CN110935480A - Vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction - Google Patents
Vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 34
- 239000010941 cobalt Substances 0.000 title claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- 239000004744 fabric Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 239000010935 stainless steel Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 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 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- DNYWTVCFDPXDAR-UHFFFAOYSA-L [OH-].[Co+2].[Co]=O.[OH-] Chemical compound [OH-].[Co+2].[Co]=O.[OH-] DNYWTVCFDPXDAR-UHFFFAOYSA-L 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- ZQVHTTABFLHMPA-UHFFFAOYSA-N 2-(4-chlorophenoxy)-5-nitropyridine Chemical compound N1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1 ZQVHTTABFLHMPA-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction, which comprises the following steps: step one, hydrothermally synthesizing a vanadium-doped cobalt oxide and cobalt hydroxide precursor growing on carbon cloth; and II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization. The invention not only has excellent integral water decomposition catalytic activity, but also has simple preparation process, good stability and repeatability, and shows certain industrial and commercial values.
Description
Technical Field
The invention relates to the technical field of production of full-hydrolysis catalysts, in particular to a vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolysis reaction.
Background
The problems of global warming and fossil energy shortage have not been solved fundamentally. In recent years, hydrogen energy is pursued by more and more researchers, and is derived from the perfect characteristics of no pollution, high calorific value and recycling, but the wide development of the hydrogen energy is limited by the preparation efficiency and the cost of the hydrogen energy. Electrocatalytic water splitting is considered to be a very promising sustainable hydrogen process, including anodic Oxygen Evolution Reaction (OER) and cathodic Hydrogen Evolution Reaction (HER).
The development of a full-hydrolytic catalytic material with high performance and low cost is very important for producing hydrogen by electrolyzing water. Currently, Ir/Ru based catalysts and Pt based catalysts are considered the most advanced catalysts for OER and HER, respectively. However, the high cost and scarcity of precious metal materials has greatly hindered their widespread use. At present, a precious metal-free electrolytic water catalytic material is urgently needed to be searched for replacing the precious metal-free electrolytic water catalytic material, so that the development of an electrolytic water hydrogen evolution catalyst which is high in cost, high in efficiency, excellent in performance and high in durability becomes a current research hotspot.
Typically, one well-behaved HER catalytic material can be paired with another well-behaved OER catalytic material in an alkaline medium to achieve bulk water splitting, but the use of two different electrode materials can cause inconvenience in the assembly of the catalyst cell and can also cause mutual contamination with each other.
Disclosure of Invention
The invention aims to solve the problems that a platinum-based noble metal water electrolysis catalyst is expensive and a non-noble metal water electrolysis catalyst is poor in performance, and provides a vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolysis reaction, which is a heterostructure catalyst, has high OER and HER catalytic activities and is good in full-hydrolysis reaction in an alkaline medium.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction comprises the following steps:
step one, hydrothermally synthesizing a vanadium-doped cobalt oxide cobalt hydroxide precursor growing on carbon cloth:
sequentially adding vanadium trichloride, cobalt nitrate, ammonium fluoride and urea into deionized water, stirring to form a uniform mixed solution, adding the pretreated carbon cloth and the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining together, and carrying out hydrothermal reaction to obtain a vanadium-doped cobalt oxide-cobalt hydroxide precursor growing on the carbon cloth;
and II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization:
and (3) placing sodium hypophosphite at the upstream of the porcelain boat, placing the vanadium-doped cobalt oxide and cobalt hydroxide precursor growing on the carbon cloth at the downstream of the same porcelain boat, heating to 300-400 ℃ in an argon atmosphere, and keeping the temperature for 2-3 hours to obtain the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth.
The invention combines the heteroatom doping technology and the hydrothermal phosphorization strategy to prepare the electrolytic water catalytic material which has excellent performance and does not contain noble metal, and has great potential to become a substitute of noble metal platinum-based catalytic material.
The vanadium-doped cobalt phosphide full-hydrolysis catalyst provided by the invention takes carbon cloth as a conductive substrate, and the vanadium-doped cobalt phosphide nano-thorn arrays are densely arranged on the surface of the carbon cloth and are tightly combined with the carbon cloth. The prepared vanadium-doped cobalt phosphide catalytic material is a nano-thorn array densely grown on carbon cloth.
Preferably, the dosage ratio of the vanadium trichloride, the cobalt nitrate, the ammonium fluoride, the urea and the deionized water is as follows: the dosage of the vanadium trichloride is 0.1mM-0.15mM, the dosage of the cobalt nitrate is 2mM-3mM, the dosage of the ammonium fluoride is 6mM-9mM, the dosage of the urea is 10mM-15mM, and the dosage of the deionized water is 30mL-40 mL. The preferable molar ratio of the vanadium trichloride, the cobalt nitrate, the ammonium fluoride and the urea is 0.05: 1: 3: 5.
preferably, the pretreatment method of the carbon cloth comprises the following steps: transferring the sheared carbon cloth and concentrated nitric acid into a stainless steel autoclave with polytetrafluoroethylene together, preserving the heat for 180 minutes at the temperature of 85 +/-5 ℃, and then ultrasonically cleaning for 5-10 minutes by using ethanol and deionized water respectively.
Preferably, the mass concentration of the concentrated nitric acid is 65-68%.
Preferably, the hydrothermal reaction temperature is 110-130 ℃, and the hydrothermal time is 6-8 h.
Preferably, the amount of sodium hypophosphite used is 4mM to 6 mM. The phosphorization procedure is divided into three stages, wherein the first stage is to heat up from room temperature to the phosphorization temperature of 300 ℃ to 400 ℃, and the heating-up speed is 5 ℃/min; the second stage is a phosphorization stage, and the heat preservation time is 2 to 3 hours; the third stage is natural cooling to room temperature. Preferably, the protective gas argon is introduced in advance for 30min until the third stage is cooled to room temperature, the gas is introduced in advance in order to exhaust the air in the tube furnace, and the flow rate of argon is 150 sccm.
Preferably, the molar ratio of sodium hypophosphite to cobalt nitrate is 2: 1.
The invention has the beneficial effects that:
the vanadium-doped cobalt phosphide nano-thorn catalytic material prepared by the invention is a bifunctional catalyst for integral water decomposition. For Hydrogen Evolution Reactions (HER), up to 10 mA/cm in a 1M KOH alkaline environment2The current density of (2) only requires 33mV of point-crossing. For Oxygen Evolution Reaction (OER), 10 mA/cm was reached in the test in a 1M KOH alkaline environment2The current density of (a) only requires a voltage of 222 mV. For the full hydrolysis reaction, 10 mA/cm was reached in the test in a 1M KOH alkaline environment2Only a voltage of 1.491V is required for the current density of (a).
The invention provides a full-hydrolytic catalytic material with high efficiency and excellent performance. The prepared vanadium-doped cobalt phosphide nano-thorn catalytic material has extremely strong stability, can ensure that the stability is not reduced for at least 40h, and shows certain industrial and commercial values. The invention not only has excellent integral water decomposition catalytic activity, but also has simple preparation process, good stability and repeatability, and shows certain industrial and commercial values.
Drawings
FIG. 1 is an X-ray diffraction (XRD) test spectrum of a vanadium-doped cobalt phosphide nano-needle catalytic material (V-CoP NTs/CC) grown on carbon cloth prepared by the embodiment of the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) representation image of a vanadium-doped cobalt phosphide nano-catalytic material (V-CoP NTs/CC) grown on carbon cloth prepared by an embodiment of the present invention.
FIG. 3 is a high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) characterization image of a vanadium-doped cobalt phosphide nano-thorn catalytic material (V-CoP NTs/CC) grown on carbon cloth, prepared by an embodiment of the invention.
FIG. 4 shows that a vanadium-doped cobalt phosphide nano-thorn catalytic material (V-CoP NTs/CC) grown on carbon cloth prepared by the embodiment of the invention is subjected to STEM (Tacnai G2F 30S-Twin, Philips-FEI) to observe STEM-EDX mapping (Tecnai G2F 30S-Twin, Philips-FEI) at an accelerating voltage of 300 kV.
FIG. 5 shows the HER-LSV test curve and stability I-T test curve of hydrogen evolution catalytic reaction in alkaline environment of 1M KOH of a vanadium-doped cobalt phosphide nano-catalyst material (V-CoP NTs/CC) grown on carbon cloth prepared by the embodiment of the invention.
FIG. 6 is an OER-LSV test curve and a stability I-T test curve of the vanadium doped cobalt phosphide nano-thorn catalytic material (V-CoP NTs/CC) grown on carbon cloth in the alkaline environment of 1M KOH.
FIG. 7 is an LSV test curve and a stability I-T test curve of the full hydrolysis reaction of a vanadium-doped cobalt phosphide nano-thorn catalytic material (V-CoP NTs/CC) grown on carbon cloth in an alkaline environment of 1M KOH, which is prepared by the embodiment of the invention.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Vanadium trichloride was purchased from sahn chemical technology (shanghai) ltd; cobalt nitrate hexahydrate from Shanghai Mecline Biotech limited; ammonium fluoride, urea and sodium hypophosphite were purchased from Shanghai Allantin Biotechnology Ltd; carbon cloth (WOS 1009) was purchased from Taiwan carbon technologies, Inc.
Example 1:
step one, hydrothermally synthesizing a vanadium-doped cobalt oxide cobalt hydroxide precursor growing on carbon cloth:
cutting carbon cloth into 1cm × 4cm large piecesAnd adding 30ml of concentrated nitric acid (68%) and the cut carbon cloth into a stainless steel autoclave with polytetrafluoroethylene, transferring the stainless steel autoclave into an electric heating air blowing drying oven, setting the temperature to be 90 ℃, keeping the temperature for 3 hours, respectively ultrasonically cleaning the stainless steel autoclave with ethanol and deionized water for 5min after the completion of the pretreatment of the carbon cloth. Followed by hydrothermal treatment, 0.1mM VCl was weighed3(vanadium trichloride), 2mMCo (NO)3)2(cobalt nitrate hexahydrate) 6mMH4FN (ammonium fluoride), 10mMCH4N2O (urea) is sequentially added into 30mL of deionized water, and the mixture is magnetically stirred for 30min to ensure that the raw materials are uniformly mixed. After the precursor mixed solution is uniformly stirred, the precursor mixed solution and a piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm are added into a stainless steel autoclave with polytetrafluoroethylene, and then the stainless steel autoclave is transferred into an electric heating forced air drying oven, the temperature is set to be 120 ℃, and the heat preservation time is 6 hours. After the hydrothermal reaction, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
And II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization:
the phosphorization process is carried out in a tubular furnace, 5mM sodium hypophosphite is placed at the upstream of a porcelain boat, carbon cloth after hydrothermal treatment is placed at the downstream of the porcelain boat, the phosphorization process is divided into three stages, the first stage is that the room temperature reaches 300 ℃, the temperature rise rate is 5 ℃/min, the second stage is a heat preservation stage, the temperature is preserved for 2 hours at 300 ℃, the third stage is natural cooling, the protective gas introduced in the phosphorization process is argon, the ventilation time is 30min before the phosphorization process starts until the phosphorization process finishes, and the flow rate of the protective gas is 150 sccm.
Example 2:
step one, hydrothermally synthesizing a vanadium-doped cobalt oxide cobalt hydroxide precursor growing on carbon cloth:
cutting the carbon cloth into a size of 1cm multiplied by 4cm, adding 30ml of concentrated nitric acid and the cut carbon cloth into a stainless steel autoclave with polytetrafluoroethylene, transferring the stainless steel autoclave into an electric heating blowing drying oven, setting the temperature to be 90 ℃, keeping the temperature for 3 hours, further ultrasonically cleaning the stainless steel autoclave with ethanol and deionized water after waiting for the completion of the pretreatment of the carbon cloth, and finishing the pretreatment of the carbon cloth. The hydrothermal treatment is followed by a hydrothermal treatment,0.15mM VCl was weighed3(vanadium (III) chloride), 3mMCo (NO)3)2(cobalt nitrate hexahydrate), 9mMH4FN (ammonium fluoride), 15mMCH4N2O (urea) is sequentially added into 30mL of deionized water, and the mixture is magnetically stirred for 30min to ensure that the raw materials are uniformly mixed. After the precursor mixed solution is uniformly stirred, the precursor mixed solution and a piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm are added into a stainless steel autoclave with polytetrafluoroethylene, and then the stainless steel autoclave is transferred into an electric heating forced air drying oven, the temperature is set to be 120 ℃, and the heat preservation time is 6 hours. After the hydrothermal reaction, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
And II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization:
the phosphorization process is carried out in a tubular furnace, 5mM sodium hypophosphite is placed at the upstream of a porcelain boat, carbon cloth after hydrothermal treatment is placed at the downstream of the porcelain boat, the phosphorization process is divided into three stages, the first stage is that the room temperature reaches 350 ℃, the temperature rise rate is 5 ℃/min, the second stage is a heat preservation stage, the temperature is preserved for 2 hours at 350 ℃, the third stage is natural cooling, the protective gas introduced in the phosphorization process is argon, the ventilation time is 30min before the phosphorization process starts until the phosphorization process finishes, and the flow rate of the protective gas is 150 sccm.
Example 3:
step one, hydrothermally synthesizing a vanadium-doped cobalt oxide cobalt hydroxide precursor growing on carbon cloth:
cutting the carbon cloth into a size of 1cm multiplied by 4cm, adding 30ml of concentrated nitric acid and the cut carbon cloth into a stainless steel autoclave with polytetrafluoroethylene, transferring the stainless steel autoclave into an electric heating blowing drying oven, setting the temperature to be 90 ℃, keeping the temperature for 3 hours, further ultrasonically cleaning the stainless steel autoclave with ethanol and deionized water after waiting for the completion of the pretreatment of the carbon cloth, and finishing the pretreatment of the carbon cloth. Followed by hydrothermal treatment, 0.1mM VCl was weighed3(vanadium (III) chloride), 2mMCo (NO)3)2(cobalt nitrate hexahydrate) 6mMH4FN (ammonium fluoride), 10mMCH4N2O (urea) is sequentially added into 30mL of deionized water, and the mixture is magnetically stirred for 30min to ensure that the raw materials are uniformly mixed. The precursor mixed solution is stirred uniformly and then is mixed withA piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm is added into a stainless steel autoclave with polytetrafluoroethylene, and then the stainless steel autoclave is transferred into an electric heating blowing drying oven, the temperature is set to be 120 ℃, and the heat preservation time is 8 hours. After the hydrothermal reaction, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
And II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization:
the phosphorization process is carried out in a tubular furnace, 5.5mM sodium hypophosphite is placed at the upstream of a porcelain boat, carbon cloth after hydrothermal treatment is placed at the downstream of the porcelain boat, the phosphorization process is divided into three stages, the first stage is that the room temperature reaches 350 ℃, the temperature rise rate is 5 ℃/min, the second stage is a heat preservation stage, the temperature is preserved for 3 hours at 350 ℃, the third stage is natural cooling, the protective gas introduced in the phosphorization process is argon, the ventilation time is 30min before the phosphorization process starts until the phosphorization process finishes, and the flow rate of the protective gas is 150 sccm.
Examples 1 to 3 are preferred embodiments obtained through a series of research experiments, and relatively good experimental results can be achieved within the scope of the claims by properly changing the doping ratio and the hydrothermal phosphating process according to the scope of the claims in the actual production.
The vanadium-doped cobalt phosphide nano-thorn catalytic material prepared by the invention is a bifunctional catalyst for integral water decomposition, and is a nano-thorn array densely grown on carbon cloth (shown in figures 1-4). For Hydrogen Evolution Reactions (HER), up to 10 mA/cm in a 1M KOH alkaline environment2The current density of (2) only requires 33mV of point-crossing. For Oxygen Evolution Reaction (OER), 10 mA/cm was reached in the test in a 1MKOH alkaline environment2The current density of (a) only requires a voltage of 222 mV. For the full hydrolysis reaction, 10 mA/cm was reached in the test in a 1M KOH alkaline environment2Only a voltage of 1.491V is required for the current density of (fig. 5-7).
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. A vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction is characterized by comprising the following steps:
step one, hydrothermally synthesizing a vanadium-doped cobalt oxide cobalt hydroxide precursor growing on carbon cloth:
sequentially adding vanadium trichloride, cobalt nitrate, ammonium fluoride and urea into deionized water, stirring to form a uniform mixed solution, adding the pretreated carbon cloth and the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining together, and carrying out hydrothermal reaction to obtain a vanadium-doped cobalt oxide-cobalt hydroxide precursor growing on the carbon cloth;
and II, preparing the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth by phosphorization:
and (3) placing sodium hypophosphite at the upstream of the porcelain boat, placing the vanadium-doped cobalt oxide and cobalt hydroxide precursor growing on the carbon cloth at the downstream of the same porcelain boat, heating to 300-400 ℃ in an argon atmosphere, and keeping the temperature for 2-3 hours to obtain the vanadium-doped cobalt phosphide nano-thorn catalytic material growing on the carbon cloth.
2. The vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction as claimed in claim 1, which is characterized in that: the dosage ratio of the vanadium trichloride, the cobalt nitrate, the ammonium fluoride, the urea and the deionized water is as follows: the dosage of the vanadium trichloride is 0.1mM-0.15mM, the dosage of the cobalt nitrate is 2mM-3mM, the dosage of the ammonium fluoride is 6mM-9mM, the dosage of the urea is 10mM-15mM, and the dosage of the deionized water is 30mL-40 mL.
3. The vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction as claimed in claim 1, which is characterized in that: the pretreatment method of the carbon cloth comprises the following steps: transferring the sheared carbon cloth and concentrated nitric acid into a stainless steel autoclave with polytetrafluoroethylene together, preserving the heat for 180 minutes at the temperature of 85 +/-5 ℃, and then ultrasonically cleaning for 5-10 minutes by using ethanol and deionized water respectively.
4. The vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction as claimed in claim 1, which is characterized in that: the molar ratio of vanadium trichloride, cobalt nitrate, ammonium fluoride and urea is 0.05: 1: 3: 5.
5. the vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction as claimed in claim 1, which is characterized in that: the hydrothermal reaction temperature is 110-130 ℃, and the hydrothermal time is 6-8 h.
6. The vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction as claimed in claim 1, which is characterized in that: the amount of sodium hypophosphite is 4mM-6 mM.
7. The vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction according to claim 7, which is characterized in that: the molar ratio of the sodium hypophosphite to the cobalt nitrate is 2: 1.
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