CN111013634A - Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof - Google Patents
Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111013634A CN111013634A CN201911368280.0A CN201911368280A CN111013634A CN 111013634 A CN111013634 A CN 111013634A CN 201911368280 A CN201911368280 A CN 201911368280A CN 111013634 A CN111013634 A CN 111013634A
- Authority
- CN
- China
- Prior art keywords
- mon
- catalyst
- comoo
- nanosheet array
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002135 nanosheet Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 229910018864 CoMoO4 Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 11
- 239000011684 sodium molybdate Substances 0.000 claims description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000006260 foam Substances 0.000 abstract description 10
- 239000010411 electrocatalyst Substances 0.000 abstract description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a non-noble metal Co/MoN composite nano array catalyst and a preparation method and application thereof, the catalyst takes foam nickel as a carrier, a rough porous nanosheet structure growing on the foam nickel is adopted, the interfaces of MoN and metal simple substance Co, namely Co/MoN interfaces, are randomly distributed in the nanosheets, the catalyst has excellent hydrogen evolution and oxygen evolution reaction catalytic performance, is a bifunctional electrocatalyst with hydrogen evolution and oxygen evolution catalytic activity, and tests show that the product has excellent catalytic activity and catalytic stability, and is a noble metal electrocatalyst Pt and RuO2Is an inexpensive alternative to (1).
Description
Technical Field
The invention relates to the technical field of electrocatalytic water decomposition, in particular to a non-noble metal Co/MoN composite nanosheet array catalyst and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Hydrogen has been considered as a substitute for traditional fossil fuels due to its high energy density and non-polluting nature of the product. In addition, hydrogen is an important raw material for synthesizing ammonia, methanol, hydrochloric acid and the like, and is widely applied to the fields of electronic industry, metallurgical industry, aerospace and the like. At present, about 4450 million tons of hydrogen come from various ways all over the world, such as petrochemical catalytic cracking and water electrolysis, wherein the hydrogen production amount of the petrochemical catalytic cracking is up to 96%, and the hydrogen production by the petrochemical catalytic cracking can generate impure hydrogen gas and toxic emissions, thereby causing serious influence on the environment. The water produced by electrocatalysis decomposition only takes hydrogen and oxygen as products, the characteristic of environmental protection is widely regarded, and with the application of novel power generation facilities such as solar power generation, wind power generation, hydroelectric power generation and the like, the electric energy generated by new energy sources can be used as a power supply for electrocatalysis decomposition of water, so that the technology which is considered to be high energy consumption for producing hydrogen by electrolysis of water in the past draws high attention of the scientific field again.
The inventors have found that at present, for the two half-reactions that constitute the electrocatalytic decomposition of water, namely the hydrogen evolution reaction and the oxygen evolution reaction, the noble metals Pt and RuO2The most efficient electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction respectively, but the scarcity and high price of noble metals Pt and Ru limit the large-scale application of the electrocatalysts as the catalysts.
Disclosure of Invention
Therefore, the invention aims to provide a non-noble metal Co/MoN composite nanosheet array catalyst, and a preparation method and application thereof. The catalyst is CoMoO attached to a foamed nickel support4The precursor nanosheet array forms a Co/MoN composite nanosheet array through air annealing and annealing under the ammonia gas condition, the catalyst nanosheet is of a rough porous structure, the active center metal simple substance Co/MoN interface is randomly distributed in the nanosheet, the catalyst nanosheet has high capability of separating out hydrogen and oxygen through electrocatalytic decomposition under the alkaline condition, and the catalyst nanosheet has good stabilityQualitative and simple preparation method, low price, easy regulation, excellent performance, easy large-scale production and suitability for industrial water electrolysis hydrogen production.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the invention, the invention provides a non-noble metal Co/MoN composite nano array catalyst, specifically, a rough porous nano sheet array structure growing on foamed nickel by taking the foamed nickel as a carrier, wherein interfaces of MoN and metal simple substance Co, namely Co/MoN interfaces, are randomly distributed in the nano sheet array.
The active center (reaction active site) of the non-noble metal Co/MoN composite nano array catalyst is a Co/MoN interface, and in the invention, the crystal faces are represented by (002) and (200) of MoN and (111) of metal simple Co.
Compared with the conventional carrier in the field, the non-noble metal Co/MoN composite nano-array catalyst has the advantages that the foamed nickel is used as the carrier, the nano-sheet array structure grown on the carrier is of a three-dimensional structure, a large number of reaction active sites, namely Co/MoN interfaces, can be exposed, and the performance of the catalyst is further enhanced.
In a second aspect of the present invention, the present invention provides a method for preparing the non-noble metal Co/MoN composite nanoarray catalyst described in the first aspect above, the method comprising: using foamed nickel as carrier, and growing CoMoO on it by hydrothermal method4Forming a CoMoO by annealing the precursor nanosheet array in air4Then carrying out ammonia annealing treatment on the bimetallic oxide nanosheet array to obtain a Co/MoN composite nanosheet array; wherein, CoMoO4And annealing and nitriding the nanosheet array by ammonia gas to form an interface structure of MoN and a metal Co simple substance.
In some embodiments of the present invention, the preparation method of the non-noble metal Co/MoN composite nano array catalyst comprises the following steps:
cobalt nitrate and sodium molybdate are used as raw materials, and foamed nickel is adoptedFirstly, putting foamed nickel into a lining of a hydrothermal reaction kettle, then controlling the molar ratio of cobalt nitrate to sodium molybdate to be (0.5-2): 1, preparing a uniform solution, transferring the uniform solution into the hydrothermal reaction kettle, reacting for 1-10 hours at 110-200 ℃, taking out, and drying to obtain CoMoO4A precursor nanosheet array;
mixing CoMoO4Transferring the precursor nanosheet array into a tube furnace, annealing under the air condition, heating to 300-900 ℃ for reacting for 1-12 hours at the heating rate of 0.5-20 ℃/min to obtain CoMoO4A nanosheet array;
annealing under ammonia gas condition to obtain CoMoO4And reacting the nanosheets at the temperature of 300-800 ℃ for 0.5-12 hours, wherein the heating rate is 0.5-20 ℃/min, and thus the non-noble metal Co/MoN composite nanosheet array catalyst can be obtained.
In some embodiments of the invention, in the CoMoO4In the preparation process of the precursor nanosheet array, the molar ratio of cobalt nitrate to sodium molybdate is 0.5-1: 1 or 1-2: 1, and preferably 1: 1.
In the embodiment of the invention, the inventor finds that when the molar ratio of the cobalt nitrate to the sodium molybdate is controlled to be (0.5-2): 1, particularly 0.5-1: 1, and particularly 1:1, the growth condition on the foamed nickel is better and more uniform, and the Co/MoN composite nanosheet array catalyst has better oxygen evolution and hydrogen evolution activity.
In some embodiments of the invention, in the CoMoO4In the preparation process of the precursor nanosheet array, the reaction temperature in the hydrothermal reaction kettle is 110-160 ℃, and preferably 140 ℃; the reaction time in the hydrothermal reaction kettle is 4-10 hours, preferably 10 hours.
In some embodiments of the invention, in the CoMoO4In the preparation process of the nanosheet array, the annealing temperature is 500-600 ℃ under the air condition, the annealing temperature is preferably 500 ℃, and the annealing time is 1-5 hours, and preferably 2 hours.
In some embodiments of the present invention, the temperature increase rate of the annealing under air condition is 0.5-10 ℃/min, preferably 2 ℃/min.
In some embodiments of the present invention, the annealing temperature under ammonia gas is 400-500 ℃, preferably 400 ℃, and the annealing time is 0.5-3 hours, preferably 2 hours.
The heating rate of annealing under the ammonia gas condition is 0.5-5 ℃/min, preferably 2 ℃/min.
In an embodiment of the invention, the CoMoO is annealed under ammonia conditions4The Co/MoN composite nanosheet array can form a large number of interfaces of metal simple substance Co and MoN, and the interfaces are used as active sites to remarkably enhance the activity of the Co/MoN composite nanosheet array catalyst in catalyzing electrolyzed water and remarkably enhance the stability.
In some embodiments of the invention, compared with a catalyst which is only subjected to air annealing and is not subjected to ammonia annealing, the overpotential for oxygen evolution and hydrogen evolution of the Co/MoN composite nanosheet array catalyst prepared by the method is greatly reduced, and the Co/MoN composite nanosheet array catalyst shows good performance of catalytically decomposing water to generate oxygen and hydrogen.
According to some embodiments of the invention, the Co/MoN composite nanosheet array catalyst prepared by sequentially performing air annealing and ammonia annealing at the annealing temperature of 500-600 ℃ for 1-5 hours under the air condition, at the annealing temperature of 400-500 ℃ under the ammonia condition and for the annealing time of 0.5-3 hours has better performance of catalyzing and decomposing water to generate oxygen and hydrogen, and particularly has better effect when the annealing temperature rise rate under the air condition is 0.5-10 ℃/min and the annealing temperature rise rate under the ammonia condition is 0.5-5 ℃/min. In particular, in some embodiments of the present invention, the performance of the prepared catalyst is optimal when the annealing temperature is 500 ℃ under air conditions, the annealing time is 2 hours, the annealing temperature is 400 ℃ under ammonia conditions, the annealing time is 2 hours, and the annealing temperature rise rate is 2 ℃/min.
In a third aspect of the invention, the invention also provides the application of the non-noble metal Co/MoN composite nano array catalyst in the first aspect in the field of water electrocatalytic decomposition; in particular to the application of the water electrolysis reaction under the alkaline condition to separate out hydrogen and/or oxygen.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes cheap cobalt nitrate and sodium molybdate as raw materials, and generates the bimetallic oxide CoMoO attached to the foam nickel carrier through simple hydrothermal reaction and annealing treatment in the air4The Co/MoN compound nanosheet array formed by annealing the nanosheet array by ammonia gas has obviously improved catalytic performance of hydrogen evolution and oxygen evolution reactions, becomes a bifunctional electrocatalyst with hydrogen evolution and oxygen evolution catalytic activity, and tests show that the product has excellent catalytic activity and catalytic stability, and becomes a noble metal electrocatalyst Pt and RuO2Is an inexpensive alternative to (1).
(1) The invention anneals CoMoO under the condition of ammonia gas4The nanosheet array, namely the Co/MoN composite nanosheet array obtained, forms a large number of interfaces of metal simple substance Co and MoN, so that the activity of catalyzing electrolyzed water is obviously enhanced, and the stability is obviously enhanced;
(2) foam nickel is used as a carrier, so that the foam nickel grows into a three-dimensional nanosheet array structure, a large number of active sites can be further exposed, and the performance of the material is further enhanced;
(3) the raw materials for synthesizing the material are wide and cheap, the synthesis method is simple and convenient, the controllability is strong, and the method is suitable for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a flow chart of the preparation of an electrocatalyst according to the invention.
FIG. 2 shows Co/MoN composite, CoMoO4XRD patterns of (1) and MoN, Co and CoMoO4Comparison of standard cards of nickel foam.
FIG. 3: a is a scanning electron microscope image of a lower multiple of the sample catalyst prepared in example 1 of the present invention, b is a scanning electron microscope image of a higher multiple of the sample catalyst prepared in example 1 of the present invention, c is a transmission electron microscope image of the sample catalyst prepared in example 1 of the present invention, and d is a high-resolution transmission electron microscope image of the sample catalyst prepared in example 1 of the present invention.
FIG. 4: a is a hydrogen evolution performance diagram when an electrochemical linear sweep voltammetry test is performed in example 3 of the present invention, b is an oxygen evolution performance diagram when an electrochemical linear sweep voltammetry test is performed in example 4 of the present invention, c is a hydrogen evolution stability test diagram when an electrochemical chronoamperometry test is performed in example 5 of the present invention, and d is a oxygen evolution stability test diagram when an electrochemical chronoamperometry test is performed in example 6 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1Preparation of non-noble metal Co/MoN composite nanosheet array catalyst
① cobalt nitrate hexahydrate and sodium molybdate dihydrate are used as raw materials, the cobalt nitrate and the sodium molybdate dihydrate are respectively 1.5mM, the molar ratio of the cobalt nitrate to the sodium molybdate is controlled to be 1, after the cobalt nitrate and the sodium molybdate dihydrate are uniformly stirred, the solution is transferred to a hydrothermal reaction kettle, after the solution reacts for 10 hours at the temperature of 140 ℃, the solution is taken out after being cooled to the room temperature, and is dried to obtain CoMoO4A precursor nanosheet array;
② the dried precursor is transferred to a tube furnace at 2 deg.C/mi in airThe speed of n is increased to 500 ℃, annealed for 2 hours, taken out after being reduced to room temperature to obtain the CoMoO4The nano-sheet array has an XRD pattern shown in figure 2;
③ CoMoO to be taken out4And (3) transferring the nanosheet array to a tubular furnace, introducing ammonia gas, raising the temperature to 400 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, and taking out the nanosheet array after the temperature is reduced to room temperature to obtain the Co/MoN composite nanosheet array catalyst, wherein the XRD (X-ray diffraction) pattern of the catalyst is shown in figure 2, and the scanning electron microscope pattern, the transmission electron microscope pattern and the high-resolution transmission electron microscope pattern of the catalyst are shown in figure 3.
Example 2Preparation of non-noble metal Co/MoN composite nanosheet array catalyst
① cobalt nitrate hexahydrate and sodium molybdate dihydrate are used as raw materials, the cobalt nitrate and the sodium molybdate dihydrate are respectively 1.5mM, the molar ratio of the cobalt nitrate to the sodium molybdate is controlled to be 1, after the cobalt nitrate and the sodium molybdate dihydrate are uniformly stirred, the solution is transferred to a hydrothermal reaction kettle, after the solution reacts for 10 hours at the temperature of 140 ℃, the solution is taken out after being cooled to the room temperature, and is dried to obtain CoMoO4A precursor nanosheet array;
② drying the CoMoO4Transferring the precursor nanosheet array to a tube furnace, raising the temperature to 600 ℃ at the speed of 2 ℃/min under the air condition, annealing for 2 hours, cooling to room temperature, and taking out to obtain the CoMoO4A nanosheet array;
③ CoMoO to be taken out4And transferring the nanosheet array to a tubular furnace, introducing ammonia gas, raising the temperature to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, and taking out the nanosheet array after the temperature is reduced to room temperature to obtain the Co/MoN composite nanosheet array catalyst, wherein an XRD (X-ray diffraction) diagram is as shown in figure 2.
Example 3
The measurement was carried out with the catalyst of example 1, and a working curve for the hydrogen evolution catalytic activity in a 1M KOH solution was plotted:
① testing with electrochemical workstation in three-electrode system, cutting the material attached to the nickel foam to a suitable size, and then clamping on an electrode clamp to make it penetrate into 1M KOH solution with the size of 0.5 x 0.5cm, using the electrode as working electrode, then using carbon rod electrode as auxiliary electrode, Hg/HgO electrode as reference electrode;
② the material performance was tested by linear sweep voltammetry with initial voltage set at-0.6V, end voltage at-1.6V, sweep rate at 2mV/s, and the working curve was recorded with the results shown in FIG. 4a4Compared with the example 1, the hydrogen evolution overpotential of the nanosheet array (obtained in the step ② in the example 1 without ammonia annealing treatment) is greatly reduced, and the Co/MoN nanosheet array has good performance of catalytically decomposing water to evolve hydrogen.
Example 4
The measurement was carried out with the catalyst of example 1, and a working curve of the oxygen evolution catalytic activity in a 1M KOH solution was plotted:
① testing with electrochemical workstation in three-electrode system, cutting the material attached to the nickel foam to a suitable size, and then clamping on an electrode clamp to make it penetrate into 1M KOH solution with the size of 0.5 x 0.5cm, using the electrode as working electrode, then using carbon rod electrode as auxiliary electrode, Hg/HgO electrode as reference electrode;
② linear sweep voltammetry was used to test the material properties, initial voltage was 0V, final voltage was 1V, sweep rate was 2mV/s, the working curve was recorded, the result is shown in FIG. 4b4Compared with the example 1, the oxygen evolution overpotential of the nanosheet array (obtained in the step ② in the example 1 without ammonia annealing treatment) is greatly reduced, and the good performance of catalyzing and decomposing water and oxygen evolution of the Co/MoN nanosheet array is shown.
Example 5
The measurement was carried out with the catalyst of example 1, and a working curve for the stability to hydrogen evolution in 1M KOH solution was plotted:
① testing with electrochemical workstation in three-electrode system, cutting the material attached to the foam nickel to proper size, and clamping on electrode clamp to make it penetrate into 1M KOH solution with the size of 1 x 1cm, using the electrode as working electrode, using carbon rod electrode as auxiliary electrode, and using Hg/HgO electrode as reference electrode;
② detecting the material performance by linear sweep voltammetry with initial voltage of-0.6V, end voltage of-1.6V and sweep rate of 2mV/s, recording to obtain initial working curve, detecting the material stability by cyclic voltammetry with set voltage of-0.8V to-1.2V and 1000 cycles, detecting the material performance by linear sweep voltammetry with initial voltage of-0.6V, end voltage of-1.6V and sweep rate of 2mV/s after the cyclic voltammetry is finished, recording to obtain working curve after 1000 cycles, and summarizing the working curves before and after cyclic voltammetry to a graph to check the stability, the result is shown in figure 4 c.
According to the graph shown in fig. 4c, the working curve after 1000 cycles of circulation is basically completely overlapped with the initial working curve, which shows that the Co/MoN composite nanosheet array catalyst of the present invention has excellent hydrogen evolution stability.
Example 6
The measurement was carried out with the catalyst of example 1, and a working curve for the stability to oxygen evolution in 1M KOH solution was plotted:
① testing with electrochemical workstation in three-electrode system, cutting the material attached to the foam nickel to proper size, and clamping on electrode clamp to make it penetrate into 1M KOH solution with the size of 1 x 1cm, using the electrode as working electrode, using carbon rod electrode as auxiliary electrode, and using Hg/HgO electrode as reference electrode;
② detecting the material performance by linear sweep voltammetry with initial voltage of 0V, end voltage of 1V and sweep rate of 2mV/s, recording to obtain initial working curve, detecting the material stability by cyclic voltammetry with set voltage of 0.3V-0.8V and 1000 cycles, detecting the material performance by linear sweep voltammetry with initial voltage of 0V, end voltage of 1V and sweep rate of 2mV/s after cyclic voltammetry, recording to obtain working curve after 1000 cycles, summarizing the working curves before and after cyclic voltammetry to a graph to check the stability, and the result is shown in FIG. 4 d.
According to the graph shown in fig. 4d, the working curve after 1000 cycles of circulation is basically overlapped with the initial working curve, which shows that the Co/MoN composite nanosheet array catalyst of the present invention has excellent oxygen evolution stability.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A non-noble metal Co/MoN composite nano array catalyst takes foamed nickel as a carrier and is a rough porous nano sheet array structure grown on the foamed nickel, and the interfaces of MoN and metal simple substance Co, namely Co/MoN interfaces, are randomly distributed in the nano sheet array.
2. The non-noble metal Co/MoN composite nanoarray catalyst of claim 1, wherein the catalyst has a Co/MoN interface as an active center, wherein the Co/MoN is represented by (002) and (200) crystal planes of MoN and (111) crystal plane of elemental metal Co.
3. A method of making the non-noble metal Co/MoN composite nanoarray catalyst of claim 1 or 2, comprising: using foamed nickel as carrier, and growing CoMoO on it by hydrothermal method4Forming a CoMoO by annealing the precursor nanosheet array in air4And then carrying out ammonia annealing treatment on the bimetallic oxide nanosheet array to obtain a Co/MoN composite nanosheet array.
4. A method according to claim 3, characterized in that the method comprises the steps of:
cobalt nitrate and sodium molybdate are used as raw materials to control the cobalt nitrateThe molar ratio of the sodium molybdate to the sodium molybdate is (0.5-2): 1, the uniform solution is prepared and then transferred to a hydrothermal reaction kettle, the reaction is carried out for 1-10 hours at the temperature of 110-200 ℃, and the solution is taken out and dried to obtain the CoMoO4A precursor nanosheet array;
mixing CoMoO4Transferring the precursor nanosheet array into a tube furnace, annealing under the air condition, heating to 300-900 ℃ for reacting for 1-12 hours at the heating rate of 0.5-20 ℃/min to obtain CoMoO4A nanosheet array;
annealing under ammonia gas condition to obtain CoMoO4And reacting the nanosheets at the temperature of 300-800 ℃ for 0.5-12 hours, wherein the heating rate is 0.5-20 ℃/min, and thus the non-noble metal Co/MoN composite nanosheet array catalyst can be obtained.
5. The method of claim 4, wherein the CoMoO is4In the preparation process of the precursor nanosheet array, the molar ratio of cobalt nitrate to sodium molybdate is 0.5-1: 1 or 1-2: 1, and preferably 1: 1.
6. The method of claim 4, wherein the CoMoO is4In the preparation process of the precursor nanosheet array, the reaction temperature in the hydrothermal reaction kettle is 110-160 ℃, and preferably 140 ℃;
preferably, the reaction time in the hydrothermal reaction kettle is 4-10 hours, preferably 10 hours.
7. The method of claim 4, wherein the CoMoO is4In the preparation process of the nanosheet array, the annealing temperature is 500-600 ℃ under the air condition, and the annealing time is 1-5 hours, preferably 2 hours;
preferably, the annealing temperature rise rate is 0.5-5 ℃/min, preferably 2 ℃/min.
8. The method according to claim 4, wherein the annealing temperature under ammonia gas is 400-500 ℃ and the annealing time is 0.5-3 hours, preferably 2 hours;
preferably, the annealing temperature rise rate is 0.5-5 ℃/min, preferably 2 ℃/min.
9. Use of the non-noble metal Co/MoN composite nanoarray catalyst of claim 1 or 2 in the field of electrocatalytic decomposition of water.
10. Use of the non-noble metal Co/MoN composite nanoarray catalyst of claim 1 or 2 in reactions in which water is electrolyzed under alkaline conditions to evolve hydrogen and/or oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911368280.0A CN111013634A (en) | 2019-12-26 | 2019-12-26 | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911368280.0A CN111013634A (en) | 2019-12-26 | 2019-12-26 | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111013634A true CN111013634A (en) | 2020-04-17 |
Family
ID=70214735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911368280.0A Withdrawn CN111013634A (en) | 2019-12-26 | 2019-12-26 | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111013634A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807418A (en) * | 2020-06-24 | 2020-10-23 | 浙江大学 | Amorphous high-conductivity quaternary metal nitride and preparation method thereof |
| CN113403641A (en) * | 2021-05-19 | 2021-09-17 | 中山大学 | Electrocatalytic material and preparation method and application thereof |
| CN113502503A (en) * | 2021-07-05 | 2021-10-15 | 福州大学 | Self-supporting transition metal nitride composite material, preparation method and application of self-supporting transition metal nitride composite material in electrocatalytic hydrogen evolution |
| CN114457388A (en) * | 2022-01-25 | 2022-05-10 | 南阳师范学院 | Electrolyzed water oxygen evolution anode and preparation method thereof |
-
2019
- 2019-12-26 CN CN201911368280.0A patent/CN111013634A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807418A (en) * | 2020-06-24 | 2020-10-23 | 浙江大学 | Amorphous high-conductivity quaternary metal nitride and preparation method thereof |
| CN111807418B (en) * | 2020-06-24 | 2021-07-27 | 浙江大学 | Amorphous high-conductivity quaternary metal nitride and preparation method thereof |
| CN113403641A (en) * | 2021-05-19 | 2021-09-17 | 中山大学 | Electrocatalytic material and preparation method and application thereof |
| CN113502503A (en) * | 2021-07-05 | 2021-10-15 | 福州大学 | Self-supporting transition metal nitride composite material, preparation method and application of self-supporting transition metal nitride composite material in electrocatalytic hydrogen evolution |
| CN114457388A (en) * | 2022-01-25 | 2022-05-10 | 南阳师范学院 | Electrolyzed water oxygen evolution anode and preparation method thereof |
| CN114457388B (en) * | 2022-01-25 | 2024-02-13 | 南阳师范学院 | Electrolytic water oxygen evolution anode and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111013634A (en) | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof | |
| CN108425131B (en) | Nickel-molybdenum-based alloy loaded on foamed nickel, amorphous carbon system, and preparation method and application thereof | |
| CN109628951B (en) | Nickel sulfide hydrogen evolution electrocatalyst and preparation method and application thereof | |
| CN112108149A (en) | Preparation method of electrocatalytic material, corresponding material and use method | |
| CN110127655B (en) | Method for preparing biomass carbon-loaded cobalt phosphide electrode material by one-step calcination method | |
| CN110538657B (en) | Iron-nickel layered double hydroxide and preparation method and application thereof | |
| CN109585861B (en) | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode | |
| CN109585856B (en) | Preparation method of dual-functional cobalt sulfide and sulfur and nitrogen doped carbon in-situ composite electrode | |
| CN109759066B (en) | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| CN109939707B (en) | Cobaltous phosphide @ nickel tungstate core-shell heterojunction material and preparation method and application thereof | |
| CN113684503B (en) | N-GO @ Co-Ni12P5-Ni3P/NCF composite electrode material and preparation method thereof | |
| CN112553643B (en) | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application | |
| CN114150341A (en) | Transition metal selenide electrocatalytic material and preparation method and application thereof | |
| CN113668008A (en) | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof | |
| CN110721720B (en) | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof | |
| CN114086202B (en) | Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production | |
| CN113355687B (en) | Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof | |
| CN112779550B (en) | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof | |
| CN114481188A (en) | Preparation method of surface nitrogen-doped electrode | |
| CN110947408B (en) | Iron monatomic catalyst and preparation method and application thereof | |
| CN114457373B (en) | Preparation method and application of monatomic material with Ni-N2+2 stereo configuration active sites | |
| CN114232017B (en) | Silver selenide nano catalyst and preparation method and application thereof | |
| CN115057479B (en) | CoAl (cobalt aluminum alloy) 2 O 4 Preparation method of electrocatalytic material and application of ENRR thereof | |
| CN115029709B (en) | Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200417 |
|
| WW01 | Invention patent application withdrawn after publication |