CN118028858A - Preparation method of molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst - Google Patents
Preparation method of molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst Download PDFInfo
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- CN118028858A CN118028858A CN202410126832.1A CN202410126832A CN118028858A CN 118028858 A CN118028858 A CN 118028858A CN 202410126832 A CN202410126832 A CN 202410126832A CN 118028858 A CN118028858 A CN 118028858A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 74
- 239000006260 foam Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 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 22
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 17
- 239000011609 ammonium molybdate Substances 0.000 claims description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims description 17
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 239000007853 buffer solution Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- -1 phosphides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SPOMEWBVWWDQBC-UHFFFAOYSA-K tripotassium;dihydrogen phosphate;hydrogen phosphate Chemical compound [K+].[K+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O SPOMEWBVWWDQBC-UHFFFAOYSA-K 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
Classifications
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- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of electrochemistry and catalysts, and particularly relates to a preparation method of a molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst. The preparation method comprises the following steps: (1) preparation of molybdenum-carbon-oxygen-foam nickel precursor; (2) Preparing the molybdenum dioxide/carbon/foam nickel composite electrocatalytic hydrogen evolution material. The molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst prepared by the invention has regular morphology, large specific surface area, higher electrocatalytic hydrogen evolution activity and stability, and can efficiently catalyze the electrolysis hydrogen evolution of water in neutral electrolyte.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and catalysts, and particularly relates to a preparation method of a molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Background
Because hydrogen energy has high energy density and the combustion product is water, sulfur dioxide, carbon dioxide and other polluted gases are not generated, the hydrogen energy is an ideal candidate energy, and the electrolyzed water is widely paid attention as a pollution-free technology capable of producing hydrogen and oxygen. At present, the theoretical voltage of hydrogen production by water electrolysis is 1.23V, and the theoretical power consumption is 3.54kWh/Nm 3. However, the actual working voltage of the process is 2.0-2.2V, and the actual power consumption is 4.5-5kWh/Nm 3, which becomes a bottleneck for restricting the industrialized development of the technology.
The most widely used hydrogen production catalysts for water electrolysis in the water electrolysis research at present are platinum noble metal simple substances such as iridium (Ir), rhodium (Rh), palladium (Pd) and platinum (Pt), and the like, because noble metal elements show higher electron transmission capacity, smaller overpotential and more proper free energy for hydrogen atom adsorption during water electrolysis catalysis, but the rare and expensive noble metal yield needs to be noticed, which directly leads to the increase of the cost of the produced hydrogen, and the reason becomes one of the bottlenecks for restricting the industrial development of the technology.
The performance of the electrolytic water hydrogen production is different under the action of different catalysts, so that high-efficiency electrocatalyst materials are needed for obtaining high-purity and high-efficiency hydrogen energy. The most studied catalyst materials today are mainly based on transition metal compounds such as carbides, phosphides, selenides, oxides, sulfides, etc. The d orbit of the outermost electron layer of the transition metal atom is easy to generate a hole and is suitable for the adsorption process of hydrogen atoms, so that simple substances, alloys and compounds of the transition metal element become the main choice for designing and searching new alternative noble metal hydrogen evolution catalysts. The molybdenum dioxide has been shown to have good hydrogen and oxygen evolution performance due to the superiority of the structure and the performance, and is a good bifunctional catalyst.
Under different electrolytes, the effect of hydrogen production by water electrolysis is also different. Acidic electrolytes (such as sulfuric acid) are one of the most effective electrolytes for electrocatalysis because they provide high concentrations of protons/hydrate as reactants. However, the acidic electrolyte can generate corrosive acid mist, pollute hydrogen and corrode the electrolytic tank. Industrial cells often use alkaline electrolytes, such as 20-30% aqueous potassium hydroxide. While alkaline electrolytes help produce high purity hydrogen gas, they also present other problems, for example, electrolytic cells employing alkaline electrolytes require expensive anion exchange membranes that must be stable under alkaline conditions and have minimal gas crossover. In addition, there is a need for electrocatalysts that are stable in strong alkaline electrolytes.
A possible way to solve the drawbacks of acidic or alkaline electrolytes is to use neutral electrolytes, which have a series of advantages: (1) They are mild and much less corrosive, thus minimizing the corrosion of the water cell; (2) The electrocatalyst does not need to work under the condition of extreme pH, and the selection range of the proper electrocatalyst is greatly enlarged under the condition of neutrality; (3) The battery stack used in the neutral electrolyte is more environment-friendly and safer. The use of neutral electrolytes may therefore significantly reduce the overall cost of industrial scale hydrogen production.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst, and the hydrogen evolution catalyst prepared by the method can be used for efficiently performing electrocatalytic hydrolysis hydrogen evolution in neutral electrolyte, so that the cost of noble metal and the defects of acidic/alkaline electrolyte in the prior art are overcome, and the catalyst has excellent catalytic performance and simultaneously has practical and economic benefits.
The invention solves the problems by the following technical proposal:
the invention provides a preparation method of a molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst, which comprises the following steps:
(1) Adding ammonium molybdate and trimesic acid into deionized water, fully and uniformly stirring, adding foam nickel, performing hydrothermal reaction at 160-200 ℃ for 20-26 hours, and cooling and drying to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) reacting the molybdenum-carbon-oxygen-foam nickel precursor for 2-5 hours at 190-220 ℃ in an inert atmosphere, heating to 560-610 ℃ and calcining for 4-7 hours to obtain the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Further, in the step (1), the molar ratio of the ammonium molybdate to the trimesic acid is 0.9: (0.7-1.2).
Further, in the step (1), the deionized water is added in an amount of 10 to 15ml per 1mmol of ammonium molybdate.
Further, in the step (1), when the ammonium molybdate is fed in an amount of less than 1mmol, the specification of the added foam nickel is 2.0cm multiplied by 3.0cm (the weight is 0.28-0.35 g), and the added foam nickel is 1eq; on this basis, every 1mmol of ammonium molybdate is added, 1eq of foam nickel is added.
Further, in the step (1), the stirring time is 5-10min.
In the step (1), the foam nickel is firstly washed by absolute ethyl alcohol for 5-10min, washed by deionized water, then washed by dilute hydrochloric acid with the concentration of 0.3-0.4mol/L for 3min, washed by deionized water, and naturally dried to obtain the foam nickel sheet with the specification of 2.0cm multiplied by 3.0 cm.
Further, in the step (2), the inert atmosphere is nitrogen and/or argon atmosphere, and the flow rate is preferably 15-20mL/min.
Further, in the step (2), the reaction temperature is preferably 200℃and the calcination temperature is preferably 600 ℃.
The invention also provides the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst prepared by the method, which has a rod-shaped structure with the diameter of 1-2 mu m, can provide rich specific surface area and further improve the electrocatalytic hydrogen evolution activity.
The invention also provides an application of the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst prepared by the method in hydrogen evolution of electrolyzed water, and the catalyst can be used as a catalytic material for hydrogen evolution of electrolyzed water.
Further, the electrolyte in the hydrogen evolution of the electrolyzed water is a neutral electrolyte, preferably a potassium hydrogen phosphate-potassium dihydrogen phosphate buffer solution with the pH value of 7, under the electrolytic system, the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst can be used as a working electrode, a calomel electrode is used as a reference electrode, and a graphite electrode is used as a counter electrode.
The invention has the beneficial effects that:
(1) The invention uses trimesic acid as a carbon source, ammonium molybdate as a molybdenum source, foamed nickel as a substrate, a precursor is obtained by a hydrothermal method, and then sintering carbonization is carried out under the protection of inert gas atmosphere to obtain the electrocatalytic hydrogen evolution composite catalyst.
(2) According to the invention, the foam nickel is used as a substrate, a small amount of active elements such as non-metallic carbon are compounded with molybdenum dioxide, and the synergistic effect of the doped elements is utilized to fully expose the active sites of the molybdenum dioxide and reduce the adsorption energy of various reaction intermediates, so that the electrocatalytic hydrogen evolution performance of the material is optimized, a catalyst for high-efficiency electrolysis of water to produce hydrogen, which has low overpotential and relatively low price in neutral electrolyte, is prepared, the threshold of electrocatalytic hydrogen evolution application is reduced, and the application of clean energy is promoted.
(3) The molybdenum dioxide/carbon/foam nickel composite material prepared by the invention has a bar-shaped micron structure, and can enrich the specific surface area, thereby improving the catalytic performance.
Drawings
Fig. 1: scanning electron microscopy of molybdenum dioxide/carbon/foamed nickel composite hydrogen evolution catalyst in example 1.
Fig. 2: x-ray powder diffraction pattern of molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst of example 1 before and after 30 hours of hydrogen production by catalytic electrolysis of water.
Fig. 3: linear sweep voltammetry plots of electrolytic hydrogen evolution of molybdenum dioxide/carbon/nickel foam composite hydrogen evolution catalyst in neutral electrolyte in example 1.
Fig. 4: potentiostatic current profile of the molybdenum dioxide/carbon/nickel foam composite hydrogen evolution catalyst of example 1 for electrolytic hydrogen evolution in neutral electrolyte.
Detailed Description
The present invention will be further described with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto. The methods, such as those commonly used in the art, referred to herein are not specifically described and the reagents, such as those specifically described, are commercially available.
Example 1:
(1) Adding 0.90mmol of ammonium molybdate and 0.70mmol of trimesic acid into a hydrothermal reaction kettle, adding 12ml of distilled water, fully magnetically stirring for 5min, placing foam nickel with the specification of 2.0cm multiplied by 3.0cm (about 0.30 g), reacting in an oven at 180 ℃ for 24 hours, cooling to room temperature, fully washing with deionized water, and naturally airing to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) putting the molybdenum-carbon-oxygen-foam nickel precursor into a porcelain boat, transferring the porcelain boat into a tube furnace, and reacting at 200 ℃ for 2 hours and 600 ℃ for 5 hours under the nitrogen atmosphere to obtain the black molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Example 2:
(1) Adding 0.90mmol of ammonium molybdate and 0.80mmol of trimesic acid into a hydrothermal reaction kettle, adding 12ml of distilled water, fully magnetically stirring for 5min, placing into a foam nickel with the specification of 2.0cm multiplied by 3.0cm (about 0.30 g), reacting for 24 hours at 180 ℃ in an oven, cooling to room temperature, fully washing with deionized water, and naturally airing to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) putting the molybdenum-carbon-oxygen-foam nickel precursor into a porcelain boat, transferring the porcelain boat into a tube furnace, and reacting at 200 ℃ for 2 hours and 600 ℃ for 5 hours under the nitrogen atmosphere to obtain the black molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Example 3:
(1) Adding 0.80mmol of ammonium molybdate and 0.70mmol of trimesic acid into a hydrothermal reaction kettle, adding 12ml of distilled water, fully magnetically stirring for 5min, placing foam nickel with the specification of 2.0cm multiplied by 3.0cm (about 0.28 g), reacting in an oven at 180 ℃ for 24 hours, cooling to room temperature, fully washing with deionized water, and naturally airing to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) putting the molybdenum-carbon-oxygen-foam nickel precursor into a porcelain boat, transferring the porcelain boat into a tube furnace, and reacting at 200 ℃ for 2 hours and 600 ℃ for 5 hours under the nitrogen atmosphere to obtain the black molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Example 4:
(1) Adding 0.70mmol of ammonium molybdate and 0.70mmol of trimesic acid into a hydrothermal reaction kettle, adding 12ml of distilled water, fully magnetically stirring for 5min, placing foam nickel with the specification of 2.0cm multiplied by 3.0cm (about 0.29 g), reacting in an oven at 180 ℃ for 24 hours, cooling to room temperature, fully washing with deionized water, and naturally airing to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) putting the molybdenum-carbon-oxygen-foam nickel precursor into a porcelain boat, transferring the porcelain boat into a tube furnace, and reacting at 200 ℃ for 2 hours and 600 ℃ for 5 hours under the nitrogen atmosphere to obtain the black molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
Example 5:
(1) Adding 0.90mmol of ammonium molybdate and 1.20mmol of trimesic acid into a hydrothermal reaction kettle, adding 12ml of distilled water, fully magnetically stirring for 5min, placing foam nickel with the specification of 2.0cm multiplied by 3.0cm (about 0.35 g), reacting in an oven at 180 ℃ for 24 hours, cooling to room temperature, fully washing with deionized water, and naturally airing to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) putting the molybdenum-carbon-oxygen-foam nickel precursor into a porcelain boat, transferring the porcelain boat into a tube furnace, and reacting at 200 ℃ for 2 hours and 600 ℃ for 5 hours under the nitrogen atmosphere to obtain the black molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
The molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst prepared in the examples 1-5 is applied to neutral electrolyte electrolyzed water hydrogen evolution, and electrochemical tests are carried out, specifically: the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst is used as a working electrode, a calomel electrode is used as a reference electrode, a graphite rod is used as a counter electrode, and the electrolyte is a potassium hydrogen phosphate-potassium dihydrogen phosphate buffer solution with pH=7.0. The resulting curve is IR compensated. The hydrogen evolution overpotential test results at a current density of 10mAcm -2 are shown in Table 1 below.
Table 1: performance of molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst
It can be seen from table 1 that the molar ratio between ammonium molybdate and trimesic acid is 0.90:0.70, reacting for 24 hours at 180 ℃ to obtain a molybdenum-carbon-oxygen-foam nickel precursor, reacting for 2 hours at 200 ℃ and reacting for 5 hours at 600 ℃ to obtain the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst with the most excellent electrocatalytic hydrogen evolution performance.
FIG. 1 is a scanning electron microscope image of a molybdenum dioxide/carbon/nickel foam composite hydrogen evolution catalyst of example 1, which can be seen to have a rod-like structure with a diameter of 1-2 μm; FIG. 2 is an X-ray powder diffraction chart of the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst of example 1 before hydrogen generation by catalytic electrolysis and after hydrogen generation for 30 hours, which demonstrates the structure and structural stability thereof; FIG. 3 is a linear sweep voltammetry graph of the electrolytic hydrogen evolution of the molybdenum dioxide/carbon/nickel foam composite hydrogen evolution catalyst in neutral electrolyte in example 1, which can be seen to have excellent catalytic electrolyzed water hydrogen evolution performance; fig. 4 is a potentiostatic current curve chart of the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst in example 1 for electrolytic hydrogen evolution in neutral electrolyte, and it can be seen that the catalyst has strong stability.
It will be understood that the above embodiments are further illustrative of the present invention and are not intended to limit the scope of the invention, and that all other modifications and variations which may be obtained without the inventive effort by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst is characterized by comprising the following steps of:
(1) Adding ammonium molybdate and trimesic acid into deionized water, fully and uniformly stirring, adding foam nickel, performing hydrothermal reaction at 160-200 ℃ for 20-26 hours, and cooling and drying to obtain a molybdenum-carbon-oxygen-foam nickel precursor;
(2) And (3) reacting the molybdenum-carbon-oxygen-foam nickel precursor for 2-5 hours at 190-220 ℃ in an inert atmosphere, heating to 560-610 ℃ and calcining for 4-7 hours to obtain the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst.
2. The method for preparing the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (1), the molar ratio of the ammonium molybdate to the trimesic acid is 0.9: (0.7-1.2).
3. The method for preparing a molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (1), the addition amount of deionized water is 10-15ml per 1mmol of ammonium molybdate.
4. The method for preparing the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (1), when the ammonium molybdate feed is less than 1mmol, the added foam nickel has a specification of 2.0cm x 3.0cm and a weight of 0.28-0.35g, which is recorded as 1eq; on this basis, every 1mmol of ammonium molybdate is added, 1eq of foam nickel is added.
5. The method for preparing the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (1), the stirring time is 5-10min.
6. The method for preparing the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (1), the foam nickel is firstly ultrasonically cleaned by absolute ethyl alcohol for 5-10min, then ultrasonically cleaned by dilute hydrochloric acid with the concentration of 0.3-0.4mol/L for 3min after being washed by deionized water, and then naturally dried to obtain foam nickel sheets with the specification of 2.0cm multiplied by 3.0cm after being washed by deionized water.
7. The method for preparing the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 1, wherein in the step (2), the inert atmosphere is a nitrogen and/or argon atmosphere.
8. A molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst prepared by the method of any one of claims 1-7.
9. Use of the molybdenum dioxide/carbon/foam nickel composite hydrogen evolution catalyst according to claim 8 in the hydrogen evolution of electrolyzed water.
10. The use according to claim 9, characterized in that the electrolyte for hydrogen evolution of electrolyzed water is a buffer solution with ph=7.
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