CN111939951B - Copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with hollow nanotube structure - Google Patents
Copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with hollow nanotube structure Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 34
- 239000002071 nanotube Substances 0.000 title claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 27
- 239000010941 cobalt Substances 0.000 title claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000004744 fabric Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 13
- 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 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 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 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 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
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 21
- 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
- 239000003054 catalyst Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
-
- 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 copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with a hollow nanotube structure, which comprises two steps of hydrothermal and phosphating. The copper-doped cobalt phosphide bifunctional water electrolysis catalytic material with the hollow nanotube structure is a special hollow nanotube array structure, has very high HER and 0ER catalytic activities, and also shows excellent catalytic activity and long-term stability when being used as anode and cathode materials for full water electrolysis catalytic reaction in alkaline medium.
Description
Technical Field
The invention relates to the technical field of water electrolysis catalytic material production, in particular to a copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with a hollow nanotube structure.
Background
Renewable electrocatalytic water splitting hydrogen production technology has been considered as the most promising way to support energy safety and protect the environment. Clean and pollution-free hydrogen energy is considered a perfect alternative to fossil energy. Currently, the preparation of hydrogen energy is mainly based on steam reforming of fossil fuels, but raw fossil energy is being increasingly consumed, and another hydrogen production technology is urgently needed. As is well known, water electrolysis is an advanced energy conversion technology, and the products are hydrogen and oxygen, which are of interest to researchers. The hydrogen production technology by water electrolysis has no other byproducts, the purity of the prepared hydrogen is very high, and the raw material is water with rich sources. However, the overall water splitting reaction is an uphill reaction, and has low efficiency, and a breakthrough is urgently needed.
At present, the problems of scarcity of noble metal water electrolysis catalytic materials, poor Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) catalytic performance of single transition metal compounds and the like have been fundamentally solved. Researches show that the heteroatom doping can more effectively adjust the appearance, lattice structure and electronic environment of the nano material, thereby further improving the catalytic performance. Moreover, the preparation of the bifunctional electrocatalyst can simultaneously enhance and improve the slow dynamic processes of HER and OER, and plays a vital role in the application of high-efficiency integral water splitting reaction.
Besides single HER and OER catalytic activities, the prepared nano catalytic material is used as a cathode and an anode, and the full water-splitting catalytic reaction activity of the nano catalytic material is studied intensively.
Disclosure of Invention
The invention aims to solve the problems of scarcity and high cost of a Pt group metal-based HER catalyst and a compound-based OER catalyst of Ir/Ru, and provides a copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with a hollow nanotube structure, which is a special hollow nanotube array structure, has very high HER and 0ER catalytic activities, and can also show excellent catalytic activity and long-term stability when being used as an anode and cathode material for full water electrolysis catalytic reaction in an alkaline medium.
The technical scheme adopted for solving the technical problems is as follows:
the copper-doped cobalt phosphide bifunctional water electrolysis catalytic material with the hollow nanotube structure is prepared by the following steps:
(1) Preparing copper doped cobalt oxide and cobalt hydroxide precursors grown on carbon cloth:
firstly, adding copper acetate, monohydrate, cobalt nitrate, hexahydrate, ammonium fluoride and urea into deionized water in sequence, magnetically stirring to form a uniform mixed solution, adding pretreated carbon cloth and the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining together, performing hydrothermal reaction to obtain copper-doped cobalt oxide and cobalt hydroxide precursors growing on the carbon cloth, cleaning and drying;
(2) Phosphating:
and weighing sodium hypophosphite, placing the sodium hypophosphite on the upstream of a porcelain boat, placing copper-doped cobalt oxide and cobalt hydroxide precursors growing on carbon cloth on the downstream of the same porcelain boat, and heating and phosphating the copper-doped cobalt phosphide in a CVD tube furnace and under an argon atmosphere to obtain the copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure. The shielding gas argon is introduced 30min in advance until the phosphating process is finished and cooled to room temperature, and the shielding gas argon is introduced 30min in advance to exhaust air in the tubular furnace, so that oxidation is avoided.
The invention prepares the double-functional copper-doped cobalt phosphide water electrolysis catalytic material which has a hollow nano tube structure and excellent performance and does not contain noble metal by using a simple hydrothermal phosphorylation two-step strategy. The inner layer and the outer layer of the hollow nanotube array structure can be in contact with electrolyte, and have larger electrochemical surface area and electrochemical active sites compared with other nanowire array structures or catalytic materials with nanorod array structures.
The copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure provided by the invention takes carbon cloth as a conductive substrate, is tightly combined with the carbon cloth, and can be directly used as a cathode catalytic material and an anode catalytic material.
Preferably, in the step (1), the amount of cobalt acetate monohydrate is 0.2mM-0.3mM, the amount of cobalt nitrate is 2mM-3mM, the amount of ammonium fluoride is 6mM-10mM, the amount of urea is 10mM-15mM, and the amount of deionized water is 30mL-40mL.
Preferably, cobalt acetate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 0.1:1:3:5.
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, preserving heat for 120-180 minutes at the temperature of 85+/-5 ℃, and respectively ultrasonically cleaning with ethanol and deionized water for 5-10 minutes after finishing.
Preferably, in the step (1), the hydrothermal reaction temperature is 110-130 ℃ and the hydrothermal time is 6-8 h.
Preferably, in the step (2), the phosphating reaction temperature is 300-400 ℃ and the heat preservation time is 2-3 h.
Preferably, in step (2), sodium hypophosphite is used in an amount of 4mM-6mM.
Preferably, the molar ratio of sodium hypophosphite to cobalt nitrate is 2:1.
The beneficial effects of the invention are as follows:
1. the copper doped cobalt phosphide double-function water electrolysis catalytic material with the hollow nanotube structure prepared by the invention is a double-function catalyst for integral water decomposition.
2. The invention provides a double-functional water electrolysis catalytic material which has high efficiency and excellent catalytic performance. When used as both anode and cathode materials, the battery can generate a voltage greater than 10 mA cm by providing a dry cell (1.5V) -2 Has great industrial and commercial application prospect.
3. The copper doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure has better catalytic activity than most existing water electrolysis catalytic materials, has extremely strong stability, can at least ensure the ultra-strong stability for 40 hours, and has huge industrial and commercial values. In addition, the dual-function water electrolysis catalytic material prepared by the invention has the advantages of simple process, low cost, good repeatability and no excessive condition limitation.
Drawings
FIG. 1 is an X-ray diffraction (XRD) test spectrum of a copper-doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-functional water electrolysis catalytic material with a hollow nanotube structure and a corresponding PDF#29-0497 card, which are prepared by the embodiment of the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) characterization image of a copper doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-function water electrolysis catalytic material with a hollow nanotube structure prepared in an embodiment of the invention under different multiplying powers.
FIG. 3 is a representation image of a copper-doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-function water electrolysis catalytic material with a hollow nanotube structure prepared by an embodiment of the invention in a Transmission Electron Microscope (TEM) with different multiplying powers.
FIG. 4 shows a graph of HER-LSV test of a hollow nanotube structured copper-doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-function water electrolysis catalyst material in 1M KOH alkaline electrolyte and after reachingj = 50 mA cm -2 40h I-T test at current density.
FIG. 5 shows the oxygen evolution OER-LSV test curve of a hollow nanotube structured copper-doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-function water electrolysis catalyst material in 1M KOH alkaline electrolyte and the time of reachingj = 50 mA cm -2 40h I-T test at current density.
FIG. 6 is a practical example of the present inventionThe copper-doped cobalt phosphide (Cu-CoP H-NTs/CC) dual-functional water electrolysis catalytic material with the hollow nanotube structure prepared in the embodiment is used as a complete water-splitting LSV test curve of a cathode electrode material and an anode electrode material in 1M KOH alkaline electrolyte and reaches the aimj = 50 mA cm -2 40h I-T test at current density.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples.
In the present invention, the 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.
Cobalt nitrate hexahydrate was purchased from Shanghai microphone Biotechnology Co., ltd; copper acetate monohydrate, ammonium fluoride, urea and sodium hypophosphite were purchased from Shanghai Ala Latin Biochemical technologies Co., ltd; carbon cloth (WOS 1009) was purchased from taiwan carbon technologies inc.
X-ray diffraction (XRD, bruker AXS GmbH, germany) testing was performed at an operating voltage of 40kV in the angle range of 10-80 ℃. The morphology of the prepared samples was characterized by field emission scanning electron microscopy (FESEM, JSM-6700, JEOL, japan). The crystal structure of the sample was observed by transmission electron microscopy (TEM, JSM-2100, JEOL, japan) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM, tecnai G2F 30S-Tain, philips-FEI).
All electrochemical tests were performed on a CHI 660E electrochemical workstation (CH Instruments, inc., shanghai) with a typical three electrode configuration in a 1M KOH electrolyte. Typically, the prepared sample, hg/HgCl electrode and graphite rod are used as the working electrode, reference electrode and counter electrode, respectively. In particular, in the total water splitting test, the prepared samples were used as both anode material and cathode material. The SCE reference electrode was pre-calibrated against the Reversible Hydrogen Electrode (RHE) during all measurements. To compensate for the decrease in ohmic voltage between the working electrode and the reference electrode,iRcompensation being necessary for the performance of the working electrode. The actual operating potential is calculated by: e (E)vs. RHE）= E（vs. SCE）+ 0.242（E Hg/HgCl ) +0.0592 XPH. The polarization curve of the prepared catalyst was recorded by Linear Sweep Voltammetry (LSV) at a sweep rate of 1mV s-1.
Pretreatment of carbon cloth: cutting carbon cloth into 1cm multiplied by 4cm, adding 30ml of concentrated nitric acid (68%) and the cut carbon cloth into a stainless steel autoclave with polytetrafluoroethylene, transferring into an electrothermal blowing drying oven, setting the temperature to 90 ℃, keeping the temperature for 2 hours, respectively ultrasonically cleaning for 5 minutes by using ethanol and deionized after finishing waiting, and finishing pretreatment of the carbon cloth.
Example 1:
preparing copper doped cobalt oxide and cobalt hydroxide precursors growing on carbon cloth in a hydrothermal process:
weigh 0.2mM C 4 H 6 CuO 4 ·H 2 O (copper acetate monohydrate), 2mM Co (NO) 3 ) 2 ·6H 2 O (cobalt nitrate hexahydrate), 6mM H 4 FN (ammonium fluoride), 10mM CH 4 N 2 O (urea) was added to 30mL deionized water and magnetically stirred for 20 min to ensure uniform mixing of the salt solution. A piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm of the precursor mixed solution is added into a stainless steel autoclave with polytetrafluoroethylene, and then the mixture is transferred into an electrothermal blowing drying oven, the hydrothermal temperature is set to be 120 ℃, and the hydrothermal time is set to be 6 hours. After the hydrothermal ending, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
Step two, phosphating:
the phosphating process is carried out in a CVD tube 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 phosphating process is divided into three stages, the first stage is a temperature rising stage, the room temperature reaches 400 ℃, the temperature rising rate is 5 ℃/min, the second stage is a heat preservation stage, the heat preservation is carried out at 400 ℃ for 2 hours, and the third stage is natural cooling. The shielding gas introduced in the phosphating process is argon, the flow rate of the shielding gas is 150sccm, the ventilation time is 30min before the start of the procedure, and the cooling to the room temperature is finished after the phosphating process. Finally, the copper doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure is prepared.
Example 2:
preparing copper doped cobalt oxide and cobalt hydroxide precursors growing on carbon cloth in a hydrothermal process:
weigh 0.3mM C 4 H 6 CuO 4 ·H 2 O (copper acetate monohydrate), 3mM Co (NO) 3 ) 2 ·6H 2 O (cobalt nitrate hexahydrate), 9 mM H 4 FN (ammonium fluoride), 15mM CH 4 N 2 O (urea) was added to 30mL deionized water and magnetically stirred for 20 min to ensure uniform mixing of the salt solution. A piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm of the precursor mixed solution is added into a stainless steel autoclave with polytetrafluoroethylene, and then the mixture is transferred into an electrothermal blowing drying oven, the hydrothermal temperature is set to be 120 ℃, and the hydrothermal time is set to be 6 hours. After the hydrothermal ending, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
Step two, phosphating:
the phosphating process is carried out in a CVD tube 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 phosphating process is divided into three stages, the first stage is a temperature rising stage, the room temperature reaches 400 ℃, the temperature rising rate is 5 ℃/min, the second stage is a heat preservation stage, the heat preservation is carried out at 400 ℃ for 2 hours, and the third stage is natural cooling. The shielding gas introduced in the phosphating process is argon, the flow rate of the shielding gas is 150sccm, the ventilation time is 30min before the start of the procedure, and the cooling to the room temperature is finished after the phosphating process. Finally, the copper doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure is prepared.
Example 3:
preparing copper doped cobalt oxide and cobalt hydroxide precursor growing on carbon cloth in a hydrothermal process:
weigh 0.2mM C 4 H 6 CuO 4 ·H 2 O (copper acetate monohydrate), 2mM Co (NO) 3 ) 2 ·6H 2 O (cobalt nitrate hexahydrate), 6mM H 4 FN (ammonium fluoride), 10mM CH 4 N 2 O (urea) was added to 30mL deionized water and magnetically stirred for 20 min to ensure uniform mixing of the salt solution. A piece of pretreated carbon cloth with the size of 1cm multiplied by 4cm of the precursor mixed solution is added into a stainless steel autoclave with polytetrafluoroethylene, and then the mixture is transferred into an electrothermal blowing drying oven, the hydrothermal temperature is set to be 120 ℃, and the hydrothermal time is set to be 6 hours. After the hydrothermal ending, the surface of the carbon cloth is washed by deionized water and then dried for 6 hours at 60 ℃.
Preparing a final copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with a hollow nanotube structure through a phosphating process:
the phosphating process is carried out in a CVD tube furnace, 4mM 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 phosphating process is divided into three stages, wherein the first stage is a temperature rising stage, the room temperature reaches 300 ℃, the temperature rising rate is 5 ℃/min, the second stage is a heat preservation stage, the heat preservation is carried out at 300 ℃ for 2 hours, and the third stage is natural cooling. The shielding gas introduced in the phosphating process is argon, the flow rate of the shielding gas is 150sccm, the ventilation time is 30min before the start of the procedure, and the cooling to the room temperature is finished after the phosphating process. Finally, the copper doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure is prepared.
Examples 1-3 are preferred embodiments obtained through a series of research experiments, and the hydrothermal phosphating process can be appropriately changed in practical production according to the scope of the claims of the invention, and relatively good experimental results can be achieved within the scope of the claims.
The microstructure and performance test of the copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with the hollow nanotube structure prepared by the embodiment of the invention are shown in figures 1-6, and the test result shows that for the cathodic hydrogen evolution HER reaction, the driving of the material in a 1M KOH alkaline environment is 10 mA cm -2 Only an initial passing point of 58 mV is required; for the anodic oxygen evolution OER reaction, 10 mA cm was reached in a test in a 1M KOH alkaline environment -2 Only an initial overpotential of 220 mV is required; the prepared nano catalyst can be used as both anode and cathode for full water decomposition reaction, and only one dry electricity of 1.5V is needed in a 1M KOH alkaline environmentThe cell voltage can be driven to be more than 10 mA cm -2 The current density of the alloy is extremely high, and the stability is extremely high, so that the ultra-strong stability of 40h can be ensured.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (1)
1. The copper-doped cobalt phosphide bifunctional water electrolysis catalytic material with the hollow nanotube structure is characterized by being prepared by the following steps:
(1) Preparing copper doped cobalt oxide and cobalt hydroxide precursors grown on carbon cloth:
firstly, sequentially adding copper acetate monohydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea into deionized water, magnetically stirring to form a uniform mixed solution, adding pretreated carbon cloth and the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining together, performing hydrothermal reaction to obtain copper doped cobalt oxide and cobalt hydroxide precursors growing on the carbon cloth, cleaning and drying;
(2) Phosphating:
weighing sodium hypophosphite, placing the sodium hypophosphite on the upstream of a porcelain boat, placing copper-doped cobalt oxide and cobalt hydroxide precursors growing on carbon cloth on the downstream of the same porcelain boat, and heating and phosphating the copper-doped cobalt phosphide precursor in a CVD tube furnace and under an argon atmosphere to obtain a copper-doped cobalt phosphide dual-functional water electrolysis catalytic material with a hollow nanotube structure;
in the step (1), the dosage of copper acetate monohydrate is 0.2mmol to 0.3mmol, the dosage of cobalt nitrate hexahydrate is 2mmol to 3mmol, the dosage of ammonium fluoride is 6mmol to 10mmol, the dosage of urea is 10mmol to 15mmol, and the dosage of deionized water is 30mL to 40mL;
copper acetate monohydrate: cobalt nitrate hexahydrate: ammonium fluoride: the molar ratio of urea is 0.1:1:3:5, a step of;
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, preserving heat for 120-180 minutes at the temperature of 85+/-5 ℃, and respectively ultrasonically cleaning with ethanol and deionized water for 5-10 minutes after finishing;
in the step (1), the hydrothermal reaction temperature is 110-130 ℃ and the hydrothermal time is 6-8 h;
in the step (2), the phosphating reaction temperature is 300-400 ℃ and the heat preservation time is 2-3 h; in the step (2), the dosage of sodium hypophosphite is 4mmol-6mmol; the molar ratio of sodium hypophosphite to cobalt nitrate hexahydrate is 2:1.
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