CN111185206B - 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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- CN111185206B CN111185206B CN202010071811.6A CN202010071811A CN111185206B CN 111185206 B CN111185206 B CN 111185206B CN 202010071811 A CN202010071811 A CN 202010071811A CN 111185206 B CN111185206 B CN 111185206B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 230000007704 transition Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001354 calcination Methods 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
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 27
- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229940011182 cobalt acetate Drugs 0.000 description 11
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- 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
- 238000001000 micrograph Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method 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
- 238000005868 electrolysis reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019239 CoFx Inorganic materials 0.000 description 2
- 229910002651 NO3 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
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052742 iron Inorganic materials 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
- -1 ketone nitrate Chemical class 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 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
- 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 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
- 230000002349 favourable effect Effects 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
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum 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
- 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/613—
-
- 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
- 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 relates to the technical field of electrocatalysis, in particular to a transition metal-phosphide catalyst, a preparation method and application thereof. The invention discloses a transition metal-phosphide catalyst, the chemical formula of which is M x ‑N 1‑x P is as follows; the transition metal-phosphide catalyst has a chestnut-shaped structure; the specific surface area of the transition metal-phosphide catalyst is 69.1-92.3m 2 /g; wherein M and N are both metals, and x is 0-1. The catalyst is in a chestnut-shaped structure and has a large specific surface area, so that the active sites of a catalytic material are increased, and the catalyst can simultaneously show 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, a preparation method and application thereof.
Background
The petroleum resources on the earth have been exhausted gradually since the 21 st century, and environmental pollution has become serious, so the development of a novel clean energy is a necessary trend. The hydrogen energy is emerging as a low-carbon and zero-carbon energy source, and the combustion product is water, so that the hydrogen energy is pollution-free and can be recycled. One of the methods for producing hydrogen is electrolysis 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 currently best-used electrocatalyst is noble metal represented by platinum, but the storage amount is limited and expensive, so that an inexpensive and efficient electrocatalyst needs to be developed. The transition metal phosphide has good development prospect in the hydrogen preparation field, and is low in cost, good in conductivity and stable in chemical property. The catalyst is used for electrolyzing water, so that the performances of hydrogen evolution and water electrolysis can be effectively improved, and the cost can be saved. With the increasing requirements of people on the catalytic performance of electrocatalysts, improving the catalytic performance of transition metal phosphide is a technical problem to be solved in the field.
At present, the document Ternary metal phosphide nanosheets as a highly efficient electrocatalyst for water reduction to hydrogen over a wide pH range from to 14 discloses that cobalt phosphide-nickel nanoplatelets CoNiP@NF are prepared on foam Nickel (NF), and 10mA cm in hydrogen evolution reaction -2 At a current density of 1M KOH at an overpotential of 155mV; document "Sulfur-doped dicobalt phosphide outperforming precious metals as a bifunctional electrocatalyst for alkaline water electrolysis" discloses the preparation of S-loaded Co on Carbon Cloth (CC) 2 P catalyst, 10mA cm in oxygen evolution reaction -2 The overpotential at 1MKOH was 290mV each. The transition metal phosphide has not high enough catalytic performance for hydrogen evolution reaction and hydrogen evolution reaction, and can not simultaneously have good catalytic performance for oxygen evolution reaction and hydrogen evolution reaction.
Disclosure of Invention
In view of the above, the invention provides a transition metal-phosphide catalyst, a preparation method and application thereof, wherein the specific surface area of the catalyst is increased, active sites are increased, and the electrocatalytic performance of the catalyst is further improved.
The specific technical scheme is as follows:
the present invention provides a transition metal-phosphide catalyst having the chemical formula M x -N 1-x P；
The transition metal-phosphide catalyst is of a chestnut-shaped structure;
the specific surface area of the transition metal-phosphide catalyst is 69.1-92.3m 2 Preferably 92.3m 2 /g；
Wherein M and N are both metals, and x is 0to 1, more preferably 0.25, 0.5, 0.75 or 1.
The metal 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 specific surface area of the transition metal-phosphide catalyst is high, the active site of the catalytic material is increased, and the catalyst shows excellent catalytic activity when being applied to hydrogen evolution reaction.
The invention also provides a preparation method of the transition metal-phosphide catalyst, which comprises the following steps:
step 1: after dissolving a first metal salt and a second metal salt in water, 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, and the ammonium fluoride is taken as a complexing agent, is a stabilizer for the whole hydrothermal reaction, is favorable for crystallization of products, and takes urea as a mineralizer to provide an alkali source for the whole reaction.
Take the transition metal-phosphide catalyst CoP as an example:
(1)Co 2+ +xF - →CoFx (x-2)-
(2)H 2 NCONH 2 +H 2 O→2NH 3 +CO 2
(3)NH 3 ·H 2 O→NH 4+ +OH -
(4)Co 2+ +I-X- & lt- & gt-X.Co 2+ (X＝COO - ，COH)
(5)CoFx (x-2)- +I-X=I-X.Co 2+ +xF -
(6) one-X.Co 2+ +2OH - first-X Co (OH) 2
The transition metal-phosphide catalyst CoP is synthesized in one step by directly annealing a phosphorus-containing compound and a cobalt precursor.
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 40mL:8mmol:15mmol:4mmol. If the ratio of the total amount of the first metal salt to the second metal salt is changed, the morphology of the metal salt is also changed.
The preparation method has the advantages that the reaction condition is mild in the whole preparation process, the operation is simple, the transition metal resource is cheaper and more available than platinum, sodium hypophosphite and the like are not used as phosphorus sources in the reaction, the harm to the environment and human body caused by the generation of phosphine gas is avoided, and the preparation method is safer and more environment-friendly.
In step 1 of the present invention, the first metal in the first metal salt and the second metal in the second metal salt are 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 hydroxyethylidene diphosphonic acid;
in the step 2 of the present invention, the size of the carbon paper is (1×1cm to 2×3 cm), preferably 2×3cm;
the hydrothermal temperature is 120-200 ℃, and the time is 6-24 hours, preferably 120 ℃ and 6 hours; 120 ℃ for 24 hours; 200 ℃ for 6 hours; 200 ℃ for 24 hours;
after the hydrothermal reaction, the method further comprises the following steps: the carbon paper obtained after the hydrothermal reaction is respectively washed by water and ethanol;
the calcining temperature is 600-800 ℃, the heating rate is 1-5 ℃/min, the heat preservation time is 1-3h, and the preferable temperature is 800 ℃, 5 ℃/min and 3h;600 ℃,1 ℃/min and 1h;600 ℃, 5 ℃/min and 1h;600 ℃,1 ℃/min and 1h.
The invention also provides a working electrode comprising the transition metal-phosphide catalyst or the transition metal-phosphide catalyst prepared by the preparation method.
The invention also provides a reaction device, comprising: the working electrode, the reference electrode and the counter electrode.
The invention also provides application of the reaction device in hydrogen evolution reaction, oxygen evolution reaction or full hydrolysis reaction.
The hydrogen evolution reaction of the invention can be carried out at full pH, and the oxygen evolution reaction and the full hydrolysis reaction can be carried out under alkaline conditions.
From the above technical scheme, the invention has the following advantages:
the invention provides a transition metal-phosphide catalyst which has a chestnut-shaped structure and a larger specific surface area, so that the active sites of a catalytic material are increased, and the catalyst can simultaneously show excellent catalytic activity on hydrogen evolution reaction and oxygen evolution reaction and has good comprehensive performance. Experimental data shows 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 invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of carbon paper provided by an embodiment of the 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;
FIG. 3 shows a chestnut-like cobalt phosphorus catalyst Cu provided in example 2 of the present invention 0.25 Co 0.75 P is a scanning electron microscope image;
FIG. 4 shows the chestnut-shaped cobalt phosphorus catalysts CoP and Cu provided in example 1 and example 2 of the present invention 0.25 Co 3.75 X-ray photoelectron spectrum of P;
FIG. 5 shows the chestnut-like cobalt phosphorus catalysts CoP and Cu provided in examples 1, 2, 6 and 7 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P and Cu 0.75 Co 0.25 P hydrogen evolution linear scan profile in alkaline medium;
FIG. 6 shows the plates according to the invention of examples 1, 2, 6 and 7Chestnut-like cobalt phosphorus catalyst CoP, cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P and Cu 0.75 Co 0.25 Oxygen evolution linear scan profile of P 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 of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the embodiments described below are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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 to obtain a cobalt acetate solution;
2. 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid are taken and added into the solution of the cobalt acetate obtained in the step 1 to be fully dissolved, so as to obtain a mixed solution;
3. adding 2X 3cm carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 6 hours at 120 ℃, and respectively washing and drying the reacted carbon paper with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high temperature furnace, heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min under a hydrogen atmosphere, and preserving the temperature for 1 hour to obtain the chestnut-shaped cobalt phosphorus catalyst CoP.
Fig. 1 is a scanning electron microscope image of the carbon paper of the present embodiment. Fig. 1 shows that the carbon paper surface is not covered with any substance.
Fig. 2 is a scanning electron microscope image of the chestnut-like cobalt phosphorus catalyst CoP of the present example. Fig. 2 shows that the entire carbon paper surface is covered with a chestnut-like nanorod array.
Example 2
The embodiment is a chestnut-shaped cobalt phosphorus catalyst Cu 0.25 Co 0.75 Preparation of P
1. Weighing copper nitrate and cobalt acetate with the molar ratio of 0.25:0.75, and adding 40mL of water for full dissolution to obtain an aqueous solution of the copper nitrate and the cobalt acetate;
2. 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid are taken and added into the aqueous solution of the ketone nitrate and the cobalt acetate obtained in the step 1 to be fully dissolved, so as to obtain a mixed solution;
3. adding 2X 3cm carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 6 hours at 120 ℃, and respectively washing and drying the reacted carbon paper with water and ethanol;
4. placing the dried product obtained in the step 3 in a high temperature furnace, heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min under a hydrogen atmosphere, preserving heat at the temperature for 1 hour, and annealing to obtain the chestnut-shaped cobalt phosphorus catalyst Cu 0.25 Co 0.75 P。
FIG. 3 shows a chestnut-like cobalt phosphorus catalyst Cu of the present embodiment 0.25 Co 0.75 Scanning electron microscope image of P. Fig. 1 shows that the surface of the carbon paper is still a chestnut-shaped nanorod array after copper doping, which is not significantly changed compared with fig. 2.
FIG. 4 shows the CoP of example 1 and Cu of this example 0.25 Co 0.75 X-ray photoelectron spectrum of P. FIG. 4 shows CoP and Cu 0.25 Co 0.75 The diffraction peaks of the P sample were matched to the orthogonal phase CoP structure (JCPDS No. 29-0497). XRD results indicate that a small amount of Cu atom doping does not damage the crystal structure of CoP.
Example 3
The embodiment is a chestnut-shaped cobalt phosphorus catalyst Cu 0.5 Co 0.5 Preparation of P
1. Weighing copper nitrate and cobalt acetate with the molar ratio of 0.50:0.50, and adding 40mL of water for full dissolution to obtain an aqueous solution of the copper nitrate and the cobalt acetate;
2. 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid are taken and added into the aqueous solution obtained in the step 1 to be fully dissolved, so as to obtain a mixed solution;
3. adding 2X 3cm carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 24 hours at 120 ℃, and respectively washing and drying the reacted carbon paper with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high temperature furnace, heating from room temperature to 600 ℃ at a heating rate of 5 ℃/min under a hydrogen atmosphere, preserving heat at the temperature for 1 hour, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 4
The embodiment is a chestnut-shaped cobalt phosphorus catalyst Cu 0.75 Co 0.25 Preparation of P
1. Weighing copper nitrate and cobalt acetate with the molar ratio of 0.75:0.25, and adding 40mL of water for full dissolution to obtain an aqueous solution of the copper nitrate and the cobalt acetate;
2. 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid are taken and added into the aqueous solution obtained in the step 1 to be fully dissolved, so as to obtain a mixed solution;
3. adding 2X 3cm carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 6 hours at 200 ℃, and respectively washing and drying the reacted carbon paper with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high temperature furnace, heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min under a hydrogen atmosphere, preserving heat at the temperature for 1 hour, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 5
The embodiment is a chestnut-shaped cobalt phosphorus catalyst Fe 0.9 Co 0.1 P is prepared by 1, weighing ferric nitrate and cobalt chloride with the molar ratio of 0.9:0.1, and adding 40mL of water for full dissolution to obtain an aqueous solution of the ketone nitrate and the cobalt acetate;
2. 8mmol of ammonium fluoride, 15mmol of urea and 4mmol of phosphoric acid are taken and added into the aqueous solution obtained in the step 1 to be fully dissolved, so as to obtain a mixed solution;
3. adding 2X 3cm carbon paper and the mixed solution obtained in the step 2 into a reaction kettle liner for hydrothermal reaction for 24 hours at 200 ℃, and respectively washing and drying the reacted carbon paper with water and ethanol;
4. and (3) placing the dried product in the step (3) in a high temperature furnace, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min under a hydrogen atmosphere, preserving heat at the temperature for 3 hours, and annealing to obtain the chestnut-shaped cobalt-phosphorus catalyst.
Example 6
This example is for example 1CoP, example 2Cu 0.25 Co 0.75 P, example 3Cu 0.5 Co 0.5 P and example 4Cu 0.75 Co 0.25 P performing electrochemical test
Electrochemical testing method: all electrochemical measurements were performed using a PGSTAT302N potentiostat (Metrohm Autolab, netherlands). Using conventional three-electrode testing, coP or Cu 0.25 Co 0.75 The P is cut to be 1 multiplied by 1cm and then is 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 2 SO 4 1.0M KOH and 1.0M PBS) are aerated with high purity nitrogen for at least 30min to remove dissolved oxygen from the electrolyte. O is required to be communicated before OER test 2 At least 30 minutes to ensure oxygen saturation of the electrolyte. At 100mV s -1 Is scanned at a scanning rate of 5mV s after 20 Cyclic Voltammetry (CV) scans are performed until the electrode reaches a steady state -1 Linear Sweep Voltammetry (LSV) was performed. The stability of the material was tested by CV scanning at a scanning rate of 100mV s -1 HER was tested in the range of 0.05V to-0.4V and oer in the range of 1.2V to 2V. All tests were iR corrected. A double-electrode test method is selected, cu-CoP/CP is used as a cathode and also used as an anode, and a full hydrolysis experiment is carried out in 1.0M KOH electrolyte.
FIG. 5 is CoP, cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P and Cu 0.75 Co 0.25 Linear sweep profile of hydrogen evolution of P in alkaline medium. FIG. 5 shows the prepared CoP and Cu - HER performance of CoP samples under alkaline conditions, at up to 10mA cm -2 At the time of CoP, cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P、Cu 0.75 Co 0.25 The overpotential of P is 180.1mV, 149.2mV, 129.2mV and 80.2mV respectively, and it can be obviously seen that the HER performance of CuCoP is obviously improved。
FIG. 6 is CoP, cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P and Cu 0.75 Co 0.25 Oxygen evolution linear scan profile of P in alkaline medium. FIG. 6 shows OER performance of the prepared CoP and Cu-CoP samples under alkaline conditions at 10mA cm -2 At the time of CoP, cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P、Cu 0.75 Co 0.25 The overpotential of P was 340.1mV, 279.7mV, 270mV and 250mV, respectively, and Cu was evident - The OER performance of the CoP is significantly improved.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A method for preparing a transition metal-phosphide catalyst, comprising the steps of:
step 1: after dissolving a first metal salt and a second metal salt in water, adding ammonium fluoride, urea and a phosphorus-containing compound to obtain a mixed solution;
step 2: adding carbon paper into the mixed solution for hydrothermal reaction, drying and calcining to obtain transition metal-phosphide;
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 40mL:8mmol:15 mmol:4mmol;
the phosphorus-containing compound is selected from phytic acid, phosphoric acid or hydroxyethylidene diphosphonic acid;
chemistry of the transition metal-phosphide catalystThe general formula is M x -N 1-x P；
The transition metal-phosphide catalyst is of a chestnut-shaped structure;
the specific surface area of the transition metal-phosphide catalyst is 69.1-92.3m 2 /g；
The transition metal-phosphide catalyst is Cu 0.25 Co 0.75 P、Cu 0.5 Co 0.5 P。
2. The method according to claim 1, wherein the hydrothermal temperature is 120-200 ℃ for 6-24 hours.
3. The preparation method according to claim 2, wherein the calcination temperature is 600-800 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-3h.
4. A working electrode comprising the transition metal-phosphide catalyst produced by the production method as claimed in any one of claims 1 to 3.
5. A reaction apparatus, comprising: the working electrode, reference electrode, and counter electrode of claim 4.
6. The use of the reaction apparatus of claim 5 in oxygen evolution or hydrogen evolution.
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| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN109967100A (en) * | 2019-05-05 | 2019-07-05 | 河南大学 | A kind of metal-doped CoP3, preparation method and application |
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| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
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