CN112705234B - Oxygen-doped carbon-based nickel carbide nanocomposite and preparation method and application thereof - Google Patents
Oxygen-doped carbon-based nickel carbide nanocomposite and preparation method and application thereof Download PDFInfo
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- CN112705234B CN112705234B CN201911018112.9A CN201911018112A CN112705234B CN 112705234 B CN112705234 B CN 112705234B CN 201911018112 A CN201911018112 A CN 201911018112A CN 112705234 B CN112705234 B CN 112705234B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 90
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- -1 alkali metal salt Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 235000011087 fumaric acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 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
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 11
- 229910052573 porcelain Inorganic materials 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229960002303 citric acid monohydrate Drugs 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000353097 Molva molva Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- 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
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/22—Carbides
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Abstract
The invention provides an oxygen-doped carbon-based nickel carbide nanocomposite, a preparation method and application thereof, wherein the nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles loaded on the carbon matrix, and a spectrum peak exists in a bonding energy range of 287 eV-290 eV in a C1s X ray photoelectron spectrum of the nanocomposite. The nanocomposite material adopts a method of pyrolyzing a metal salt precursor, and the nanocomposite material containing a carbon matrix rich in oxygen doping and nickel carbide nano particles loaded on the carbon matrix is obtained through strictly and accurately controlling reaction conditions, so that the material has good application prospects in catalytic hydrogenation reaction or electrocatalytic reaction and the like.
Description
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 nanocomposite material, a preparation method and application thereof.
Background
Transition metal carbides are a class of mesenchymal compounds produced by intercalation of carbon atoms into a transition metal lattice, and have the characteristics of covalent solids, ionic crystals and transition metals.
Transition metal carbides have many excellent properties including high hardness, high melting point, high conductivity, and are used in the fields of supercapacitors, catalysis, and electrocatalysis, and thus have received extensive attention from researchers.
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), 23085-2392) deposited nickel carbide films at 300℃by atomic deposition techniques with nickel acetylacetonate as the nickel source and ethanol as the reducing agent. Ghosh et al (Journal of Alloys and Compounds,2009,479 (1-2): 193-200) prepared nickel carbide nanoparticles by mechanical ball milling in an inert atmosphere. Leng et al (Journal of nanoscience and nanotechnology,2006,6 (1): 221-226.) prepared 40nm nickel carbide nanoparticles by a liquid phase method in a diphenyl ether solution containing oleylamine and oleic acid using nickel formate as a precursor.
The vapor deposition method for preparing the carbide nano material 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 needs a large amount of organic solvent, causes pollution and the cost of the metal organic precursor adopted by the partial liquid phase method is higher.
In addition, nickel carbide is applied in the electrocatalytic direction, and its surface charge density has an important effect on catalytic performance. In the field of carbon catalysis, the regulation and control of oxygen-containing functional groups of a carbon matrix is an effective means of carbon material electrophilic performance. The existing preparation method is difficult to regulate and control the heteroatom doping of the composite material.
In summary, the present art still lacks a green, simple and low-cost method for preparing small-size carbon-based nickel carbide nanoparticles doped with abundant oxygen atoms, which is also one of the difficulties in this field.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides an oxygen-doped carbon-based nickel carbide nanocomposite, a preparation method and application thereof, wherein the nanocomposite is prepared by adopting a method for pyrolyzing a metal salt precursor, and the nanocomposite containing rich oxygen-doped carbon matrix and nickel carbide nano particles loaded on the carbon matrix is obtained through strictly controlling reaction conditions, and has good application prospects in catalytic hydrogenation reaction or electrocatalytic reaction and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
one aspect of the invention provides an oxygen-doped carbon-based nickel carbide nanocomposite, the nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, and a spectrum peak exists in a binding energy range of 287 eV-290 eV in a C1s X ray photoelectron spectrum of the nanocomposite.
According to one embodiment of the invention, the carbon content is 15-50%, the oxygen content is 4-20%, the hydrogen content is 1-4% and the nickel content is 35-75% 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 diameter of 12nm to 30nm, preferably 15nm to 25nm.
The invention also provides a preparation method of the oxygen-doped carbon-based nickel carbide nanocomposite, which comprises the following steps: mixing a nickel source, an organic carboxylic acid free of nitrogen and an alkali metal salt to prepare a precursor; pyrolyzing the precursor in inert atmosphere to obtain a nanocomposite; wherein the pyrolysis temperature is 310-340 ℃, preferably 315-340 ℃.
According to one embodiment of the invention, the step of preparing the precursor comprises: heating and stirring a nickel source, organic carboxylic acid without nitrogen and alkali metal salt in a solvent to form a homogeneous solution, and removing the solvent to obtain a precursor; or placing the nickel source and the organic carboxylic acid without nitrogen in a solvent, heating and stirring to form a homogeneous solution, and mixing the solid after removing the solvent with alkali metal salt to obtain the precursor.
According to one embodiment of the present 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, basic nickel carbonate and nickel acetate, and the non-nitrogen containing 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 invention, the molar ratio of the nickel source, the carboxyl group and the alkali metal salt in the organic carboxylic acid is 1 (2-8): 0.1-20, preferably 1 (3-6): 1-10.
According to one embodiment of the invention, the temperature of the heating and stirring is 30 to 150 ℃, preferably 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 0.2-10 ℃/min, the temperature of the constant temperature section is 310-340 ℃, and the constant temperature time is 10-600 min. Preferably, the temperature rising rate is 0.5 ℃/min-1.5 ℃/min, the constant temperature section temperature is 315 ℃ to 340 ℃ and the constant temperature time is 20 min-300 min.
According to one embodiment of the invention, further comprising treating the pyrolyzed product with water.
The third aspect of the invention provides the use of the oxygen doped carbon based nickel carbide nanocomposite described above as a catalyst in a catalytic hydrogenation reaction or an electrocatalytic reaction.
According to one embodiment of the 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 nanocomposite and the preparation method and application thereof provided by the invention have the advantages and positive effects that:
the oxygen-doped carbon-based nickel carbide nanocomposite provided by the invention adopts a method of pyrolyzing a metal salt precursor, strictly controls reaction conditions, obtains a composite material containing an oxygen-doped carbon matrix and nickel carbide nano particles loaded on the carbon matrix, can regulate and control the catalytic performance of the material by influencing the center electron density of nickel carbide through oxygen-containing functional groups, and has good application prospects in catalytic hydrogenation reactions, electrocatalytic reactions and the like; the preparation method of the nanocomposite is environment-friendly, simple in process and low in cost, the utilization rate of nickel in the precursor preparation process can reach 100%, no heavy metal-containing wastewater is generated, and the method is suitable for large-scale industrial production.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to 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 micrograph at various 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 provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Any terms not directly defined herein should be construed to have the 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" of the present invention means oxygen element, wherein "oxygen content" of the nanocomposite means content of oxygen element, specifically, oxygen element existing in various forms is contained in the carbon-forming layer during the preparation of the nanocomposite, and the "oxygen content" is total content of all forms of oxygen element.
One aspect of the invention provides an oxygen-doped carbon-based nickel carbide nanocomposite, the nanocomposite comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, and a spectrum peak exists in a binding energy range of 287 eV-290 eV in a C1s X ray photoelectron spectrum of the nanocomposite.
According to the present invention, nickel carbide, as a typical class of transition metal carbides, has many excellent properties including high hardness, high melting point, high electrical conductivity. The nanocomposite of the present invention, through specific preparation methods and reaction conditions, yields a nanocomposite containing nickel carbide, in particular, comprising an oxygen-doped carbon matrix and nickel carbide nanoparticles supported 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. Because the carbon matrix has carboxyl groups, in the C1s X ray photoelectron spectrum, a spectrum peak exists at the position of 287 eV-290 eV of the binding energy, which is different from the spectrum peak of the existing carbon-coated nickel carbide material, so that the composite material obtained by the special preparation method is substantially different from other materials in microstructure. In addition, the oxygen-containing functional group affects the center electron density of the nickel carbide, and the catalytic performance of the nickel carbide can be further regulated and controlled, so that the material performance 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 25nm.
The invention also provides a preparation method of the oxygen-doped carbon-based nickel carbide nanocomposite, which comprises the following steps:
mixing a nickel source, an organic carboxylic acid free of nitrogen and an alkali metal salt to prepare a precursor;
pyrolyzing the precursor in inert atmosphere to obtain a nanocomposite; wherein the pyrolysis temperature is 310-340 ℃.
According to the present invention, in early studies, the inventors found that a carbon-coated nickel nanocomposite could be obtained by a method of precursor pyrolysis, for example, patent CN 109309213a discloses a carbon-coated nickel nanocomposite and a method of preparing the same, in which the precursor constant temperature section temperature is 425 ℃ to 800 ℃. In fact, the preparation temperature ranges for the prior art pyrolysis methods for preparing carbon-coated nickel nanoparticles are also typically carried out at the aforementioned temperatures. However, the inventor discovers that the green, simple and low-cost preparation of the novel nickel carbide nanocomposite 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 does not need to use an organic solvent and a surfactant, and does not need to introduce combustible reducing gases such as hydrogen and the like 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 in the traditional method, and the method brings possibility to industrial mass production and has important significance.
In some embodiments, the step of preparing the precursor comprises: heating and stirring a nickel source, organic carboxylic acid without nitrogen and alkali metal salt in a solvent to form a homogeneous solution, and removing the solvent to obtain a precursor; or placing the nickel source and the organic carboxylic acid without nitrogen in a solvent, heating and stirring to form a homogeneous solution, and mixing the solid after removing the solvent with alkali metal salt to obtain the precursor. In particular, the solvent removal may be carried out by evaporation of the solvent, the temperature and process of which may be carried out by any of the available techniques, 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, basic nickel carbonate, and nickel acetate, and the non-nitrogen containing 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 known by those skilled in the art, the preparation of nickel carbide is relatively difficult, and generally the required reaction conditions, especially the reaction temperature, are severe, and accurate control is required to obtain the nickel carbide. The inventors of the present invention have found that by adding a certain amount of alkali metal salt as a stabilizer, a stable nickel carbide phase is more advantageously formed, and a nickel carbide composite material can be formed in a relatively wide reaction temperature range.
In some embodiments, the molar ratio of the nickel source, the carboxyl group in the organic carboxylic acid, and 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 0.2-10 ℃/min, the temperature of the constant temperature section is 310-340 ℃, and the constant temperature time is 10-600 min. Preferably, the temperature rising rate is 0.5 ℃/min-1.5 ℃/min, the constant temperature section temperature is 315 ℃ to 340 ℃ and the constant temperature time is 20 min-300 min. As previously mentioned, the nanocomposite of the present invention can be better obtained by strictly controlling the reaction conditions.
In some embodiments, treating the pyrolyzed product with water is also included. So as to remove the soluble substances possibly contained in the obtained product, and then filtering and drying the product to obtain the nanocomposite.
The third aspect of the invention provides the use of the oxygen doped carbon based nickel carbide nanocomposite described above as a catalyst in a catalytic hydrogenation reaction or an electrocatalytic reaction.
Taking catalytic hydrogenation reaction as an example, the nanocomposite is applied to the catalytic hydrogenation reaction, and the reaction substrate is an organic matter containing a reducible group. 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 can be controlled between 0.5MPa and 5MPa. 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 between 1MPa and 3MPa.
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 percent, 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 the invention is not limited thereby. Unless otherwise indicated, all reagents used in the present invention were analytically pure.
Instrument and test
The elements of the material surface were detected by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar。
Information such as the composition of the material, the structure or morphology of atoms or molecules within the material, and the like is obtained by XRD. The XRD diffractometer is XRD-6000 type X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, ka radiation (wavelength λ=0.154 nm), tube voltage 40kV, tube current 200mA, scan speed 10 ° (2θ)/min.
The surface topography of the material was characterized by High Resolution Transmission Electron Microscopy (HRTEM). The model 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 200kV. The particle size of the nano particles in the sample is measured by an electron microscope picture.
Analysis of three elements of carbon (C), hydrogen (H), and oxygen (O) was performed on a Elementar Micro Cube elemental analyzer. The specific operation method and conditions are as follows: 1-2mg of sample is weighed in a tin cup, put in an automatic sample feeding disc, put in a combustion tube through a ball valve for combustion, the combustion temperature is 1000 ℃ (in order to remove atmospheric interference during sample feeding, helium purging is adopted), and then reduction copper is used for reducing the burnt gas, carbon dioxide and water. The mixed gas is separated by a desorption column and sequentially enters a TCD detector for detection. The analysis of oxygen element is to convert oxygen in the sample into CO by pyrolysis under the action of a carbon catalyst, and then detect the CO by TCD.
The content of the metal element is normalized after the material is deducted to remove the content of carbon, hydrogen and oxygen.
Example 1
This example is presented to illustrate the preparation of oxygen doped carbon based nickel carbide nanocomposite materials of the present invention.
1) 10.51g (50 mmol) of citric acid monohydrate, 4.64g (50 mmol) of nickel hydroxide and 5.84g (100 mmol) of sodium chloride are weighed 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, placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen, heating to 330 ℃ at a speed of 1 ℃/min at a flow rate of 100mL/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, performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nanocomposite material.
Characterization of materials:
FIG. 1 is an X-ray diffraction pattern of the nanocomposite prepared in example 1. It can be seen from fig. 1 that the diffraction peaks of 2θ=39.3°, 41.6 °, 44.7 °, 58.6 °, 71.2 °, 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 formula. The content of the nano material C is 25.94%, the content of H is 2.06%, the content of O is 10.18% and the content of Ni is 61.82% after normalization. It can be seen that the composite material is doped with a large amount of oxygen element. FIG. 2 is a C1s X ray photoelectron spectrum of the nanocomposite prepared in example 1. After the spectrograms are subjected to peak-by-peak fitting, the oxygen-containing functional groups on the carbon matrix are mainly hydroxyl and carboxyl functional groups, wherein obvious spectral peaks exist at the positions of 287 eV-290 eV. Fig. 3 is a transmission electron micrograph at various magnifications of the nanocomposite prepared in example 1. It can be seen from fig. 3 (a) that nickel carbide is dispersed on the carrier carbon at a high density; from fig. 3 (b), the morphology of the support carbon and the lattice fringes of the nickel carbide nanoparticles can be seen.
Example 2
This example is presented to illustrate the preparation of oxygen doped carbon based nickel carbide nanocomposite materials of the present invention.
1) 10.51g (50 mmol) of citric acid monohydrate, 4.64g (50 mmol) of nickel hydroxide and 11.69g (200 mmol) of sodium chloride are weighed 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) 8g of the precursor in the step 1) is placed in a porcelain boat, then the porcelain boat is placed in a constant temperature area of a tube furnace, nitrogen is introduced, the flow is 100mL/min, the temperature is raised to 330 ℃ at the speed of 1.5 ℃/min, heating is stopped after the temperature is kept constant for 150min, and the porcelain boat is cooled 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, performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nanocomposite material.
Characterization of materials:
fig. 4 is an XRD pattern of the nanocomposite prepared in example 2. Similar to example 1, fig. 4 also shows diffraction peaks of nickel carbide. The average particle size of the nickel carbide nanoparticles was likewise 21.1nm, calculated according to the scherrer formula. The content of the nano material C is 24.07%, the content of H is 1.68%, the content of O is 7.92% and the content of Ni is 66.32% after normalization. FIG. 5 is a C1s X ray photoelectron spectrum of the nanocomposite prepared in example 2. After the spectrograms are subjected to peak-by-peak fitting, the oxygen-containing functional groups on the carbon matrix are mainly hydroxyl and carboxyl functional groups, and obvious spectral peaks exist at the positions with the binding energy of 287 eV-290 eV.
Example 3
1) 10.51g (50 mmol) of citric acid monohydrate, 4.64g (50 mmol) of nickel hydroxide and 5.84g (100 mmol) of sodium chloride are weighed 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, placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen, 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, performing suction filtration, and drying a filter cake at 105 ℃ to obtain the oxygen-doped carbon-based nickel carbide nanocomposite material.
Fig. 6 is an XRD pattern of the nanocomposite prepared in example 3. Similar to fig. 4, fig. 6 also shows diffraction peaks of nickel carbide. The average particle size of the nickel carbide nanoparticles was 21.1nm, calculated according to the scherrer formula.
Comparative example 1
Nanocomposite materials were prepared by the method of example 1, except that no sodium chloride was added to the precursor.
Characterization of materials: fig. 7 is an X-ray diffraction pattern of the nanocomposite prepared in comparative example 1. From the figure, only the diffraction peak corresponding to face centered cubic (fcc) Ni and the diffraction peak of NiO can be seen, and there is no corresponding Ni 3 Diffraction peak of C.
Therefore, the alkali metal salt can be used as a stabilizer to promote the generation of nickel carbide, and when the precursor is free of the alkali metal salt, the carbon-based nickel carbide nanocomposite cannot be prepared.
Application example 1
The application example is used for explaining the reaction of catalyzing the hydrogenation of styrene by using the oxygen doped carbon-based nickel carbide nanocomposite as a catalyst.
100mg of solidThe nanocomposite of example 1, 208mg of styrene, 30mL of absolute ethanol were added to the reactor, and H was introduced 2 After 4 times of replacement, the pressure in the reaction kettle is maintained to be 1.0MPa, and the air inlet valve is closed. Stirring, heating to 120 ℃, starting timing, continuously reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking out the product for chromatographic analysis. Reactant conversion and target product selectivity were calculated by the following formulas:
conversion = mass of reacted reactant/amount of reactant added x 100%
Selectivity = target product mass/reaction product mass x 100%
After analysis, the conversion of styrene was 100% and the selectivity to ethylbenzene was 100%.
It can be seen that the composite material of the present invention exhibits a relatively good catalytic activity in hydrogenation reactions.
In summary, the method for pyrolyzing the metal salt precursor is adopted, and the oxygen doped carbon-based nickel carbide nanocomposite is obtained by controlling specific reaction conditions.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (13)
1. The preparation method of the oxygen-doped carbon-based nickel carbide nanocomposite is characterized by comprising the following steps of:
mixing a nickel source, an organic carboxylic acid free of nitrogen and an alkali metal salt to prepare a precursor;
pyrolyzing the precursor in an inert atmosphere to obtain the nanocomposite;
wherein the pyrolysis temperature is 310-340 ℃;
the alkali metal salt is selected from one or more of sodium chloride and potassium chloride;
the molar ratio of the nickel source to the carboxyl in the organic carboxylic acid to the alkali metal salt is 1:2-8:0.1-20.
2. The method of preparing according to claim 1, wherein the step of preparing the precursor comprises:
heating and stirring the nickel source, the organic carboxylic acid without nitrogen and the alkali metal salt in a solvent to form a homogeneous solution, and removing the solvent to obtain the precursor; or (b)
And placing the nickel source and the organic carboxylic acid without nitrogen in a solvent, heating and stirring to form a homogeneous solution, and mixing the solid after removing the solvent with the alkali metal salt to obtain the precursor.
3. The method of claim 1, wherein the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, basic nickel carbonate, and nickel acetate, and the non-nitrogen containing 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.
4. The method according to claim 2, wherein the temperature of the heating and stirring is 30 ℃ to 150 ℃.
5. The method of claim 2, wherein the solvent is selected from one or more of water, alcohols, and N, N-dimethylformamide.
6. The method of preparation of claim 1, wherein the pyrolyzing comprises: heating the precursor to a constant temperature section in an inert atmosphere, and keeping the constant temperature in the constant temperature section;
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.
7. The method of claim 1, further comprising treating the pyrolyzed product with water.
8. An oxygen-doped carbon-based nickel carbide nanocomposite material, characterized in that the nanocomposite material is prepared by the preparation method of any one of claims 1-7, the nanocomposite material comprises an oxygen-doped carbon matrix and nickel carbide nanoparticles supported on the carbon matrix, and a spectral peak exists in a binding energy range of 287 ev-290 ev in a C1s X ray photoelectron spectrum of the nanocomposite material.
9. The nanocomposite of claim 8, wherein the nanocomposite comprises, based on the total mass of the nanocomposite, 15% -50% carbon, 4% -20% oxygen, 1% -4% hydrogen, and 35% -75% nickel.
10. The nanocomposite of claim 8, wherein the nickel carbide nanoparticles have an average particle size of 12nm to 30nm.
11. Use of the oxygen-doped carbon-based nickel carbide nanocomposite according to any of claims 8-10 as a catalyst in catalytic hydrogenation reactions or electrocatalytic reactions.
12. The use according to claim 11, characterized in that the reaction substrate in the catalytic hydrogenation reaction is an organic substance containing a reducible group.
13. The use according to claim 12, 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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