CN116081691A - Preparation of W by utilizing oxygen defect 18 O 49 /WO 3 Method for heterogeneous electrocatalyst, electrocatalyst and application - Google Patents
Preparation of W by utilizing oxygen defect 18 O 49 /WO 3 Method for heterogeneous electrocatalyst, electrocatalyst and application Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001301 oxygen Substances 0.000 title claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 20
- 230000007547 defect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000011049 filling Methods 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- -1 W 20 O 58 (W 2 O 9 ) Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- 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
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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
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention discloses a method for preparing W by utilizing oxygen defects 18 O 49 /WO 3 A method of heterogeneous electrocatalyst, electrocatalyst and use, the method comprising: respectively weighing tungsten chloride, cuprous oxide and urea, grinding the tungsten chloride, the cuprous oxide and the urea to uniformly mix the tungsten chloride, the cuprous oxide and the urea, adding the obtained mixture into a methanol solution, and stirring to obtain a uniformly mixed solution; filling the obtained uniformly mixed solution into a lining of an autoclave, mounting the lining into a stainless steel high-temperature high-pressure reaction kettle, putting the sealed reaction kettle into an electric blast drying box, setting parameters, and reacting at 120-220 ℃ for 1-36h, after the hydrothermal kettle is cooled to room temperature after the reaction is finished, removing the kettle, and carrying out suction filtration, cleaning and drying on the solution after the hydrothermal reaction to obtain a final product W 18 O 49 /WO 3 The method comprises the steps of carrying out a first treatment on the surface of the W prepared by the invention 18 O 49 /WO 3 The electrocatalytic material has better electrocatalytic hydrogen production performance in alkaline electrolyte.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a composite electrocatalytic material, and in particular relates to a method for preparing W by utilizing oxygen defects 18 O 49 /WO 3 Methods of heterogeneous electrocatalyst, electrocatalyst and use thereof.
Background
Global energy crisis and environmental issues have driven the development of hydrogen economy, and strategies to develop hydrogen for sustainable production of economy are critical to its practical use. The electrolytic water hydrogen production reaction (HER) has attracted increasing attention due to its potential low cost and cleanliness, providing a promising solution to the fossil energy crisis. In order to realize large-scale hydrogen production using electrolyzed water technology, it is critical to develop an efficient, stable, low cost Hydrogen Evolution Reaction (HER) electrocatalyst. Currently, high efficiency electrocatalysts for total electrolyzed water are mainly noble metals, such as platinum (Pt) and iridium oxide (IrO) 2 ) Catalysts considered to be the most excellent in Hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER), respectively [ Tiwari J N, sultans, myung C W, et al multicomponents electrocatalyst with ultralow Pt loading and high hydrogenevolution activity [ J ]].Nature Energy,2018,3(9):773-782.]. However, these noble metal catalysts, as high cost products, must stimulate the production of terminal hydrogen and oxygen, and are difficult to be promoted on a large scale in the market. Thus, the search for low cost electrocatalysts with comparable performance is a viable way to reduce the cost of decomposing water, promoting practical applications.
Compared with transition metal-based sulfides, nitrides and phosphides, the transition metal oxides have the characteristics of easy availability, environmental friendliness, low cost and the like, and have potential and wide application in the aspects of energy storage and conversion of photocatalysis, fuel cells and the like [ Ni Z, wen H, zhang S, et al, recent advances in layered tungsten disulfide as electrocatalyst for water splitting [ J ]. ChemCatchem,2020,12 (20): 4962-4999 ]. Besides the economic and environmental protection, the optimized material can meet the requirement of high efficiency and stability of the reaction system.
WO 3 Is a transition metal oxide composed of perovskite units, and is known for its non-stoichiometric nature in that its crystal lattice can withstand a considerable number of oxygen defects. Oxygen vacancies are an unavoidable structural defect in tungsten oxide and are the result of oxygen atoms being eliminated during synthesis. Only part of WO needs to be eliminated 3 Can influence the electron band structure and greatly increase the conductivity thereof [ Wondimu T H, bayeh A W, kabtamu D M, et al, recent progress on tungsten oxide-based materials for the hydrogen and oxygen evolution reactions [ J ]].International Journal of Hydrogen Energy,2022.]. Tungsten oxide is WO 6 Octahedra are composed by sharing the corners and sides of the octahedra. WO sharing edges and corners 6 WO with octahedron sharing edges with parts 6 The octahedra are alternately arranged to produce non-stoichiometric tungsten oxide with varying degrees of oxygen defects, noted as WO 3-x Wherein 0 is<x<1 represents the degree of oxygen vacancies. Thus, these oxides are also known as anoxic tungsten oxides, e.g. W 20 O 58 (W 2 O 9 )，W 5 O 14 (WO 2.8 )，W 4 O 11 (WO 2.75 )，W 18 O 49 (WO 2.72 )，W 3 O 8 (WO 2.67 ) And W is 2 O 5 (WO 2.5 ). In these non-stoichiometric tungsten oxides, W 18 O 49 Is unique and flexible, has proven beneficial properties compared to other stoichiometric and non-stoichiometric oxides. Thus W is 18 O 49 Composite WO 3 The electrocatalyst with the hydrogen evolution efficiency is expected to be prepared.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing W by utilizing oxygen defects 18 O 49 /WO 3 Method for preparing heterogeneous electrocatalyst, electrocatalyst and application thereof, and prepared W with adjustable heterogeneous interface and good electrocatalytic hydrogen evolution performance in alkaline solution 18 O 49 /WO 3 The heterogeneous electrocatalyst has mild preparation condition and simple process.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
preparation of W by utilizing oxygen defect 18 O 49 /WO 3 A method of heterogeneous electrocatalyst comprising the steps of:
firstly, respectively weighing 0.10122g-0.24588g of tungsten chloride, 0.04336g-0.10234g of cuprous oxide and 0.062g-0.138g of urea, grinding the tungsten chloride, the cuprous oxide and the urea to uniformly mix the tungsten chloride, the cuprous oxide and the cuprous oxide, the cuprous oxide and the urea, adding the obtained mixture into 30mL-60mL of methanol solution, and stirring to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a liner of an autoclave, mounting the liner into a stainless steel high-temperature high-pressure reaction kettle, putting the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 120-220 ℃, the reaction time is 1-36h, after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration, cleaning and drying on the hydrothermal solution to obtain a final product W 18 O 49 /WO 3 。
Preferably, the grinding in the first step is grinding for 10-20min by an agate mortar.
Preferably, the stirring in the first step is magnetic stirring for 20-60min.
Preferably, the filling ratio of the liner volume of the autoclave in the second step is 20-70%.
Preferably, the lotion in the second step is washed 3-5 times with absolute ethanol and deionized water respectively.
Preferably, the drying in the second step is to put the wet powder into a culture dish, and dry the wet powder in a vacuum oven at 30-70 ℃ or a freeze drying oven for 3-10 hours.
The invention also protects W prepared by the method 18 O 49 /WO 3 Heterogeneous electrocatalysts and their use in the electrocatalytic production of hydrogen from alkaline electrolytes.
Compared with the prior art, the invention has the following technical effects:
the invention synthesizes W by a hydrothermal method 18 O 49 /WO 3 Composite material, successfully W 18 O 49 And WO 3 Compounding, due to WO 3 And W is 18 O 49 With different energy band structures, WO is provided 3 And W is 18 O 49 Recombination, which can form an internal electric field at the interface and drive charge separation; at the same time, WO 3 And W is 18 O 49 The catalyst has the same element composition and matched crystal lattice, and is beneficial to reducing interface impedance, thereby improving charge separation efficiency and catalytic hydrogen evolution efficiency;
the method has the advantages of simple reaction conditions, easy preparation, lower cost, environmental friendliness and no bad products;
the invention can well regulate the shape and size of the product and the content of oxygen defects in the product by controlling the content of the precursor, the content of the additive, the hydrothermal reaction temperature, the reaction time and the like;
w prepared by the invention 18 O 49 /WO 3 The electrocatalytic material has better electrocatalytic hydrogen production performance in alkaline electrolyte.
Drawings
FIG. 1 is a drawing of W prepared in example 1 18 O 49 /WO 3 An XRD pattern of (a);
FIG. 2 is a W prepared in example 1 18 O 49 /WO 3 SEM photographs of (2);
FIG. 3 is a W prepared in example 1 18 O 49 /WO 3 LSV curve of (c).
Detailed Description
The following examples illustrate the invention in further detail.
Example 1:
step one, weighing 0.10122g of tungsten chloride (WCl) respectively 6 ) 0.04336g of cuprous oxide (Cu) 2 O) and 0.062g of urea (CH) 4 N 2 O), putting them into agate mortar respectively, grinding them for 10min, mixing them uniformly, then adding the mixture into 30mL of methanol (CH) 3 OH) magnetically stirring for 20min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled to be 30%;
placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 120 ℃, and the reaction time is 5 hours; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed by absolute ethyl alcohol and deionized water for 5 times; finally, placing the culture dish filled with the wet powder in a vacuum oven at 40 ℃ for drying for 4 hours to obtain a final product W 18 O 49 /WO 3 。
FIG. 1 is a drawing of W prepared in example 1 18 O 49 /WO 3 As can be seen from the figure, the surface of the material contains W 18 O 29 、WO 3 Indicating successful preparation of these two phases;
FIG. 2 is a W prepared in example 1 18 O 49 /WO 3 From the SEM photograph of (C), it can be derived that W is prepared 18 O 49 /WO 3 The surface particles are piled up, the specific surface area is large, and the active sites are more;
FIG. 3 is a W prepared in example 1 18 O 49 /WO 3 LSV curve, W 18 O 49 /WO 3 Under alkaline conditions, the current density at the drive was 10mA/cm 2 The overpotential was 137mV.
Example 2
Step one, weighing 0.14944g of tungsten chloride (WCl) respectively 6 ) 0.06302g of cuprous oxide (Cu) 2 O) and 0.087g of urea (CH 4 N 2 O), respectively putting it into agateGrinding in mortar for 20min, mixing, and adding the mixture into 40mL of methanol (CH 3 OH) magnetically stirring for 30min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled to be 50%; placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature parameters are 150 ℃, and the reaction time is 12 hours; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed with absolute ethyl alcohol and deionized water for 3 times; placing the culture dish filled with the wet powder in a vacuum freeze drying oven at 50 ℃ for drying for 5 hours to obtain a final product W 18 O 49 /WO 3 。
Example 3:
step one, weighing 0.19766g of tungsten chloride (WCl) respectively 6 ) 0.08268g of cuprous oxide (Cu) 2 O) and 0.112g of urea (CH 4 N 2 O), putting them into agate mortar respectively, grinding them for 15min, mixing them uniformly, then adding the mixture into 50mL of methanol (CH) 3 OH) magnetically stirring for 60min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled to be 50%; placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 180 ℃, and the reaction time is 18 hours; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed by absolute ethyl alcohol and deionized water for 4 times; finally, placing the culture dish filled with the wet powder in a vacuum oven at 50 ℃ for drying for 8 hours to obtain a final product W 18 O 49 /WO 3 An electrode material.
Example 4:
step one, weighing 0.24588g of tungsten chloride (WCl) respectively 6 ) 0.10234g of oxygenCuprous oxide (Cu) 2 O) and 0.138g of urea (CH 4 N 2 O), putting them into agate mortar respectively, grinding them for 20min, mixing them uniformly, then adding the mixture into 60mL of methanol (CH) 3 OH) magnetically stirring for 60min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled to be 60%; placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 220 ℃, and the reaction time is 24 hours; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed by absolute ethyl alcohol and deionized water for 5 times; finally, placing the culture dish filled with the wet powder in a vacuum oven at 60 ℃ for drying for 10 hours to obtain a final product W 18 O 49 /WO 3 。
Example 5:
step one, weighing 0.24588g of tungsten chloride (WCl) respectively 6 ) 0.10234g of cuprous oxide (Cu) 2 O) and 0.138g of urea (CH 4 N 2 O), putting them into agate mortar respectively, grinding them for 20min, mixing them uniformly, then adding the mixture into 60mL of methanol (CH) 3 OH) magnetically stirring for 60min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled at 20%; placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 200 ℃, and the reaction time is 1h; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed by absolute ethyl alcohol and deionized water for 4 times; finally, placing the culture dish filled with the wet powder in a vacuum oven at 30 ℃ for drying for 10 hours to obtain a final product W 18 O 49 /WO 3 。
Example 6:
step one, weighing 0.24588g of tungsten chloride (WCl) respectively 6 ) 0.10234g of cuprous oxide (Cu) 2 O) and 0.138g of urea (CH 4 N 2 O), putting them into agate mortar respectively, grinding them for 20min, mixing them uniformly, then adding the mixture into 60mL of methanol (CH) 3 OH) magnetically stirring for 30min to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, and mounting the lining into a high-temperature high-pressure stainless steel reaction kettle, so that good tightness is ensured, and the volume filling ratio of the inner kettle is controlled to be 70%; placing the sealed reaction kettle into an electric blast drying box, setting parameters, wherein the temperature is 120 ℃, and the reaction time is 36 hours; after the reaction is finished, cooling the hydrothermal kettle to room temperature, removing the kettle, and carrying out suction filtration on the solution after the hydrothermal reaction, wherein the solution is respectively washed by absolute ethyl alcohol and deionized water for 5 times; finally, placing the culture dish filled with the wet powder in a vacuum oven at 70 ℃ for drying for 3 hours to obtain a final product W 18 O 49 /WO 3 。
It should be noted that while the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention.
Claims (8)
1. Preparation of W by utilizing oxygen defect 18 O 49 /WO 3 A method of heterogeneous electrocatalyst comprising the steps of:
firstly, respectively weighing 0.10122g-0.24588g of tungsten chloride, 0.04336g-0.10234g of cuprous oxide and 0.062g-0.138g of urea, grinding the tungsten chloride, the cuprous oxide and the urea to uniformly mix the tungsten chloride, the cuprous oxide and the cuprous oxide, the cuprous oxide and the urea, adding the obtained mixture into 30mL-60mL of methanol solution, and stirring to obtain a uniformly mixed solution;
step two, filling the uniformly mixed solution obtained in the step one into a lining of an autoclave, mounting the lining into a stainless steel high-temperature high-pressure reaction kettle, putting the sealed reaction kettle into an electric blast drying box, and setting parametersThe temperature is 120-220 ℃, the reaction time is 1-36h, after the reaction is finished, the hydrothermal kettle is cooled to room temperature, the kettle is disassembled, and the solution after the hydrothermal reaction is subjected to suction filtration, cleaning and drying to obtain a final product W 18 O 49 /WO 3 。
2. The method for producing W by utilizing oxygen defects as set forth in claim 1 18 O 49 /WO 3 The heterogeneous electrocatalyst method is characterized in that grinding in the first step is grinding for 10-20min by an agate mortar.
3. The method for producing W by utilizing oxygen defects as set forth in claim 1 18 O 49 /WO 3 The heterogeneous electrocatalyst method is characterized in that the stirring in the step one is magnetic stirring for 20-60min.
4. The method for producing W by utilizing oxygen defects as set forth in claim 1 18 O 49 /WO 3 The heterogeneous electrocatalyst process, characterized in that the autoclave liner volume filling ratio in step two is 20-70%.
5. The method for producing W by utilizing oxygen defects as set forth in claim 1 18 O 49 /WO 3 The heterogeneous electrocatalyst method is characterized in that the lotion in the second step is washed 3-5 times with absolute ethanol and deionized water respectively.
6. The method for producing W by utilizing oxygen defects as set forth in claim 1 18 O 49 /WO 3 The heterogeneous electrocatalyst method is characterized in that the drying in the second step is to put wet powder into a culture dish to be dried for 3-10 hours in a vacuum oven or a freeze drying oven at 30-70 ℃.
7. A W prepared by the method of any one of claims 1-6 18 O 49 /WO 3 Heterogeneous electrocatalysts.
8. A kind of rightW as claimed in claim 7 18 O 49 /WO 3 The application of heterogeneous electrocatalyst in hydrogen production by electro-catalysis of alkaline electrolyte.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109596595A (en) * | 2018-12-06 | 2019-04-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application and detection method of the semiconducting compound in benzaldehyde specific detection |
| CN109731580A (en) * | 2019-02-28 | 2019-05-10 | 陕西科技大学 | A kind of W18O49The preparation method of/NF self-supporting electrocatalysis material |
| CN113289665A (en) * | 2021-06-23 | 2021-08-24 | 淮北师范大学 | Heterojunction photocatalyst and preparation method thereof |
| CN114452994A (en) * | 2020-10-22 | 2022-05-10 | 陕西科技大学 | W-shaped steel plate18O49CoO/NF self-supporting electrocatalytic material and preparation method thereof |
| CN115583670A (en) * | 2022-09-23 | 2023-01-10 | 河南理工大学 | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109596595A (en) * | 2018-12-06 | 2019-04-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application and detection method of the semiconducting compound in benzaldehyde specific detection |
| CN109731580A (en) * | 2019-02-28 | 2019-05-10 | 陕西科技大学 | A kind of W18O49The preparation method of/NF self-supporting electrocatalysis material |
| CN114452994A (en) * | 2020-10-22 | 2022-05-10 | 陕西科技大学 | W-shaped steel plate18O49CoO/NF self-supporting electrocatalytic material and preparation method thereof |
| CN113289665A (en) * | 2021-06-23 | 2021-08-24 | 淮北师范大学 | Heterojunction photocatalyst and preparation method thereof |
| CN115583670A (en) * | 2022-09-23 | 2023-01-10 | 河南理工大学 | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| NAYAK, AK ET AL.: "Facile Synthesis of N-Doped WS2 Nanosheets as an Efficient and Stable Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media", 《 CATALYSTS》, vol. 10, no. 11, 30 November 2020 (2020-11-30), pages 1 - 9 * |
| PENG DU ET AL.: "Synthesis of GQDs/W18O49/tetragonal WO3 homostructures for improving the photoelectric properties", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 893, 7 October 2021 (2021-10-07), pages 1 - 13 * |
| SHIRKE YOGITA MANIKRAO ET AL.: "Selective synthesis of WO3and W18O49nanostructures: ligand-free pH-dependent morphology-controlled self-assembly of hierarchical architectures from 1D nanostructure and sunlight-driven photocatalytic degradation", 《 CRYSTENGCOMM. 》, vol. 19, no. 15, 1 January 2017 (2017-01-01), pages 2096 - 2105 * |
| 吴湘伟;罗劲松;陆必治;谢晨辉;皮志明;胡茂中;徐涛;吴国根;余志明;易丹青;: "Crystal growth of tungsten during hydrogen reduction of tungsten oxide at high temperature", TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA, no. 3, 15 December 2009 (2009-12-15), pages 785 - 789 * |
| 海国娟: "W18O49基自支撑电极材料的制备及其电催化性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, no. 6, 15 June 2022 (2022-06-15), pages 015 - 8 * |
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