CN111514912A - Three-dimensional Co-doped WP2Nanosheet array electrocatalyst and preparation method thereof - Google Patents
Three-dimensional Co-doped WP2Nanosheet array electrocatalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 57
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052786 argon Inorganic materials 0.000 claims abstract description 27
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
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- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
- UYRCYAHUJKWJDF-UHFFFAOYSA-N P.P.[W] Chemical compound P.P.[W] UYRCYAHUJKWJDF-UHFFFAOYSA-N 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
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- 238000004321 preservation Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011159 matrix material Substances 0.000 claims description 3
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- 239000002071 nanotube Substances 0.000 claims description 2
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 4
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
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- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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Abstract
The invention provides three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of: (1) placing the conductive substrate material in a polytetrafluoroethylene reaction kettle containing a mixed solution of ethanol, oxalic acid, tungsten hexachloride and cobalt chloride, carrying out solvothermal reaction for 6-12h at the temperature of 100-220 ℃, and sintering in a muffle furnace to obtain Co-doped WO3A nanosheet array; (2) sodium hypophosphite is used as a phosphorus source, and vacuum gas is subjected to double temperature controlIn-situ phosphorization reduction method is used in an atmosphere tube furnace, under argon environment, cobalt-doped tungsten trioxide nanosheet array on conductive substrate material is phosphorized and reduced into cobalt-doped tungsten diphosphide nanosheet array, and Co-doped WP is obtained2The nano-sheet array electrocatalytic hydrogen evolution electrode material. Three-dimensional Co-doped WP prepared by the method2The nano-sheet array electrode material has larger exposed specific surface area, higher electrocatalytic hydrogen evolution activity and stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis and hydrogen evolution electrode materials, and particularly relates to three-dimensional Co-doped WP (WP)2Nanosheet array electrocatalyst and to the three-dimensional Co-doped WP2A preparation method of a nanosheet array electrocatalyst.
Background
With the development of society, people face the problems of continuous consumption of fossil energy (petroleum, coal, natural gas and the like) and increasingly serious environmental pollution, so that the development of renewable energy (solar energy, hydrogen energy, hydroenergy, tidal energy, wind energy, biomass energy and the like) arouses great interest, and the advantages of zero hydrogen energy carbon footprint, high energy density and the like are widely concerned and researched. The hydrogen production process by electrolyzing water in a plurality of hydrogen production technologies is simple, environment-friendly and pollution-free, and accords with the strategy of sustainable development, so the method has great application prospect.
The most studied non-noble metal electrocatalysts in recent years have mainly focused on transition metal compounds (Fe, Co, Ni, W, Mo, etc.), among which Transition Metal Phosphides (TMPs) have been extensively studied for their high mechanical strength, electrical conductivity and stability. In addition, most hydrogen evolution electrocatalysts are powders, require high molecular polymer binders, Nafion or PTFE, to be effectively immobilized on the electrode, which may increase the series resistance or reduce the active sites, hindering electron diffusion, and thus inhibiting the activity of the catalyst. In view of this, there is a need to provide a hydrogen evolution active electrode material with high electrocatalytic activity.
Disclosure of Invention
The invention aims to provide three-dimensional Co-doped WP2Nanosheet array electrocatalystThe preparation method solves the problems of few reaction active sites and low catalytic activity of the existing electrocatalyst.
The second purpose of the invention is to provide three-dimensional Co-doped WP prepared by the method2A nanosheet array electrocatalyst.
The first purpose of the invention is realized by the following technical scheme:
three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of:
(1) placing the conductive substrate material in a polytetrafluoroethylene reaction kettle containing a mixed solution of ethanol, oxalic acid, tungsten hexachloride and cobalt chloride, carrying out solvothermal reaction for 6-12h at the temperature of 100-220 ℃, and sintering in a muffle furnace to obtain Co-doped WO3A nanosheet array;
(2) in the method, sodium hypophosphite is used as a phosphorus source, and an in-situ phosphorization reduction method is used in a double-temperature-control vacuum atmosphere tube furnace, under the argon environment, a cobalt-doped tungsten trioxide nanosheet array on a conductive substrate material is phosphorized and reduced into a cobalt-doped tungsten diphosphide nanosheet array, so that Co-doped WP (tungsten phosphide) is obtained2The nano-sheet array electrocatalytic hydrogen evolution electrode material.
The method firstly prepares a cobalt-doped tungsten trioxide nanosheet array with a three-dimensional structure on a conductive substrate material with a self-supporting three-dimensional nanostructure through a solvothermal method, and then prepares three-dimensional Co-doped WP (tungsten trioxide) which grows on the conductive substrate material in an interlaced manner through an in-situ phosphorization reduction method2A nanosheet array material. The self-supporting three-dimensional nanostructures on the conductive substrate not only provide a large electrochemically active surface area, but also accelerate electron transport and enhance gas evolution.
The preparation method of the invention can be further improved as follows:
volume of ethanol in the mixed solution: 10-60mL, and the mass of oxalic acid is: 0.1-1g, mass of tungsten hexachloride: 0.1-0.5g, mole percent of cobalt chloride (Co: W): 0.5 to 20 percent.
In the step (1), the muffle furnace sintering heating rate is 1-5 ℃/min, the temperature is raised to 400-600 ℃, and sintering is carried out for 1-5 h.
Performing hydrophilic treatment on the conductive matrix material by using nitric acid before performing solvothermal reaction in the step (1), and then performing ultrasonic cleaning in acetone, deionized water and ethanol respectively.
Further, each ultrasonic cleaning time was 20 min.
The conductive substrate material is carbon cloth, carbon paper, FTO, carbon nanotube, TiO2A nanotube.
The mass of the sodium hypophosphite in the step (2) is 1-5 g.
The argon in the step (2) is argon with the purity of 99.99 percent.
In the step (2), in-situ phosphorization reduction is carried out in a double-temperature-control vacuum atmosphere tube furnace, and the specific operation is as follows: placing sodium hypophosphite in a quartz boat in a central heating zone at the upstream of the two-temperature zone tube furnace, and doping the Co obtained in the step (1) with WO3The nano-sheet array is arranged on another quartz boat which is positioned in a central heating zone at the downstream of the double-temperature zone tube furnace; introducing argon to remove air, heating the downstream central heating zone to 800 ℃ at the temperature rise rate of 2-10 ℃/min under the atmospheric pressure, simultaneously heating the upstream central heating zone to 350 ℃ at the temperature of 250 ℃ and preserving heat for 1-3 h.
Further, the operation of introducing argon to remove air is as follows: before the heating process, introducing argon for 20 min; and in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m.
The second purpose of the invention is realized by the following technical scheme:
three-dimensional Co-doped WP2The nanosheet array electrocatalyst is prepared by the above method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to three-dimensional Co-doped WP2Preparation method of nanosheet array electrocatalyst for preparing three-dimensional Co-doped WP on conductive substrate material2The nano-sheet array electrode material has larger exposed specific surface area, higher electrocatalytic hydrogen evolution activity and stability; when the doping concentration is 1 percent, the electrolyte has the optimum different electrocatalytic hydrogen evolution performance in 0.5mol/L H2SO4 electrolyteThe current density was 10mA cm-2The overpotential is 122mV, and the corresponding Tafel slope is 75mV dec-1。
(2) The method is simple, low in cost and easy to control reaction conditions. Provides an effective method for preparing a high-activity three-dimensional electrocatalytic hydrogen evolution electrode material by using a transition metal heteroatom doping method on a conductive matrix material, which is beneficial to the progress and development of an electrocatalytic water decomposition technology.
Drawings
FIG. 1 shows the Co-doped WP obtained from examples 1-4 of the present invention2An XRD (X-ray diffraction) spectrum of the nano-sheet array electro-catalysis hydrogen evolution electrode material.
FIG. 2 shows the Co-doped WP obtained in example 1 of the present invention2SEM image of the nano-sheet array electro-catalysis hydrogen evolution electrode material.
FIG. 3 shows the Co-doped WP obtained from examples 1-4 of the present invention2LSV curve diagram of the nano-sheet array electro-catalysis hydrogen evolution electrode material.
FIG. 4 shows the Co-doped WP obtained from examples 1-4 of the present invention2Tafel curve diagram of nano-sheet array electro-catalysis hydrogen evolution electrode material.
Detailed Description
The present invention is further described below in conjunction with specific examples to better understand and implement the technical solutions of the present invention for those skilled in the art.
Example 1
Three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of:
(1) firstly, performing hydrophilic treatment on cut carbon cloth (1cm × 3cm) by using nitric acid, then ultrasonically cleaning the carbon cloth in acetone, deionized water and ethanol for 20min respectively, weighing 40mL of ethanol, putting the ethanol into a 100mL polytetrafluoroethylene reaction kettle, and adding 0.6g H2C2O4(oxalic acid) to dissolve it. CoCl with a W: Co molar ratio of 1% concentration was then added2·6H2O (cobalt chloride hexahydrate) solution, and then 0.3g of WCl was weighed in a glove box6(tungsten hexachloride) is poured into the mixed solution; vertically placing the pretreated carbon cloth on a prepared counterPerforming solvothermal reaction for 10 hours in a reaction kettle at 180 ℃, after the reaction kettle is naturally cooled, washing the surface of the substrate with ethanol, and then drying the substrate in an oven at 60 ℃. Heating the dried sample to 500 ℃ in a muffle furnace at the heating rate of 2 ℃/min and sintering for 2h to obtain Co-doped WO3A nanosheet array.
(2) The samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. During the synthesis, 3.0g of NaH is added2PO2·H2O (sodium hypophosphite monohydrate) was placed in a quartz boat located in the upstream central heating zone. Placing the cobalt-doped tungsten trioxide nanosheet array material obtained in the step (1) in a central heating zone at the downstream of a two-temperature-zone tubular furnace, and ventilating the tubular furnace with high-purity argon (99.99%) for 20min to remove air and reduce the pollution of other gases to the experiment before the heating process. Then, the downstream central heating zone was heated to 700 ℃ at a rate of 5 ℃/min under atmospheric pressure, while the upstream central heating zone was heated to 300 ℃ and held at this temperature for 2h after reaching the set temperature. And in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m. Obtaining three-dimensional Co-doped WP after the temperature of the tube furnace is reduced to room temperature2A nanosheet array material.
Example 2
Three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of:
(1) firstly, performing hydrophilic treatment on cut carbon cloth (1cm × 3cm) by using nitric acid, then ultrasonically cleaning the carbon cloth in acetone, deionized water and ethanol for 20min respectively, weighing 40mL of ethanol, putting the ethanol into a 100mL polytetrafluoroethylene reaction kettle, and adding 0.6g H2C2O4(oxalic acid) to dissolve it. CoCl with a W to Co molar ratio of 3% concentration was then added2·6H2O (cobalt chloride hexahydrate) solution, and then 0.3g of WCl was weighed in a glove box6(tungsten hexachloride) is poured into the mixed solution; vertically placing the pretreated carbon cloth in a prepared reaction kettle, carrying out solvothermal reaction for 10 hours at 160 ℃, after the reaction kettle is naturally cooled, washing the surface of the substrate with ethanol, and then placing the substrate in a 60 ℃ drying oven for drying. The dried sample is placed in a horseHeating the mixture in a muffle furnace at the heating rate of 2 ℃/min to 500 ℃ and sintering the mixture for 2 hours to obtain Co-doped WO3A nanosheet array.
(2) The samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. During the synthesis, 3.0g of NaH is added2PO2·H2O (sodium hypophosphite monohydrate) was placed in a quartz boat located in the upstream central heating zone. Placing the cobalt-doped tungsten trioxide nanosheet array material obtained in the step (1) in a central heating zone at the downstream of a two-temperature-zone tubular furnace, and ventilating the tubular furnace with high-purity argon (99.99%) for 20min to remove air and reduce the pollution of other gases to the experiment before the heating process. Then, the downstream central heating zone was heated to 700 ℃ at a rate of 5 ℃/min under atmospheric pressure, while the upstream central heating zone was heated to 300 ℃ and held at this temperature for 2h after reaching the set temperature. And in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m. Obtaining three-dimensional Co-doped WP after the temperature of the tube furnace is reduced to room temperature2A nanosheet array material.
Example 3
Three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of:
(1) firstly, ultrasonically cleaning cut carbon paper (1cm × 3cm) in acetone, deionized water and ethanol for 20min, weighing 40mL of ethanol, putting the ethanol into a 100mL polytetrafluoroethylene reaction kettle, and simultaneously adding 0.4g H2C2O4(oxalic acid) to dissolve it. CoCl with a W to Co molar ratio of 5% concentration was then added2·6H2O (cobalt chloride hexahydrate) solution, and then 0.2g WCl was weighed in a glove box6(tungsten hexachloride) is poured into the mixed solution; vertically placing the pretreated carbon cloth in a prepared reaction kettle, carrying out solvothermal reaction for 8 hours at 180 ℃, washing the surface of the substrate with ethanol after the reaction kettle is naturally cooled, and then placing the substrate in a 60 ℃ drying oven for drying. Heating the dried sample to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min and sintering for 2h to obtain Co-doped WO3A nanosheet array.
(2) The samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. In the course of synthesisIn (1), 3.0g of NaH2PO2·H2O (sodium hypophosphite monohydrate) was placed in a quartz boat located in the upstream central heating zone. Placing the cobalt-doped tungsten trioxide nanosheet array material obtained in the step (1) in a central heating zone at the downstream of a two-temperature-zone tubular furnace, and ventilating the tubular furnace with high-purity argon (99.99%) for 20min to remove air and reduce the pollution of other gases to the experiment before the heating process. Then, the downstream central heating zone was heated to 650 ℃ at a heating rate of 2 ℃/min under atmospheric pressure, while the upstream central heating zone was heated to 300 ℃ and held at this temperature for 2h after reaching the set temperature. And in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m. Obtaining three-dimensional Co-doped WP after the temperature of the tube furnace is reduced to room temperature2A nanosheet array material.
Example 4
Three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst comprises the following steps of:
(1) firstly, ultrasonically cleaning cut carbon paper (1cm × 3cm) in acetone, deionized water and ethanol for 20min, weighing 40mL of ethanol, putting the ethanol into a 100mL polytetrafluoroethylene reaction kettle, and simultaneously adding 0.2g H2C2O4(oxalic acid) to dissolve it. CoCl with a W: Co molar ratio of 10% concentration was then added2·6H2O (cobalt chloride hexahydrate) solution, and then 0.1g WCl was weighed in a glove box6(tungsten hexachloride) is poured into the mixed solution; vertically placing the pretreated carbon cloth in a prepared reaction kettle, carrying out solvothermal reaction for 10 hours at 180 ℃, after the reaction kettle is naturally cooled, washing the surface of the substrate with ethanol, and then placing the substrate in a 60 ℃ drying oven for drying. Heating the dried sample to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min and sintering for 2h to obtain Co-doped WO3A nanosheet array.
(2) The samples were synthesized using a dual temperature controlled vacuum atmosphere tube furnace. During the synthesis, 3.0g of NaH is added2PO2·H2O (sodium hypophosphite monohydrate) was placed in a quartz boat located in the upstream central heating zone. Preparing the cobalt-doped tungsten trioxide nanosheet array material obtained in the step (1)The material is placed in a central heating zone at the downstream of a double-temperature zone tube furnace, and before the heating process, high-purity argon (99.99%) is used for ventilating the tube furnace for 20min to remove air so as to reduce the pollution of other gases to the experiment. Then, the downstream central heating zone was heated to 750 ℃ at a rate of 5 ℃/min under atmospheric pressure, while the upstream central heating zone was heated to 350 ℃ and held at this temperature for 2h after reaching the set temperature. And in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m. Obtaining three-dimensional Co-doped WP after the temperature of the tube furnace is reduced to room temperature2A nanosheet array material.
And (3) electrochemical performance testing: directly doping the three-dimensional Co prepared in the example with WP2Nanosheet array material as working electrode (area of 1 cm)2) The graphite rod is an auxiliary electrode, and the calomel electrode is a reference electrode. 0.5mol/L H saturated with nitrogen at room temperature2SO4And carrying out electrocatalytic hydrogen evolution performance test in the electrolyte.
As shown in fig. 1, an XRD pattern of the electrode material prepared in example 1. For Co-WP2NS/CC sample, WP2The characteristic diffraction peaks of (1) appear at 2 theta of 20.97 degrees, 26.11 degrees, 31.10 degrees, 36.10 degrees, 43.95 degrees and 46.60 degrees, and the characteristic diffraction peaks of the monoclinic crystal structure WP2Is perfectly matched with the standard card (JCPDS No. 76-2365).
As shown in fig. 2, is an SEM image of the electrode material prepared in example 2. Co-doped WP can be seen from the figure2The nano-sheet arrays are closely staggered and vertically grown on the carbon cloth, and the morphology has large specific surface area and more reactive active sites, which is beneficial to the hydrogen evolution reaction.
As shown in fig. 3, which is a LSV plot of the electrode materials prepared in examples 1-4. It can be seen from the graph that the most excellent hydrogen evolution performance is obtained at a doping concentration of 1%, and the performance becomes worse as the doping concentration increases.
As shown in fig. 4, a Tafel plot is shown for the electrode materials prepared in examples 1-4. It can be seen from the graph that the same rule as that in fig. 3 is provided, the Tafel slope is gradually increased along with the increase of the doping concentration, and the Tafel slope is the smallest at the doping concentration of 1%, which indicates that the electrocatalytic hydrogen evolution performance is the most excellent.
The above embodiments illustrate various embodiments of the present invention in detail, but the embodiments of the present invention are not limited thereto, and those skilled in the art can achieve the objectives of the present invention based on the disclosure of the present invention, and any modifications and variations based on the concept of the present invention fall within the scope of the present invention, which is defined by the claims.
Claims (9)
1. Three-dimensional Co-doped WP2The preparation method of the nanosheet array electrocatalyst is characterized by comprising the following steps of:
(1) placing the conductive substrate material in a polytetrafluoroethylene reaction kettle containing a mixed solution of ethanol, oxalic acid, tungsten hexachloride and cobalt chloride, carrying out solvothermal reaction for 6-12h at the temperature of 100-220 ℃, and sintering in a muffle furnace to obtain Co-doped WO3A nanosheet array;
(2) in the method, sodium hypophosphite is used as a phosphorus source, and an in-situ phosphorization reduction method is used in a double-temperature-control vacuum atmosphere tube furnace, under the argon environment, a cobalt-doped tungsten trioxide nanosheet array on a conductive substrate material is phosphorized and reduced into a cobalt-doped tungsten diphosphide nanosheet array, so that Co-doped WP (tungsten phosphide) is obtained2The nano-sheet array electrocatalytic hydrogen evolution electrode material.
2. The three-dimensional Co-doped WP of claim 12The preparation method of the nanosheet array electrocatalyst is characterized in that the volume of ethanol in the mixed solution is as follows: 10-60mL, and the mass of oxalic acid is: 0.1-1g, mass of tungsten hexachloride: 0.1-0.5g, mole percent of cobalt chloride (Co: W): 0.5 to 20 percent.
3. The three-dimensional Co-doped WP of claim 12The preparation method of the nanosheet array electrocatalyst is characterized in that in the step (1), the muffle furnace sintering temperature rise rate is 1-5 ℃/min, the temperature rises to 400-600 ℃ and the sintering lasts for 1-5 h.
4. Three-dimensional Co-doped WP according to any one of claims 1 to 32The preparation method of the nanosheet array electrocatalyst is characterized in that the conductive matrix material in the step (1) is subjected to hydrophilic treatment by using nitric acid before being subjected to solvothermal reaction, and then is subjected to ultrasonic cleaning in acetone, deionized water and ethanol respectively.
5. The three-dimensional Co-doped WP of claim 12The preparation method of the nanosheet array electrocatalyst is characterized in that the conductive substrate material is carbon cloth, carbon paper, FTO, carbon nanotubes and TiO2A nanotube.
6. The three-dimensional Co-doped WP of claim 12The preparation method of the nanosheet array electrocatalyst is characterized in that the mass of the sodium hypophosphite in the step (2) is 1-5 g.
7. The three-dimensional Co-doped WP of claim 12The preparation method of the nanosheet array electrocatalyst is characterized in that in the step (2), in-situ phosphorization reduction is carried out in a double-temperature-control vacuum atmosphere tube furnace, and the specific operation is as follows: placing sodium hypophosphite in a quartz boat in a central heating zone at the upstream of the two-temperature zone tube furnace, and doping the Co obtained in the step (1) with WO3The nano-sheet array is arranged on another quartz boat which is positioned in a central heating zone at the downstream of the double-temperature zone tube furnace; introducing argon to remove air, heating the downstream central heating zone to 800 ℃ at the temperature rise rate of 2-10 ℃/min under the atmospheric pressure, simultaneously heating the upstream central heating zone to 350 ℃ at the temperature of 250 ℃ and preserving heat for 1-3 h.
8. The three-dimensional Co-doped WP of claim 72The preparation method of the nanosheet array electrocatalyst is characterized in that the operation of introducing argon to remove air is as follows: before the heating process, introducing argon for 20 min; and in the temperature rise process, the argon flow of the gas path system is set to be 100s.c.c.m, and in the heat preservation stage, the argon flow is switched to be 20 s.c.c.m.
9. Three-dimensional Co-doped WP2Nanosheet array electrocatalyst characterized by being prepared by the method of any one of claims 1 to 8.
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