its preparation method and application
CN109304475A (en) * 2017-07-28 2019-02-05 中国石油化工股份有限公司 Carbon-coating nickel composite material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
H.H. NERSISYAN 等: "Self-propagating high-temperature synthesis of nano-sized titanium carbide powder", 《MATERIALS RESEARCH》 *
JING HAO等: "Controlled synthesis of Ni3C/nitrogen-doped carbon nanoflakes for efficient oxygen evolution", 《ELECTROCHIMICA ACTA》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116020079A (en) * 2021-10-27 2023-04-28 中国石油化工股份有限公司 Catalytic hydrodechlorination process
CN116020079B (en) * 2021-10-27 2024-05-17 中国石油化工股份有限公司 Catalytic hydrodechlorination process

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