CN111185206A - Transition metal-phosphide catalyst and preparation method and application thereof - Google Patents
Transition metal-phosphide catalyst and preparation method and application thereof Download PDFInfo
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- CN111185206A CN111185206A CN202010071811.6A CN202010071811A CN111185206A CN 111185206 A CN111185206 A CN 111185206A CN 202010071811 A CN202010071811 A CN 202010071811A CN 111185206 A CN111185206 A CN 111185206A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 230000007704 transition Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 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 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000467 phytic acid Substances 0.000 claims description 2
- 229940068041 phytic acid Drugs 0.000 claims description 2
- 235000002949 phytic acid Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 35
- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 16
- 229940011182 cobalt acetate Drugs 0.000 description 15
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 phosphorus compound Chemical class 0.000 description 5
- 241001070941 Castanea Species 0.000 description 4
- 235000014036 Castanea Nutrition 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910019239 CoFx Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 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 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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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
- B01J27/185—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本发明涉及电催化技术领域，尤其涉及一种过渡金属‑磷化物催化剂及其制备方法与应用。本发明公开了一种过渡金属‑磷化物催化剂，过渡金属‑磷化物催化剂的化学式为Mx‑N1‑xP；过渡金属‑磷化物催化剂为板栗状结构；过渡金属‑磷化物催化剂的比表面积为69.1‑92.3m2/g；其中，M和N均为金属,x为0～1。该催化剂呈现为板栗状结构，比表面积较大，从而增加了催化材料的活性位点，将该催化剂可同时对析氢反应和析氧反应表现出优异的催化活性。
The invention relates to the technical field of electrocatalysis, in particular to a transition metal-phosphide catalyst and a preparation method and application thereof. The invention discloses a transition metal-phosphide catalyst. The chemical formula of the transition metal-phosphide catalyst is M x -N 1-x P; the transition metal-phosphide catalyst has a chestnut-like structure; the ratio of the transition metal-phosphide catalyst is The surface area is 69.1-92.3m 2 /g; wherein, M and N are both metals, and x is 0-1. The catalyst has a chestnut-like structure and a large specific surface area, thereby increasing the active site of the catalytic material, and the catalyst can simultaneously exhibit excellent catalytic activity for hydrogen evolution reaction and oxygen evolution reaction.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a transition metal-phosphide catalyst and a preparation method and application thereof.
Background
Since the 21 st century, the oil resources on the earth have been gradually exhausted and the environmental pollution has become serious, so that it is a necessary trend to develop a new clean energy. Hydrogen energy is emerging as a low-carbon energy source and a zero-carbon energy source, and the combustion product is water, so that the method is pollution-free and can be recycled. One of the methods for producing hydrogen is to electrolyze water, which can be decomposed into hydrogen and oxygen under the action of electricity, but the hydrolysis process requires a large amount of electric energy, and the electrocatalyst with the best service performance at present is a precious metal represented by platinum, but the storage capacity is limited and the price is high, so that a cheap and efficient electrocatalyst needs to be developed. The transition metal phosphide has a good development prospect in the field of hydrogen production, and is cheap, good in conductivity and stable in chemical property. The catalyst is used for electrolyzing water, so that not only can the performance of hydrogen evolution and water electrolysis be effectively improved, but also the cost can be saved. With the increasing requirement on the catalytic performance of electrocatalysts, the improvement of the catalytic performance of transition metal phosphide is a technical problem which needs to be solved urgently in the field.
At present, the document "Terry metal nanoparticles as a high purity effective electrochemical catalyst for water reduction to hydrogen over a wide range of pH from 0to 14" discloses the preparation of cobalt-nickel phosphide nanosheets CoNiP @ NF on Nickel Foam (NF) in a hydrogen evolution reaction of 10mA cm-2The overpotential at 1M KOH of (1) is 155 mV; the document "Sulfur-doped cobalt dioxide forming a preliminary metal as a biofunctional electrochemical analysis for an alkalinewater electrolysis" discloses the preparation of S-loaded Co on a Carbon Cloth (CC)2P catalyst, 10mA cm in oxygen evolution reaction-2The overpotential at 1MKOH was 290mV, respectively. The transition metal phosphide has not high enough catalytic performance for hydrogen evolution reaction and hydrogen evolution reaction, and cannot simultaneously have good catalytic performance for oxygen evolution reaction and hydrogen evolution reaction.
Disclosure of Invention
In view of the above, the present invention provides a transition metal-phosphide catalyst, and a preparation method and an application thereof, wherein the catalyst has a high specific surface area and a high number of active sites, thereby improving the electrocatalytic performance.
The specific technical scheme is as follows:
the invention provides a transition metal-phosphide catalyst, which has a chemical formula of Mx-N1-xP；
The transition metal-phosphide catalyst is of a chestnut-shaped structure;
the transition metal-phosphide catalyst has a specific surface area of 69.1 to 92.3m2A,/g, preferably 92.3m2/g；
Wherein M and N are both metal, and x is 0-1, more preferably 0.25, 0.5, 0.75 or 1.
The metal in the invention is one or more of Fe, Co, Ni, Cu, Mo, W, Cr, Ti, Nb, Mn, Pd, Pt, Ir, Ru, Rh, Ag, Au, Os and Zr.
In the invention, the transition metal-phosphide catalyst has high specific surface area, increases the active sites of the catalytic material, and shows excellent catalytic activity when applied to the hydrogen evolution reaction.
The invention also provides a preparation method of the transition metal-phosphide catalyst, which comprises the following steps:
step 1: dissolving a first metal salt and a second metal salt in water, and adding ammonium fluoride, urea and a phosphorus-containing compound to obtain a mixed solution;
step 2: and adding carbon paper into the mixed solution for hydrothermal reaction, drying and calcining to obtain the transition metal-phosphide catalyst.
In the invention, ammonium fluoride and urea can play a role in regulating the morphology of the transition metal-phosphide catalyst, the ammonium fluoride is used as a complexing agent and is a stabilizer of the whole hydrothermal reaction, which is beneficial to crystallization of a product, and the urea is used as a mineralizer and provides an alkali source for the whole reaction.
Taking the transition metal-phosphide catalyst CoP as an example:
(1)Co2++xF-→CoFx(x-2)-
(2)H2NCONH2+H2O→2NH3+CO2
(3)NH3·H2O→NH4++OH-
(4)Co2++ X → I-X. Co2+(X＝COO-，COH)
(5)CoFx(x-2)-+ X-Co2++xF-
(6) I-X-Co2++2OH-→ I-X. Co (OH)2
The transition metal-phosphide catalyst CoP is synthesized in one step by directly annealing the precursors containing the phosphorus compound and the cobalt.
The molar ratio of the first metal salt to the second metal salt is x (1-x), wherein x is 0-1;
the ratio of the water, the ammonium fluoride, the urea to the sum of the first metal salt and the second metal salt is 40 mL: 8 mmol: 15 mmol: 4 mmol. If the ratio of the total amount of the first metal salt and the second metal salt is changed, the morphology of the first metal salt and the second metal salt is also changed.
The whole preparation process of the invention has mild reaction conditions and simple operation, the transition metal resources are cheaper and more easily obtained than platinum, and sodium hypophosphite and the like are not used as phosphorus sources in the reaction, so that the harm of the generation of phosphine gas to the environment and human bodies is avoided, and the invention is safer and more environment-friendly.
In step 1 of the invention, the first metal in the first metal salt and the second metal in the second metal salt are both one or more of Fe, Co, Ni, Cu, Mo, W, Cr, Ti, Nb, Mn, Pd, Pt, Ir, Ru, Rh, Ag, Au, Os and Zr;
the phosphorus-containing compound is selected from phytic acid, phosphoric acid or hydroxy ethylidene diphosphonic acid;
in step 2 of the invention, the size of the carbon paper is (1 × 1 cm-2 × 3cm), preferably 2 × 3 cm;
the hydrothermal temperature is 120-200 ℃, the time is 6-24h, preferably 120 ℃, 6 h; 120 ℃ for 24 hours; 200 ℃ for 6 h; 200 ℃ for 24 h;
after the hydrothermal reaction, the method further comprises the following steps: washing the carbon paper obtained after the hydrothermal reaction with water and ethanol respectively;
the calcining temperature is 600-800 ℃, the heating rate is 1-5 ℃/min, the heat preservation time is 1-3h, preferably 800 ℃, 5 ℃/min and 3 h; 600 ℃, 1 ℃/min and 1 h; 600 ℃, 5 ℃/min and 1 h; 600 ℃, 1 ℃/min and 1 h.
The invention also provides a working electrode which comprises the transition metal-phosphide catalyst or the transition metal-phosphide catalyst prepared by the preparation method.
The present invention also provides a reaction apparatus comprising: the working electrode, the reference electrode and the counter electrode.
The invention also provides the application of the reaction device in hydrogen evolution reaction, oxygen evolution reaction or total hydrolysis reaction.
The hydrogen evolution reaction can be carried out under the full pH condition, and the oxygen evolution reaction and the full hydrolysis reaction can be carried out under the alkaline condition.
According to the technical scheme, the invention has the following advantages:
the invention provides a transition metal-phosphide catalyst which is in a chestnut-shaped structure and has a large specific surface area, so that active sites of a catalytic material are increased, the catalyst can simultaneously show excellent catalytic activity on a hydrogen evolution reaction and an oxygen evolution reaction, and the comprehensive performance is good. The experimental data show that the catalytic performance of the chestnut-shaped cobalt-phosphorus catalyst is improved in the hydrogen evolution reaction and the oxygen evolution reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a scanning electron microscope image of a carbon paper provided in an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a chestnut-shaped cobalt phosphorus catalyst CoP provided in example 1 of the present invention;
figure 3 is the bookThe chestnut-shaped cobalt-phosphorus catalyst Cu provided by the embodiment 2 of the invention0.25Co0.75P, scanning electron micrograph;
FIG. 4 shows chestnut-like cobalt-phosphorus catalysts CoP and Cu provided in examples 1 and 2 of the present invention0.25Co3.75An X-ray photoelectron spectrum of P;
FIG. 5 shows chestnut-shaped cobalt-phosphorus catalysts CoP and Cu provided in examples 1, 2, 6 and 7 of the present invention0.25Co0.75P、Cu0.5Co0.5P and Cu0.75Co0.25A linear scanning profile of P evolution of hydrogen in alkaline medium;
FIG. 6 shows chestnut-shaped cobalt-phosphorus catalysts CoP and Cu provided in examples 1, 2, 6 and 7 of the present invention0.25Co0.75P、Cu0.5Co0.5P and Cu0.75Co0.25Linear scan plot of P evolution in alkaline medium.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention relates to a preparation method of a chestnut-shaped cobalt-phosphorus catalyst CoP
1. Adding 40mL of water into 4mmol of cobalt acetate to fully dissolve the cobalt acetate to obtain a cobalt acetate solution;
2. adding 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid into the cobalt acetate solution obtained in the step 1 for full dissolution to obtain a mixed solution;
3. adding 2 x 3cm of carbon paper and the mixed solution obtained in the step 2 into an inner container of a reaction kettle for hydrothermal reaction for 6 hours at 120 ℃, and respectively washing and drying the carbon paper after the reaction by using water and ethanol;
4. and (3) placing the dried product in the step (3) in a high-temperature furnace, heating the product from room temperature to 600 ℃ at the heating rate of 1 ℃/min in the hydrogen atmosphere, and preserving the heat at the temperature for 1 hour to obtain the chestnut-shaped cobalt-phosphorus catalyst CoP.
FIG. 1 is a scanning electron micrograph of the carbon paper of this example. Figure 1 shows that the carbon paper surface is not covered with any substance.
FIG. 2 is a scanning electron micrograph of the chestnut-like CoP catalyst of this example. FIG. 2 shows that the whole carbon paper surface is covered by chestnut-like nanorod arrays.
Example 2
This example is chestnut like cobalt phosphorus catalyst Cu0.25Co0.75Preparation of P
1. Weighing copper nitrate and cobalt acetate with a molar ratio of 0.25:0.75, and adding 40mL of water to fully dissolve the copper nitrate and the cobalt acetate to obtain an aqueous solution of ketone nitrate and the cobalt acetate;
2. adding 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid into the aqueous solution of the ketone nitrate and the cobalt acetate obtained in the step 1, and fully dissolving to obtain a mixed solution;
3. adding 2 x 3cm of carbon paper and the mixed solution obtained in the step 2 into an inner container of a reaction kettle for hydrothermal reaction for 6 hours at 120 ℃, and respectively washing and drying the carbon paper after the reaction by using water and ethanol;
4. putting the product dried in the step 3 into a high-temperature furnace, heating the product from room temperature to 600 ℃ at the heating rate of 1 ℃/min in the hydrogen atmosphere, preserving the heat for 1 hour at the temperature, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst Cu0.25Co0.75P。
FIG. 3 shows the chestnut-shaped Co-P catalyst Cu of this example0.25Co0.75Scanning electron micrograph of P. FIG. 1 shows that the carbon paper surface is still chestnut-shaped nanorod array after copper doping, and is not obviously changed compared with FIG. 2.
FIG. 4 shows CoP of example 1 and Cu of this example0.25Co0.75An X-ray photoelectron spectrum of P. FIG. 4 shows CoP and Cu0.25Co0.75The diffraction peaks of the P samples all matched the orthorhombic CoP structure (JCPDS No. 29-0497). XRD resultsIt is shown that the small amount of Cu atom doping does not damage the crystal structure of CoP.
Example 3
This example is chestnut like cobalt phosphorus catalyst Cu0.5Co0.5Preparation of P
1. Weighing copper nitrate and cobalt acetate with a molar ratio of 0.50:0.50, and adding 40mL of water to fully dissolve the copper nitrate and the cobalt acetate to obtain an aqueous solution of ketone nitrate and the cobalt acetate;
2. adding 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid into the aqueous solution obtained in the step 1 for full dissolution to obtain a mixed solution;
3. adding 2 x 3cm of carbon paper and the mixed solution obtained in the step 2 into an inner container of a reaction kettle for hydrothermal reaction at 120 ℃ for 24 hours, and respectively washing and drying the carbon paper after the reaction with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high-temperature furnace, heating the product from room temperature to 600 ℃ at the heating rate of 5 ℃/min in the hydrogen atmosphere, preserving the heat at the temperature for 1 hour, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 4
This example is chestnut like cobalt phosphorus catalyst Cu0.75Co0.25Preparation of P
1. Weighing copper nitrate and cobalt acetate with a molar ratio of 0.75:0.25, and adding 40mL of water to fully dissolve the copper nitrate and the cobalt acetate to obtain an aqueous solution of ketone nitrate and the cobalt acetate;
2. adding 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid into the aqueous solution obtained in the step 1 for full dissolution to obtain a mixed solution;
3. adding 2 x 3cm of carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 6 hours at the temperature of 200 ℃, and respectively washing and drying the carbon paper after the reaction by using water and ethanol;
4. and (3) placing the dried product in the step (3) in a high-temperature furnace, heating the product from room temperature to 600 ℃ at the heating rate of 1 ℃/min in the hydrogen atmosphere, preserving the heat at the temperature for 1 hour, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 5
This example is chestnut like cobalt phosphorus catalyst Fe0.9Co0.1Preparing P1, weighing ferric nitrate and cobalt chloride with a molar ratio of 0.9:0.1, and adding 40mL of water to fully dissolve to obtain an aqueous solution of nitrone and cobalt acetate;
2. adding 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid into the aqueous solution obtained in the step 1 for full dissolution to obtain a mixed solution;
3. adding 2 x 3cm of carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction at 200 ℃ for 24 hours, and respectively washing and drying the carbon paper after the reaction with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high-temperature furnace, heating the product from room temperature to 800 ℃ at the heating rate of 5 ℃/min in the hydrogen atmosphere, preserving the heat at the temperature for 3 hours, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 6
In this example, CoP of example 1 and Cu of example 2 were used0.25Co0.75P, example 3Cu0.5Co0.5P and example 4Cu0.75Co0.25P electrochemical test
Electrochemical test method: all electrochemical measurements were performed using a PGSTAT302N potentiostat/galvanostat (MetrohmAutolab, Netherlands). Using a conventional three-electrode test, CoP or Cu0.25Co0.75The P is cut to1 × 1cm and directly used as a working electrode, a graphite plate is used as a counter electrode, and a Reversible Hydrogen Electrode (RHE) is used as a reference electrode. All electrolytes (0.5 MH) prior to HER testing2SO41.0M KOH and 1.0M PBS) were aerated with high purity nitrogen gas for at least 30min to remove dissolved oxygen from the electrolyte. Before OER test, it is necessary to pass O2At least 30min to ensure oxygen saturation of the electrolyte. At 100mV s-1The scan rate of (2) was first 20 Cyclic Voltammetry (CV) scans until the electrodes reached steady state, then 5mVs-1Linear Sweep Voltammetry (LSV) was performed. The stability of the material was tested by CV scanning at a scanning rate of 100mV s-1HER was tested in the range of 0.05V to-0.4V and OER in the range of 1.2V to 2V. All testsiR corrections were made. A double-electrode test method is selected, Cu-CoP/CP is used as a cathode and is also used as an anode, and a full-hydrolysis experiment is carried out in a 1.0M KOH electrolyte.
FIG. 5 shows CoP and Cu0.25Co0.75P、Cu0.5Co0.5P and Cu0.75Co0.25Linear scan plot of P evolution in alkaline medium. FIG. 5 shows the CoP and Cu produced-HER performance of CoP sample under alkaline condition, reaching 10mA cm-2In time of, CoP, Cu0.25Co0.75P、Cu0.5Co0.5P、Cu0.75Co0.25The overpotential of P is 180.1mV, 149.2mV, 129.2mV and 80.2mV respectively, and the HER performance of CuCoP can be obviously improved.
FIG. 6 shows CoP and Cu0.25Co0.75P、Cu0.5Co0.5P and Cu0.75Co0.25Linear scan plot of P evolution in alkaline medium. FIG. 6 shows the OER performance of the prepared CoP and Cu-CoP samples under alkaline conditions, up to 10mA cm-2In time of, CoP, Cu0.25Co0.75P、Cu0.5Co0.5P、Cu0.75Co0.25The overpotential of P is 340.1mV, 279.7mV, 270mV and 250mV respectively, and Cu can be obviously seen-The OER performance of the CoP is obviously improved.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
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