CN112808286A - Cobalt/molybdenum carbide nano catalyst and preparation method and application thereof - Google Patents
Cobalt/molybdenum carbide nano catalyst and preparation method and application thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 69
- 239000010941 cobalt Substances 0.000 title claims abstract description 69
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 69
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 65
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- 238000004321 preservation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- -1 aldehyde ketone Chemical class 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical class ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical class O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
The invention discloses a cobalt/molybdenum carbide nano catalyst and a preparation method and application thereof. (1) Dissolving a cobalt source to obtain a solution A; (2) taking and dissolving a molybdenum source to obtain a solution B; (3) adding the solution A into the solution B, heating for reaction, filtering, washing and drying to obtain a pre-product; (4) grinding the pre-product, respectively carrying out three times of carbonization reactions in the mixed atmosphere of methane and hydrogen after grinding, and then cooling to obtain the cobalt/molybdenum carbide nano catalyst. The application comprises the following steps: the cobalt/molybdenum carbide nano catalyst is used in nitrobenzene hydrogenation reaction. The preparation method is simple, the conditions are easy to control, the raw materials are easy to obtain, the synthesis route is simple, the atom economic efficiency is high, the foundation is laid for controllably synthesizing the cobalt/molybdenum carbide catalyst, the cobalt/molybdenum carbide nano catalyst is used for nitrobenzene hydrogenation reaction, the conversion rate and the selectivity of the catalyst are high, and the cobalt/molybdenum carbide nano catalyst has great application potential in the field of industrial catalyst and fine chemical synthesis.
Description
Technical Field
The invention relates to the technical field of organic synthesis of fine chemicals, in particular to a cobalt/molybdenum carbide nano catalyst and a preparation method and application thereof.
Background
Aniline has been widely used in the pharmaceutical, polymer, dye, pesticide, etc. industries, and hydrogen has been gradually gaining attention as a clean and efficient reducing agent in addition to the conventional reducing agents such as sodium hyposulfite, hydrazine hydrate, etc. However, nitrobenzene hydrogenation reactions often suffer from low selectivity to the desired product and formation of by-products (nitrosobenzenes, hydroxyanilines, etc.). Based on this background, the synthesis of nitrobenzene catalysts with high selectivity and activity has become a hot point of research.
In conventional synthesis processes, such as Au, Pt [ T.Su et al ], ACS Catal, 11(2016) 7844-7854; g.bond et al, Catal.Rev.41(1999), 319-. However, the large-scale application is hindered by factors such as high price, low resource distribution, poor thermal stability and the like. Non-noble metal catalysts are ideal alternatives to noble metals because they are inexpensive and readily available. In particular the transition metals iron, cobalt and nickel [ H.Wei et al, nat. Commun.5(2014) 5631-; tan, Yuan, et al, Angewandte Chemie 56.10(2017):2709-2713] shows great potential in the efficient hydrogenation of nitrobenzene.
Molybdenum carbide is used as a carrier to activate metal in a hydrogenation reaction due to a unique electronic structure, and has a great promotion effect on the activity and stability of the reaction (B.M. Wyvrat et al, ACS Catal.6(2016), 5797-containing 5806), and metal cobalt is usually used as a hydrogenation catalyst of an organic compound, can be used for hydrogenation reduction reaction of compounds containing unsaturated bonds such as aldehyde ketone and the like, and can be used as an effective hydrogenation catalyst. At present, a liquid phase reduction method or a deposition method is mainly used for loading cobalt on a carrier, such as molybdenum carbide, in the method, a cobalt component can be lost in a synthesis process, a synthesis route cannot achieve atom economy, and metal between the molybdenum carbide carrier and the cobalt has weak interaction with the carrier, so that the activity of the molybdenum carbide carrier in the reaction is poor.
Based on the problems, the invention aims to provide an in-situ synthesis cobalt/molybdenum carbide catalyst, a preparation method and application thereof, so as to solve the technical problems and achieve the purpose of further contributing to the actual industrial catalyst requirements and chemical fine synthesis.
Disclosure of Invention
The preparation method has the advantages of simple operation steps, easily controlled preparation conditions, easily obtained raw materials, simple synthesis route, in-situ synthesis and high atom economic efficiency, and lays a foundation for controllably synthesizing the cobalt/molybdenum carbide catalyst; the cobalt/molybdenum carbide nano catalyst synthesized by the preparation method has the characteristics of uniform appearance, stable structure, excellent catalytic reaction performance and the like; the cobalt/molybdenum carbide nano catalyst prepared by the invention can be used as a catalyst for nitrobenzene hydrogenation reaction, and has great application potential in the field of industrial catalyst and fine chemical product synthesis.
The invention is realized by the following technical scheme:
a preparation method of a cobalt/molybdenum carbide nano catalyst comprises the following steps:
(1) dissolving a cobalt source to obtain a solution A;
(2) taking and dissolving a molybdenum source to obtain a solution B;
(3) adding the solution A into the solution B, then heating for reaction, filtering after reaction, washing and drying to obtain a pre-product;
(4) and grinding the pre-product, respectively carrying out three times of carbonization reactions in the mixed atmosphere of methane and hydrogen after grinding, and then cooling to obtain the cobalt/molybdenum carbide nano catalyst.
Further, step (1) is to take Co (NO)3)2·6H2Dissolving O in deionized water and stirring uniformly to obtain solution A.
Further, the solution A contains Co2+The ion concentration is 0.1-0.5 mol/L.
Further, step (2) of taking (NH)4)6Mo7O24·4H2Dissolving the O crystal in deionized water and stirring uniformly to obtain solution B.
Further, Mo in the solution B2+The ion concentration is 0.01-1.0 mol/L.
Further, the solution A is completely added into the solution B in the step (3) and is uniformly stirred, then the solution A is heated to 50-150 ℃ to react for 1-10 hours, the hot solution is filtered after the reaction, then the solution is washed by deionized water, and then the solution is dried for 1-5 hours at 70-90 ℃ to obtain a pre-product; and the volume ratio of the solution A to the solution B is 1: (3-5).
Further, grinding the pre-product in the step (4), heating to 100-500 ℃ in a mixed atmosphere of methane and hydrogen to perform a first carbonization reaction for 20-50 minutes, and cooling to room temperature after the reaction; then heating to the temperature of 200-900 ℃ for a second carbonization reaction for 1-10 hours, and cooling to the room temperature after the reaction; finally, the temperature is raised to 200-900 ℃ again for the third carbonization reaction, the reaction time is 1-10 hours, and the cobalt/molybdenum carbide nano catalyst is obtained after the reaction and the cooling to the room temperature.
Further, the volume ratio of the methane to the hydrogen in the mixed gas of methane and hydrogen is 1: (1-10), and the flow rate of the mixed gas is 1-20 ml/min; the heating rate of the third heating is 0.5-10 ℃/min.
A cobalt/molybdenum carbide nano catalyst is prepared by the preparation method.
The application of the cobalt/molybdenum carbide nano catalyst is characterized in that the cobalt/molybdenum carbide nano catalyst prepared by the preparation method is used in nitrobenzene hydrogenation reaction.
The invention has the beneficial effects that:
the preparation method for synthesizing the cobalt/molybdenum carbide nano catalyst in situ provided by the invention has the advantages of simple preparation process, easily controlled preparation conditions, easily obtained raw materials, simple synthesis route, in-situ synthesis and high atom economic efficiency, and lays a foundation for controllably synthesizing the cobalt/molybdenum carbide catalyst; the cobalt/molybdenum carbide nano catalyst synthesized by the preparation method has the characteristics of uniform appearance, stable structure, excellent catalytic reaction performance and the like; the cobalt/molybdenum carbide nano catalyst prepared by the method is used in nitrobenzene hydrogenation reaction, has high conversion rate and selectivity, and has great application potential in the field of industrial catalyst and fine chemical product synthesis.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a transmission electron microscope image of a cobalt/molybdenum carbide nano-catalyst prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a cobalt/molybdenum carbide nanocatalyst prepared in example 1 of the present invention;
fig. 3 is a graph showing the change of conversion and selectivity of the cobalt/molybdenum carbide nano catalyst prepared in example 1 in the nitrobenzene hydrogenation reaction system along with the reaction time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a cobalt/molybdenum carbide nano catalyst comprises the following steps:
(1) 0.847g (about 0.003mol) of Co (NO) was taken3)2·6H2Adding O (cobalt nitrate hexahydrate) into 20.0ml of deionized water, and uniformly stirring to obtain a solution A;
(2) 5.0g (about 0.004mol) of (NH) was taken4)6Mo7O24·4H2Adding O (ammonium heptamolybdate tetrahydrate) into 80.0ml of deionized water, and uniformly stirring to obtain a solution B;
(3) adding the solution A into the solution B, stirring uniformly, heating to 100 ℃, reacting for 2 hours at the temperature, filtering while the solution is hot after the reaction, washing the filtrate with deionized water, and drying for 2 hours at 80 ℃ to obtain a pre-product;
(4) grinding the obtained pre-product, transferring the ground pre-product into a reaction test tube, heating to 300 ℃ at a heating rate of 5 ℃/min under a methane and hydrogen mixed atmosphere (wherein the volume ratio of methane to hydrogen in the mixed atmosphere is 1: 10, and the flow rate of the mixed gas is 10ml/min), carrying out a first carbonization reaction, keeping the temperature for 30 minutes after the heating is finished, and cooling to room temperature after the reaction; then heating to 500 ℃ at the heating rate of 2 ℃/min for a second carbonization reaction, carrying out heat preservation reaction for 3 hours after the second heating is finished, and cooling to room temperature after the second carbonization reaction; finally, heating to 700 ℃ at the speed of 1 ℃/min for a third carbonization reaction, carrying out heat preservation reaction for 5 hours after the third temperature rise is finished, and cooling to room temperature after the reaction to obtain the cobalt/molybdenum carbide nano catalyst (Co @ Mo)2C)。
Example 2
A preparation method of a cobalt/molybdenum carbide nano catalyst comprises the following steps:
(1) 1.89g (about 0.0065mol) of Co (NO) was taken3)2·6H2Adding O (cobalt nitrate hexahydrate) into 20.0ml of deionized water, and uniformly stirring to obtain a solution A;
(2) 2.0g (about 0.0016mol) of (NH) were taken4)6Mo7O24·4H2Adding O (ammonium heptamolybdate tetrahydrate) into 80.0ml of deionized water, and uniformly stirring to obtain a solution B;
(3) adding the solution A into the solution B, stirring uniformly, heating to 60 ℃, reacting for 10 hours at the temperature, filtering while the solution is hot after the reaction, washing the filtrate with deionized water, and drying for 4 hours at 70 ℃ to obtain a pre-product;
(4) grinding the obtained pre-product, transferring the ground pre-product into a reaction test tube, heating to 100 ℃ at a heating rate of 1 ℃/min under a methane and hydrogen mixed atmosphere (wherein the volume ratio of methane to hydrogen in the mixed atmosphere is 1: 5, and the flow rate of the mixed gas is 5ml/min), carrying out a first carbonization reaction, keeping the temperature for 50 minutes after the heating is finished, and cooling to room temperature after the reaction; then heating to 300 ℃ at the heating rate of 5 ℃/min for a second carbonization reaction, carrying out heat preservation reaction for 5 hours after the second heating is finished, and cooling to room temperature after the second carbonization reaction; finally, heating to 900 ℃ at the speed of 10 ℃/min for a third carbonization reaction, carrying out heat preservation reaction for 3 hours after the third temperature rise is finished, and cooling to room temperature after the reaction to obtain the cobalt/molybdenum carbide nano catalyst (Co @ Mo)2C)。
Example 3
A preparation method of a cobalt/molybdenum carbide nano catalyst comprises the following steps:
(1) 2.87g (about 0.01mol) of Co (NO) was taken3)2·6H2Adding O (cobalt nitrate hexahydrate) into 20.0ml of deionized water, and uniformly stirring to obtain a solution A;
(2) 9.0g (about 0.007mol) of (NH) was taken4)6Mo7O24·4H2Adding O (ammonium heptamolybdate tetrahydrate) into 80.0ml of deionized water and stirring uniformly to obtain the productSolution B;
(3) adding the solution A into the solution B, stirring uniformly, heating to 130 ℃, reacting for 5 hours at the temperature, filtering while the solution is hot after the reaction, washing the filtrate with deionized water, and drying for 3 hours at 90 ℃ to obtain a pre-product;
(4) grinding the obtained pre-product, transferring the ground pre-product into a reaction test tube, heating to 500 ℃ at a heating rate of 10 ℃/min under a methane and hydrogen mixed atmosphere (wherein the volume ratio of methane to hydrogen in the mixed atmosphere is 1: 1, and the flow rate of the mixed gas is 20ml/min), carrying out a first carbonization reaction, keeping the temperature for 20 minutes after the heating is finished, and cooling to room temperature after the reaction; then heating to 800 ℃ at the heating rate of 8 ℃/min for a second carbonization reaction, carrying out heat preservation reaction for 6 hours after the second heating is finished, and cooling to room temperature after the second carbonization reaction; finally, heating to 200 ℃ at the speed of 5 ℃/min for a third carbonization reaction, carrying out heat preservation reaction for 8 hours after the third temperature rise is finished, and cooling to room temperature after the reaction to obtain the cobalt/molybdenum carbide nano catalyst (Co @ Mo)2C)。
Test example 1
The cobalt/molybdenum carbide nano-catalyst (Co @ Mo) prepared in the above example 1 was used2C) The cobalt/molybdenum carbide nanocatalyst (Co @ Mo) prepared in example 1 of the present invention can be seen from FIG. 1, which is shown by the results of the Japanese JEOL 2100 Transmission Electron Microscope (TEM)2C) The components are uniformly distributed, which shows that the cobalt has high dispersity on the molybdenum carbide material and is in the shape of nanoparticles.
Test example 2
The cobalt/molybdenum carbide nano-catalyst (Co @ Mo) prepared in the above example 1 was used2C) And adopting a Japanese physical D/max 2500PC autorotation X-ray diffractometer for analysis, wherein the X-ray is Cu target Ka voltage of 40kV, the current of 100mA, the step length is 0.02 degrees, and the scanning range is 5-80 degrees. The X-ray diffraction pattern of the cobalt/molybdenum carbide nanocatalyst is shown in fig. 2 (in the figure: the abscissa is the angle 2 theta and the unit is DEG (degree), and the ordinate is the diffraction intensity and the unit is a.u (absolute unit)), and it can be seen from fig. 2 that the cobalt/molybdenum carbide nanomaterial is formed into a cobalt/molybdenum carbide nanocatalystIn the successful synthesis, only the characteristic peak of molybdenum carbide appears in fig. 2, and the characteristic peak of cobalt oxide does not appear, which shows that cobalt is highly dispersed on the surface of molybdenum carbide.
Test example 3
The cobalt/molybdenum carbide nano-catalyst (Co @ Mo) prepared in the above example 1 was used2C) And an inductively coupled plasma emission spectrum ICPS-8100 is adopted for analysis, the test condition is that the wavelength of 850nm, the power is 1.8kW, and the frequency is 27.12 MHz. The elemental analysis of the cobalt/molybdenum carbide nanocatalyst is shown in table 1, and it can be seen from table 1 that the cobalt/molybdenum carbide nanomaterial was successfully synthesized, and the molar ratio of the cobalt element to the molybdenum element was 1: 4.
table 1 shows the elemental analysis results of the cobalt/molybdenum carbide nanocatalyst prepared in example 1
| ICP (element) | Mass concentration (mg/L) |
| Co | 72.43 |
| Mo | 471.43 |
Application example 1
The cobalt/molybdenum carbide nanocatalyst (Co @ Mo) prepared in the above example 12C) The method is used for nitrobenzene hydrogenation reaction and specifically comprises the following steps: dispersing 5.0mg of cobalt/molybdenum carbide nano catalyst into 2.0mL of water, then adding 50.0mg of nitrobenzene, adding 2MPa of H2 into a reaction system, heating to 140 ℃, reacting for 4 hours at the temperature, and then extracting and centrifuging by using 10mL of ethyl acetate; the cobalt/molybdenum carbide nanocatalysts prepared in example 1 were then examined for their reactivity with the results shownFIG. 3 is a schematic view; it can be seen from fig. 3 that the selectivity of the catalyst after 4 hours of reaction reaches 100% at 140 ℃, the conversion rate reaches about 93% at 140 ℃, and the conversion rate and the selectivity are high, which indicates that the cobalt/molybdenum carbide nano-catalyst prepared in example 1 of the present invention exhibits excellent catalytic reaction activity.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. The preparation method of the cobalt/molybdenum carbide nano catalyst is characterized by comprising the following steps of:
(1) dissolving a cobalt source to obtain a solution A;
(2) taking and dissolving a molybdenum source to obtain a solution B;
(3) adding the solution A into the solution B, then heating for reaction, filtering after reaction, washing and drying to obtain a pre-product;
(4) and grinding the pre-product, respectively carrying out three times of carbonization reactions in the mixed atmosphere of methane and hydrogen after grinding, and then cooling to obtain the cobalt/molybdenum carbide nano catalyst.
2. The method for preparing the cobalt/molybdenum carbide nano catalyst according to claim 1, wherein Co (NO) is taken in the step (1)3)2·6H2Dissolving O in deionized water and stirring uniformly to obtain solution A.
3. The method for preparing cobalt/molybdenum carbide nano catalyst according to claim 2, wherein Co in the solution A is2+The ion concentration is 0.1-0.5 mol/L.
4. The method for preparing cobalt/molybdenum carbide nano catalyst according to claim 1, wherein the step (2) is to take (NH)4)6Mo7O24·4H2O crystalDissolving the solution in deionized water and stirring to obtain solution B.
5. The method for preparing cobalt/molybdenum carbide nano-catalyst according to claim 4, wherein Mo in the solution B2+The ion concentration is 0.01-1.0 mol/L.
6. The method for preparing cobalt/molybdenum carbide nano catalyst according to claim 1, wherein the solution A is completely added into the solution B in the step (3) and is uniformly stirred, then the solution is heated to 50-150 ℃ to react for 1-10 hours, the hot solution is filtered after the reaction, then the solution is washed by deionized water, and then the solution is dried for 1-5 hours at 70-90 ℃ to obtain a pre-product; and the volume ratio of the solution A to the solution B is 1: (3-5).
7. The method as claimed in claim 1, wherein the step (4) comprises grinding the pre-product, heating to 100-500 ℃ in a mixed atmosphere of methane and hydrogen to perform a first carbonization reaction for 20-50 min, and cooling to room temperature; then heating to the temperature of 200-900 ℃ for a second carbonization reaction for 1-10 hours, and cooling to the room temperature after the reaction; finally, the temperature is raised to 200-900 ℃ again for the third carbonization reaction, the reaction time is 1-10 hours, and the cobalt/molybdenum carbide catalyst is obtained after the reaction and the cooling to the room temperature.
8. The method for preparing a cobalt/molybdenum carbide nano catalyst according to claim 7, wherein the volume ratio of the methane to the hydrogen in the mixed gas of the methane and the hydrogen is 1: (1-10), and the flow rate of the mixed gas is 1-20 ml/min; the heating rate of the third heating is 0.5-10 ℃/min.
9. A cobalt/molybdenum carbide nanocatalyst prepared by the preparation method of any one of claims 1 to 8.
10. The application of the cobalt/molybdenum carbide nano catalyst is characterized in that the cobalt/molybdenum carbide catalyst prepared by the preparation method of any one of claims 1 to 8 is used in nitrobenzene hydrogenation reaction.
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