CN115537840A - Composite electro-catalytic material and preparation method thereof - Google Patents
Composite electro-catalytic material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 239000010411 electrocatalyst Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
-
- 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
- C25B11/065—Carbon
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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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
This patent relates to a Mo 2+ The doped vanadium carbide/carbon cloth composite electrocatalytic material and the preparation method thereof have the general formula: v 1‑x C/CC:xMo 2+ Wherein 0 is<x is less than or equal to 0.05, and belongs to the technical field of novel clean energy and functional materials. The V is 1‑x C/CC:xMo 2+ The composite material is loaded with V on CC in situ 1‑x C:xMo 2+ And calcining to obtain the catalyst. The composite material has the characteristics of excellent hydrogen production performance by electrocatalytic decomposition of water, good acid and alkali resistance and the like. Wherein, under alkaline conditions, V 0.96 C/CC:0.4Mo 2+ Compared with pure CC, the overpotential of the method is reduced by 45.22 percent, and the Tafel slope is reduced by 58.44 percent; the overpotential is reduced by 17.36 percent compared with VC/CC, and the Tafel slope is reduced43.90 percent. The electrocatalyst prepared by the invention has important application potential in the aspect of novel high-efficiency clean energy.
Description
Technical Field
The invention relates to Mo 2+ A doped vanadium carbide/carbon cloth (VC/CC) composite electro-catalytic material and a preparation method thereof belong to the technical field of novel clean energy and functional materials.
Background
Over the past century, economic development has continued to increase in energy demand, with demand being projected to reach 16 trillion watts in 2010 to 24 trillion watts in 2030 and even 31 trillion watts in 2050. However, the reserves of traditional energy sources limit the continuous increase of consumption and also bring about a series of serious environmental problems of carbon dioxide and sulfur dioxide emission. Therefore, there is a need to find new renewable, environmentally friendly alternative energy sources. Among a plurality of alternative energy sources, hydrogen energy has very high energy density, and combustion products only contain water, so that secondary pollution is avoided; meanwhile, hydrogen can exist in the forms of gas, liquid or solid metal hydride and the like, and can meet the application requirements of different fields, so that the hydrogen becomes the most promising alternative clean energy. However, most of the hydrogen production industry currently uses hydrocarbons from fossil energy sources to reform the hydrocarbons by different methods to obtain hydrogen energy. These processes not only consume a large amount of fossil energy, but also have low conversion efficiency due to the limited raw materials, and also emit a large amount of carbon dioxide during the reforming process. Therefore, numerous researchers are dedicated to developing a hydrogen production process with easily available raw materials, simple process, high yield and environmental protection. In the hydrogen production scheme reported at present, the hydrogen production by electrolyzing water is concerned due to the characteristics of zero pollution, high product purity and the like.
The electrolytic water hydrogen evolution reaction is a four-electron reaction, in order to improve the efficiency of the electrolytic water process and reduce the energy consumption, the electrolytic water process is usually completed by an electrocatalyst, the currently reported platinum-based catalyst shows excellent performance in the electrocatalytic hydrogen evolution reaction, but the storage capacity of platinum (Pt) in the nature is small, and the cost is high, so that the large-scale industrial application of the platinum-based catalyst is not facilitated. Therefore, it is imperative to find a low cost, manageable, high inventory and efficient stable alternative catalyst. Vanadium Carbide (VC) is important for industrial applications because of its excellent high temperature strength, high chemical and thermal stability. As a transition metal carbide, the cheaper VC has the electronic property similar to Pt and excellent hydrogen adsorption performance, and can be used as a novel hydrogen evolution electrocatalyst.
Some studies of VC as an electrocatalyst are reported in the technology, for example, chinese patent document with publication number CN108598505A reports that a composite material VC/CC with VC as a substrate and loaded is prepared as an electrocatalyst, a hydrothermal method is adopted to grow VC on the CC, however, the hydrothermal growth method cannot ensure the growth uniformity of VC grains, and the overpotential is low; chinese patent publication No. CN109592683A reports an electrocatalyst with ultra-small vanadium carbide embedded in carbon nanotube material, which introduces iron, cobalt, and nickel as metal catalysts formed by VC, however, the product is powder, and the powder needs to be loaded on the electrode, which is not suitable for large-scale application on the electrolytic water electrode.
Therefore, how to prepare an electrocatalyst with large-scale application and high stability is very important.
Disclosure of Invention
The first technical problem solved by the present invention is to prepare an electrocatalyst material with good homogeneity.
V 1-x C/CC:xMo 2+ The composite material comprises the following components: mo is sprayed and dried 2+ The doped VC is loaded on CC, and the loading is formed by spraying 250ml of solution.
Invention V 1-x C/CC:xMo 2+ The composite material can provide V due to the mesh structure of the carbon cloth 1-x C:xMo 2+ Loading site of (a) by spray drying to give V 1-x C:xMo 2+ Precursor particles are uniformly loaded on the CC with a net structure, and the CC can inhibit V 1-x C:xMo 2+ Agglomeration is an advantage.
The second technical problem solved by the invention is to provide a method for preparing V on a large scale 1-x C/CC:xMo 2+ A method of electrocatalyst material.
V 1-x C/CC:xMo 2+ Preparation method of electrocatalytic materialThe method comprises the following steps:
a. taking dicyanodiamine (C) 2 H 4 N 4 ) Ammonium metavanadate (NH) 4 VO 3 ) And polyvinyl alcohol in 250ml of deionized water to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, continuously heating at 85 ℃ until the polyvinyl alcohol is completely dissolved, then cooling to room temperature, and adding a certain amount of ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) and is dissolved uniformly.
b. And c, uniformly spraying and granulating the solution obtained in the step a on a Carbon Cloth (CC) by using a small spray dryer.
c. Transferring the CC loaded particles obtained in the step b into a tubular furnace in argon atmosphere, and heating for the first time to obtain a precursor; heating for the second time to obtain V 1-x C/CC:xMo 2+ A composite electrocatalytic material.
In one embodiment, in step a, the amount x of ammonium molybdate tetrahydrate is 0.01 to 0.05; preferably, the amount is 0.04.
In one embodiment, in step b, the inlet temperature of the spray drying is 160 to 180 ℃; preferably, the inlet temperature is 180 ℃.
In one embodiment, in step b, the outlet temperature of the spray drying is 60 to 80 ℃; preferably, the outlet temperature is 70 ℃.
In one embodiment, in step b, the feed flow rate for spray drying is 220 to 250ml/h; preferably, the feed flow rate is 240ml/h.
In one embodiment, in step c, the first heating temperature is 200 to 400 ℃; preferably, the calcination temperature is 300 ℃.
In one embodiment, in step c, the second heating temperature is 800 to 1100 ℃; preferably, the elevated temperature calcination temperature is 1100 ℃.
In one embodiment, in step c, the second heating and holding time is 1 to 3 hours; preferably, the temperature-rising calcination time is 2 hours.
The invention has the beneficial effects that:
1. the invention is as describedV of 1-x C/CC:xMo 2+ The composite electro-catalytic material takes CC as a substrate of the self-supporting electrode by virtue of good conductive performance of the CC; by virtue of its good network structure, can provide attachment sites for electrocatalysts; and then the electrocatalyst is uniformly attached to the surface of the CC in a spray drying mode.
2. The invention prominently uses Mo 2+ And (3) doping, namely successfully doping the V site in the VC/CC matrix partially, and further improving the electrocatalytic performance of VC.
3. The vanadium source used in the preparation method of the invention has wide source and simple and convenient operation.
Drawings
FIG. 1 shows V obtained in example 1 0.99 C/CC:0.01Mo 2+ XRD pattern of the composite.
FIG. 2 shows V obtained in example 1 0.99 C/CC:0.01Mo 2+ LSV profile of the composite.
FIG. 3 shows V obtained in example 1 0.99 C/CC:0.01Mo 2+ Taffy slope plot of the composite.
FIG. 4 shows V obtained in example 2 0.98 C/CC:0.02Mo 2+ XRD pattern of the composite.
FIG. 5 shows V obtained in example 2 0.98 C/CC:0.02Mo 2+ LSV profile of the composite.
FIG. 6 shows V obtained in example 2 0.98 C/CC:0.02Mo 2+ Taffy slope plot of the composite.
FIG. 7 shows V obtained in example 3 0.96 C/CC:0.04Mo 2+ XRD pattern of the composite.
FIG. 8 shows V obtained in example 3 0.96 C/CC:0.04Mo 2+ LSV profile of the composite.
FIG. 9 shows V obtained in example 3 0.96 C/CC:0.04Mo 2+ Taffy slope plot of the composite.
Detailed Description
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Electrocatalytic testing
The electrocatalytic hydrogen evolution reaction test is carried out in a KOH solution with the concentration of 1M, V 1-x C/CC:xMo 2+ The size of the composite material is 1.2 x 1.3cm, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a glassy carbon electrode clamp is used for clamping V 1-x C/CC:xMo 2+ The composite material was the working electrode and the electrochemical performance test was performed on an electrochemical workstation DH7000 (the east hua test).
Example 1
The synthesis process comprises the following steps:
1) Weighing 1.76g C 2 H 4 N 4 、0.4632g NH 4 VO 3 And 0.05g of polyvinyl alcohol in 250mL of deionized water, placing the mixed solution in a magnetic stirrer at 85 ℃, continuously heating and stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, and adding 0.0071g of (NH) into the mixed solution 4 ) 6 Mo 7 O 24 ·4H 2 And O, uniformly stirring for later use.
2) Placing the CC to be used in the middle of a spray dryer, spraying the solution obtained in the step 1), wherein the inlet temperature is 170 ℃, the outlet temperature is 60 ℃, the feeding flow rate is 250ml/h, and finally, collecting the CC loaded with the powder for later use.
3) Placing the sample obtained in the step 2) into a corundum crucible, transferring the corundum crucible into a tube furnace for calcination, heating to 200 ℃ for calcination for 2 hours, heating to 800 ℃ again for calcination for 3 hours, and cooling along with the furnace to obtain CC (namely V) loaded with black solid products 0.99 C/CC:0.01Mo 2+ An electrocatalytic composite material.
FIG. 1 shows V obtained in example 1 of the present invention 0.99 C/CC:0.01Mo 2+ The XRD pattern of the electrocatalytic composite material can be known from FIG. 1: example 1 prepared V 0.99 C/CC:0.01Mo 2+ The XRD result of (1) is consistent with the standard diffraction peak, and no other impurity peak is generated.
FIG. 2 shows V obtained in example 1 of the present invention 0.99 C/CC:0.01Mo 2+ The LSV diagram of the composite electrocatalytic material under alkaline conditions is shown in fig. 2: v obtained in example 1 0.99 C/CC:0.01Mo 2+ The current density of the composite electro-catalysis material is 10mAcm -2 Over-potential of time is385mV。
FIG. 3 shows V obtained in example 1 of the present invention 0.99 C/CC:0.01Mo 2+ The Tafel diagram of the composite electro-catalytic material under alkaline conditions is shown in FIG. 3: v obtained in example 1 0.99 C/CC:0.01Mo 2+ The Tafel slope of the composite electrocatalytic material is 71.38mV dec -1 。
Example 2
The synthesis process comprises the following steps:
1) Weighing 1.76g C 2 H 4 N 4 、0.4586g NH 4 VO 3 And 0.05g of polyvinyl alcohol in 250mL of deionized water, placing the mixed solution in a magnetic stirrer at 85 ℃, continuously heating and stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, and adding 0.0142g (NH) of the mixed solution into the mixed solution 4 ) 6 Mo 7 O 24 ·4H 2 And O, uniformly stirring for later use.
2) Placing the CC to be used in the middle of a spray dryer, spraying the solution obtained in the step 1), wherein the inlet temperature is 160 ℃, the outlet temperature is 80 ℃, the feeding flow rate is 220ml/h, and finally, collecting the CC loaded with the powder for later use.
3) Placing the sample obtained in the step 2) into a corundum crucible, transferring the corundum crucible into a tubular furnace for calcination, heating to 150 ℃ for calcination for 2 hours, heating to 1000 ℃ again for calcination for 1 hour, and cooling along with the furnace to obtain CC (namely V) loaded with a black solid product 0.98 C/CC:0.02Mo 2+ An electrocatalytic composite material.
FIG. 4 shows V obtained in example 2 of the present invention 0.98 C/CC:0.02Mo 2+ The XRD pattern of the electrocatalytic composite material can be known from FIG. 4: example 2 preparation of V 0.98 C/CC:0.02Mo 2+ The XRD result of (a) is consistent with the standard diffraction peak, and no other impurity peak appears.
FIG. 5 shows V obtained in example 2 of the present invention 0.98 C/CC:0.02Mo 2+ The LSV diagram of the composite electrocatalytic material under alkaline conditions is shown in fig. 5: v obtained in example 2 0.98 C/CC:0.02Mo 2+ The current density of the composite electro-catalytic material is 10mA cm -2 The overpotential at this time was 372mV.
FIG. 6 is a graph showing the results obtained in example 2 of the present inventionV 0.98 C/CC:0.02Mo 2+ The Tafel diagram of the composite electro-catalytic material under alkaline conditions is shown in FIG. 6: v obtained in example 2 0.98 C/CC:0.02Mo 2+ The Tafel slope of the composite electro-catalytic material is 65.95mV dec -1 。
Example 3
The synthesis process comprises the following steps:
1) Weighing 1.76g C 2 H 4 N 4 、0.4492g NH 4 VO 3 And 0.05g of polyvinyl alcohol in 250mL of deionized water, placing the mixed solution in a magnetic stirrer at 85 ℃, continuously heating and stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, and adding 0.0284g (NH) into the mixed solution 4 ) 6 Mo 7 O 24 ·4H 2 And O, uniformly stirring for later use.
2) Placing the CC to be used in the middle of a spray dryer, spraying the solution obtained in the step 1), wherein the inlet temperature is 180 ℃, the outlet temperature is 70 ℃, the feeding flow rate is 240ml/h, and finally, collecting the CC loaded with the powder for later use.
3) Placing the sample obtained in the step 2) into a corundum crucible, transferring the corundum crucible into a tube furnace for calcination, heating to 300 ℃ for calcination for 2h, heating to 1100 ℃ again for calcination for 2h, and cooling along with the furnace to obtain CC (namely V) loaded with a black solid product 0.96 C/CC:0.04Mo 2+ An electrocatalytic composite material.
FIG. 7 shows V obtained in example 3 of the present invention 0.96 C/CC:0.04Mo 2+ The XRD pattern of the electrocatalytic composite material can be known from FIG. 3: example 3 prepared V 0.96 C/CC:0.04Mo 2+ The XRD result of (1) is consistent with the standard diffraction peak, and no other impurity peak is generated.
FIG. 8 shows V obtained in example 3 of the present invention 0.96 C/CC:0.04Mo 2+ The LSV diagram of the composite electrocatalytic material under alkaline conditions is shown in fig. 8: v obtained in example 3 0.96 C/CC:0.04Mo 2+ The current density of the composite electro-catalytic material is 10mA cm -2 The overpotential is 338mV, and the electrocatalytic performance is better.
FIG. 9 shows V obtained in example 3 of the present invention 0.96 C/CC:0.04Mo 2+ Composite electrocatalysisThe Tafel plot of the chemical substance under alkaline conditions is shown in FIG. 9: v obtained in example 3 0.96 C/CC:0.04Mo 2+ The Tafel slope of the composite electro-catalytic material is 46.4mV dec -1 。
Claims (10)
1. Mo 2+ The doped vanadium carbide/carbon cloth (VC/CC) composite electrocatalytic material is characterized in that: in the composite electrocatalytic material, V 1-x C/CC:xMo 2+ Wherein 0 is<x≤0.05。
2. V according to claim 1 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps:
a. taking dicyanodiamine (C) 2 H 4 N 4 ) Ammonium metavanadate (NH) 4 VO 3 ) And polyvinyl alcohol in 250ml of deionized water to obtain a mixed solution, placing the mixed solution on a magnetic stirrer, continuously heating at 85 ℃ until the polyvinyl alcohol is completely dissolved, then cooling to room temperature, and adding a certain amount of ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) and is dissolved uniformly.
b. And c, uniformly spraying and granulating the solution obtained in the step a on a Carbon Cloth (CC) by using a small spray dryer.
c. Transferring the CC loaded particles obtained in the step b into a tubular furnace in argon atmosphere, and heating for the first time to obtain a precursor; heating for the second time to obtain V 1-x C/CC:xMo 2+ A composite electrocatalytic material.
3. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step a, the dosage x of the ammonium molybdate tetrahydrate is 0.01-0.05.
4. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step b, the inlet temperature of the spray dryer is 160-180 ℃.
5. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step b, the outlet temperature of the spray dryer is 60-80 ℃.
6. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step b, the feeding speed of the spray dryer is 220-250 ml/h.
7. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step c, the first heating temperature is 200-400 ℃.
8. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step c, the second heating temperature is 800-1100 ℃.
9. V according to claim 2 1-x C/CC:xMo 2+ The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: in the step c, the second heating and heat preservation time is 1-3 h.
10. V according to claim 1 1-x C/CC:xMo 2+ Composite electrocatalytic material or V prepared by the preparation method of any one of claims 2 to 11 1-x C/CC:xMo 2+ The application of the composite electro-catalytic material is characterized in that the composite electro-catalytic material is used as a catalyst for an electrolytic water hydrogen evolution reaction.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248682A (en) * | 1979-09-27 | 1981-02-03 | Prototech Company | Carbon-cloth-based electrocatalytic gas diffusion electrodes, assembly and electrochemical cells comprising the same |
| KR20070067265A (en) * | 2005-12-23 | 2007-06-28 | 주식회사 두산 | Catalyst support, and manufacturing method of membrane electrode assembly including catalyst support and fuel cell using the same |
| US20100279117A1 (en) * | 2009-05-04 | 2010-11-04 | Meecotech, Inc. | Electrode active composite materials and methods of making thereof |
| WO2013182535A1 (en) * | 2012-06-06 | 2013-12-12 | Basf Se | Method for producing nitrogen-doped transition metal catalysts and use thereof for the electrochemical oxidation of s(iv) compounds |
| US20140080694A1 (en) * | 2011-03-01 | 2014-03-20 | GM Global Technology Operations LLC | Synthesis of nanosized metal carbides on graphitized carbon as supporting materials for electrocatalysts |
| CN108598505A (en) * | 2018-05-09 | 2018-09-28 | 陕西科技大学 | A kind of preparation method and product of vanadium carbide/carbon cloth composite material |
| CN109967105A (en) * | 2019-04-22 | 2019-07-05 | 陕西科技大学 | A kind of preparation method of Co, Mo codope vanadium carbide |
| CN112382513A (en) * | 2020-10-01 | 2021-02-19 | 桂林理工大学 | Preparation method of double-ion water system energy storage device |
| CN112877728A (en) * | 2020-12-10 | 2021-06-01 | 上海航天智慧能源技术有限公司 | Novel platinum-carbon-layer-containing loaded foam nickel electrolytic water electrode and preparation method thereof |
| US20220025531A1 (en) * | 2020-07-23 | 2022-01-27 | Shaanxi University Of Science & Technology | Ultra-thin carbon-layer composite material modified by nickel nanoclusters and vanadium carbide particles and its preparation method and application |
| CN114457365A (en) * | 2022-01-20 | 2022-05-10 | 成都理工大学 | Pt-Ni composite material, preparation method thereof and application thereof as catalyst for hydrogen production by electrolyzing water |
-
2022
- 2022-10-12 CN CN202211246616.8A patent/CN115537840A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248682A (en) * | 1979-09-27 | 1981-02-03 | Prototech Company | Carbon-cloth-based electrocatalytic gas diffusion electrodes, assembly and electrochemical cells comprising the same |
| KR20070067265A (en) * | 2005-12-23 | 2007-06-28 | 주식회사 두산 | Catalyst support, and manufacturing method of membrane electrode assembly including catalyst support and fuel cell using the same |
| US20100279117A1 (en) * | 2009-05-04 | 2010-11-04 | Meecotech, Inc. | Electrode active composite materials and methods of making thereof |
| US20140080694A1 (en) * | 2011-03-01 | 2014-03-20 | GM Global Technology Operations LLC | Synthesis of nanosized metal carbides on graphitized carbon as supporting materials for electrocatalysts |
| WO2013182535A1 (en) * | 2012-06-06 | 2013-12-12 | Basf Se | Method for producing nitrogen-doped transition metal catalysts and use thereof for the electrochemical oxidation of s(iv) compounds |
| CN108598505A (en) * | 2018-05-09 | 2018-09-28 | 陕西科技大学 | A kind of preparation method and product of vanadium carbide/carbon cloth composite material |
| CN109967105A (en) * | 2019-04-22 | 2019-07-05 | 陕西科技大学 | A kind of preparation method of Co, Mo codope vanadium carbide |
| US20220025531A1 (en) * | 2020-07-23 | 2022-01-27 | Shaanxi University Of Science & Technology | Ultra-thin carbon-layer composite material modified by nickel nanoclusters and vanadium carbide particles and its preparation method and application |
| CN112382513A (en) * | 2020-10-01 | 2021-02-19 | 桂林理工大学 | Preparation method of double-ion water system energy storage device |
| CN112877728A (en) * | 2020-12-10 | 2021-06-01 | 上海航天智慧能源技术有限公司 | Novel platinum-carbon-layer-containing loaded foam nickel electrolytic water electrode and preparation method thereof |
| CN114457365A (en) * | 2022-01-20 | 2022-05-10 | 成都理工大学 | Pt-Ni composite material, preparation method thereof and application thereof as catalyst for hydrogen production by electrolyzing water |
Non-Patent Citations (2)
| Title |
|---|
| 王玥;朱婧;黄德顺;岳国宗;赵鹏翔;林金辉;: "Pd-NPs@alkyne-PVA/GO复合材料制备及其电催化析氢性能", 工业催化, no. 07, 15 July 2020 (2020-07-15), pages 61 - 67 * |
| 章冬云;吴曦;马紫峰;LEVI T.THAMPSON;: "基于碳化钼的燃料电池阴极催化剂的制备及其作用机理", 催化学报, no. 04, 15 April 2009 (2009-04-15), pages 319 - 322 * |
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