CN116815239A - NiCuP@CeO 2 Preparation method and application of/NF oxygen evolution electrocatalyst - Google Patents
NiCuP@CeO 2 Preparation method and application of/NF oxygen evolution electrocatalyst Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001301 oxygen Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 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 abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 49
- 229910003322 NiCu Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- NQAOOXILUKVBAU-UHFFFAOYSA-N CO.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] Chemical compound CO.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] NQAOOXILUKVBAU-UHFFFAOYSA-N 0.000 claims description 4
- NGKWYRANVWGTGG-UHFFFAOYSA-N [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NGKWYRANVWGTGG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 20
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
Abstract
The invention belongs to the field of composite material preparation, and in particular relates to NiCuP@CeO 2 Preparation method and application of NF oxygen evolution electrocatalyst; the method comprises the following steps: (1) Respectively dissolving nickel nitrate hexahydrate, copper nitrate trihydrate and cerium nitrate hexahydrate in a methanol solution to form a uniform metal salt methanol solution; (2) Respectively measuring different metal salt methanol solutions, adding urea and the methanol solutions, uniformly mixing, adding foam nickel NF, performing hydrothermal reaction, and naturally cooling to room temperature; (3) Respectively placing the product of the step (2) and sodium hypophosphite into two porcelain boats, placing the porcelain boats into a tube furnace for calcination, and cooling to room temperature to obtain NiCuP@CeO 2 a/NF catalyst; the material prepared by the invention has excellent oxygen evolution capability, and the current density can reach 10 mA cm only by 220 mV overpotential ‑2 Catalytic oxygen evolution performance is even better than noble metal catalysts; stability measurements up to 15 hoursIn the test, the catalytic activity was not attenuated.
Description
Technical Field
The invention belongs to the field of composite material preparation, and relates toElectrolytic water catalytic material technology, in particular to NiCuP@CeO 2 Preparation method and application of NF oxygen evolution electrocatalyst.
Background
The continuous increase in fossil fuel consumption is accompanied by an increasing rise in environmental pollution, and energy shortage and climate change have become problems that humans have to face. Scientists have been striving to explore high energy density, sustainability, and environmentally friendly energy sources. Hydrogen (H) 2 ) As a clean and green energy carrier, the energy-saving device has the characteristics of high energy conversion efficiency, high energy density, zero emission of carbon dioxide, good environmental compatibility and the like, can replace the traditional non-renewable energy sources to a certain extent, and reduces the dependence of human beings on fossil fuels. Renewable resources are adopted for the electrocatalytic water splitting hydrogen production, and the method accords with the sustainable development of modern society and economy. Over the past few decades, researchers have extensively explored electrocatalytic OER and designed a wide variety of catalysts in an effort to improve electrode kinetics and chemical stability in different electrolyte environments. To date, iridium dioxide (IrO) 2 ) And ruthenium dioxide (RuO) 2 ) Is the OER electrocatalyst with the best overall performance and the most widely used, however, the high cost and low abundance of these noble metal materials severely hampers their large-scale commercial application. Therefore, there is a need to develop a low-cost, high-performance and stable non-noble metal catalyst instead of a noble metal catalyst.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a NiCuP@CeO 2 A method for preparing NF oxygen evolution electrocatalyst. The invention adopts CeO on the surface 2 The modification strategy regulates and controls the surface electron distribution of the bimetallic phosphide, thereby realizing the enhancement of OER activity. The CeO is synthesized by taking foam Nickel (NF) as a substrate, adding a certain amount of metal salts and adopting a simple hydrothermal-calcining method 2 Catalyst with NiCuP nanoflower modified on nanosphere surface (NiCuP@CeO) 2 /NF), to redistribute surface electrons, promote electron transfer from NiCuP to CeO 2 And (5) transferring. The results show that NiCuP@CeO 2 The electron structure of/NF reduces the reaction energy barrier, accelerates charge transfer, and behavesGood OER catalytic performance is obtained. The invention has simple operation, low production cost and easy realization of scale, and the NiCuP@CeO prepared by the method 2 the/NF can maintain the microstructure and good catalytic activity of the NF under alkaline conditions for a long time, and has potential industrial application value in the aspect of electrocatalytic oxygen evolution.
In order to solve the technical problems, the invention adopts the following technical scheme: niCuP@CeO 2 The preparation method of the NF oxygen evolution electrocatalyst comprises the following steps:
(1) Respectively dissolving nickel nitrate hexahydrate, copper nitrate trihydrate and cerium nitrate hexahydrate in a methanol solution to form a uniform metal salt methanol solution;
(2) Respectively measuring different metal salt methanol solutions in the step (1), adding urea and the methanol solution, magnetically stirring until the solutions are uniformly mixed, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel reaction kettle, adding foam nickel NF, performing hydrothermal reaction, and after naturally cooling to room temperature, respectively washing the foam nickel with water and ethanol to obtain NiCu@Ce pre-reactor;
(3) Respectively placing the obtained NiCu@Ce pre-reactor and sodium hypophosphite into two porcelain boats, calcining in a tube furnace, cooling to room temperature to obtain NiCuP@CeO 2 a/NF catalyst.
Further, in the step (1), the concentration of the nickel nitrate methanol solution is 0.5 mol/L, the concentration of the copper nitrate methanol solution is 0.5 mol/L, and the concentration of the cerium nitrate methanol solution is 0.5 mol/L.
Further, in the step (2), the volume ratio of the nickel nitrate methanol solution, the copper nitrate methanol solution, the cerium nitrate methanol solution and the methanol solution is 80:1:0-2:64-66.
Further, in the step (2), the volume-mass ratio of the methanol solution to the urea is 64-66mL:3g; the mass ratio of urea in the step (2) to sodium hypophosphite in the step (3) is 6:1.
Preferably, the nickel foam in step (2) has a size of 2.2X3.5 cm 2 The temperature of the hydrothermal reaction in the step (2) is 120 ℃, and the reaction time is 10 hours.
Preferably, the calcination in step (3) is carried out under Ar atmosphere, heated to 350 ℃ at a rate of 5 ℃/min and maintained at 1 h.
In addition, the invention also provides NiCuP@CeO prepared by the preparation method 2 Use of a/NF catalyst in the electrocatalytic oxygen evolution of electrolyzed water.
Further, the application method is to apply NiCuP@CeO 2 the/NF catalyst sample was cut to 1X 0.5 cm 2 Size, taking the electrode as a working electrode, testing by using an electrochemical workstation, and precious metal IrO 2 Mixing with naphthol solution to obtain mixed solution, and dripping onto 1×0.5. 0.5 cm 2 The test was performed on a large and small blank nickel foam NF.
Preferably, the concentration of the naphthol solution is 5 Wt%, irO 2 The preparation method of the naphthol mixed solution comprises the following steps: 10 mg IrO 2 Placed in 1 mL 5 Wt% naphthol solution and sonicated for 30 min.
Preferably, the testing method adopts a three-electrode working system, adopts Hg/HgO as a reference electrode, adopts a carbon rod as a counter electrode and adopts potassium hydroxide solution as electrolyte under alkaline conditions.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst prepared by the invention has the advantages of low cost of raw materials, short operation period, high repeatability and easy mass production.
2. In the preparation method, only the ultrasonic instrument, the magnetic stirrer, the oven, the tube furnace and other conventional reaction equipment are needed, the equipment is cheap and easy to obtain, and the operation is simple.
3. The material prepared by the invention has excellent oxygen evolution capability, and the current density can reach 10 mA cm only by 220 mV overpotential -2 Catalytic oxygen evolution performance is even better than noble metal catalysts; in stability tests up to 15 hours, the catalytic activity did not decay.
4. The invention makes full use of excellent electronic conductivity of the foam nickel substrate, and successfully prepares NiCuP@CeO with synergistic effect by a simple and easily available experimental method 2 The NF catalyst improves the active site of the catalytic material, so that the catalyst has good electrocatalytic performance.
Drawings
FIG. 1 shows NiCuP@CeO obtained in example 1 2 XRD spectrum of NF catalyst.
FIG. 2 is NiCuP@CeO prepared in example 1 2 SEM photograph of NF catalyst.
FIG. 3 is NiCuP@CeO obtained in example 1 2 EDX mapping graph of NF catalyst.
FIG. 4 shows NiCuP@CeO obtained in example 1 2 N/NF, niCu@Ce presurer, niCuP/NF obtained in example 2, irO 2 And linear sweep voltammograms of NF catalysts.
FIG. 5 shows NiCuP@CeO obtained in example 1 2 NiCuP@CeO obtained in example 3 2 NiCuP@CeO obtained in/NF-1 and example 4 2 Linear sweep voltammogram of NF-2 catalyst.
FIG. 6 is NiCuP@CeO obtained in example 1 2 N/NF, niCu@Ce presurer, niCuP/NF and IrO obtained in example 2 2 And tafel plot for NF catalysts.
FIG. 7 is NiCuP@CeO obtained in example 1 2 N/NF, niCu@Ce presurer, niCuP/NF and IrO obtained in example 2 2 And EIS test plots for NF catalysts.
FIG. 8 is NiCuP@CeO obtained in example 1 2 Voltage versus time stability test plot of NF catalyst in alkaline (1M KOH) electrolyte.
Description of the embodiments
The invention is further illustrated below with reference to specific examples.
Examples
Cut out size 2.2X3.5 cm 2 Ultrasonic cleaning with 3 mol/L hydrochloric acid, acetone and ethanol respectively for 10 min, and then drying the foam nickel in a vacuum drying oven for standby. 2.9672 g Ni (NO) 3 ) 2 ∙6H 2 O，2.4282 g Cu(NO 3 ) 2 ∙3H 2 O，4.3640 g Ce(NO 3 ) 3 ∙6H 2 O is dissolved in 20. 20 ml methanol solution respectively, and the concentration is 0.5 mol/L. The solutions (1.6 mL Ni (NO) 3 ) 2 ∙6H 2 O-methanol solution, 0.2 mL Cu (NO) 3 ) 2 ∙3H 2 O-methanol solution, 0.2 mL Ce (NO 3 ) 3 ∙6H 2 O-methanol solution), 0.6. 0.6 g urea and 13. 13 mL methanol were added and magnetically stirred for 30 min until the solution was well mixed.
Transferring the mixed solution into a stainless steel reaction kettle with a 20 mL polytetrafluoroethylene lining, adding a piece of pretreated foam nickel, sealing the high-pressure reaction kettle, performing hydrothermal reaction at 120 ℃ for 10h, and naturally cooling to room temperature. And respectively using deionized water and ethanol to wash foam nickel after thermal reaction, and drying the obtained sample in a vacuum oven at 50 ℃ for 12h to obtain NiCu@Ce prescuror. Then NiCu@Ce pre-cursor is combined with 1 g NaH 2 PO 2 Respectively put into two porcelain boats, naH 2 PO 2 The porcelain boat is positioned at the upstream of the tube furnace, and the NiCu@Ce pre-reactor porcelain boat is positioned at the downstream of the tube furnace. Heating to 350 ℃ at a speed of 5 ℃/min under Ar atmosphere, keeping 1 h, and finally cooling to room temperature to obtain NiCuP@CeO 2 a/NF catalyst.
Examples
As in example 1, except that 0.2 mL of Ce (NO 3 ) 3 ∙6H 2 The O-methanol solution and the 13 mL methanol solution are changed into 13.2 mL methanol solution, and other synthesis conditions are not changed, so that the NiCuP/NF catalyst can be obtained.
Examples
As in example 1, except that 0.2 mL of Ce (NO 3 ) 3 ∙6H 2 The O-methanol solution and the 13 mL methanol solution were changed to 0.1 mL Ce (NO) 3 ) 3 ∙6H 2 The O-methanol solution and the 13.1 mL methanol solution are not changed in other synthesis conditions, and NiCuP@CeO can be obtained 2 NF-1 catalyst.
Examples
As in example 1, except that 0.2 mL of Ce (NO 3 ) 3 ∙6H 2 The O-methanol solution and the 13 mL methanol solution were changed to 0.4 mL Ce (NO) 3 ) 3 ∙6H 2 The O-methanol solution and the 12.8 mL methanol solution are not changed in other synthesis conditions,NiCuP@CeO can be obtained 2 NF-2 catalyst.
Examples
As in example 1, niCuP was synthesized by changing the hydrothermal reaction time from 10 to h to 8 hours 1 @CeO 2 /NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 298 mV.
Examples
As in example 1, niCuP was synthesized by changing the hydrothermal reaction time from 10 to h to 12 hours 2 @CeO 2 /NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 276 mV.
Examples
As in example 1, niCuP@CeO was synthesized by changing the calcination temperature of the tube furnace from 350℃to 300 ℃ 2 -1/NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 335 mV.
Examples
As in example 1, niCuP@CeO was synthesized by changing the calcination temperature of the tube furnace from 350℃to 400 ℃ 2 -2/NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 312 mV.
Examples
As in example 1, niCuP@CeO was synthesized by changing the calcination time of the tube furnace from 1 h to 0.5 h 2 -3/NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 350 mV.
Examples
As in example 1, niCuP@CeO was synthesized by changing the calcination time of the tube furnace from 1 h to 2h 2 -4/NF. When the current density is 10 mA cm under alkaline solution -2 At this time, the overpotential was 307 mV.
The catalyst prepared by the method is subjected to necessary structural characterization and electrochemical performance test. FIG. 1 shows a catalyst NiCuP@CeO 2 X-ray diffraction (XRD) pattern of/NF, niCuP@CeO 2 The X-ray diffraction peaks of/NF at 41.1℃and 49.2℃correspond to CuP, respectively 2 A kind of electronic device(121) Crystal plane and crystal plane(221) Crystal face (JCPDS No. 18-0882) showing CuP 2 Is generated. Further, at 54.4 ° and 55.2 ° correspond to Ni, respectively 2 The (100) and (211) crystal planes of P (JCPDS No. 65-9706) indicate Ni 2 And (3) generating P. And the (111) crystal plane at 44.0℃corresponding to NiCu (JCPCDS No. 65-9047) further confirmed NiCuP@CeO 2 Formation of bimetallic NiCu in/NF. At the same time, the foam nickel NF and CeO can be clearly seen 2 Is matched with standard card (Ni JCCPDF No. 62-2865 and CeO) 2 JCDF No. 65-5923) to indicate CeO 2 Is a successful doping of (c). Taken together, we have shown that NiCuP@CeO was successfully synthesized 2 a/NF catalyst.
FIG. 2 shows a catalyst NiCuP@CeO 2 SEM photograph of NF, it can be seen that it has a flower-like structure and CeO is present on the sheet 2 Nanospheres, which greatly enhance the specific surface area of the catalyst and further promote NiCuP@CeO 2 OER catalytic activity of/NF. FIG. 3 shows the obtained NiCuP@CeO 2 According to the EDX mapping graph of/NF, the material contains Ni, cu, P, ce, O elements, and the five elements are uniformly distributed in the material.
The catalyst material prepared by the method is subjected to an electrocatalytic water splitting Oxygen Evolution (OER) performance test in a standard three-electrode electrolytic cell; wherein, the cyclic scanning range is 0-1.0V, and the scanning rate is 2 mV/s. All potentials obtained in the electrocatalytic test with the Hg/HgO electrode as a reference electrode were converted to reversible hydrogen electrode potentials in the performance diagram.
FIG. 4 is NiCuP@CeO 2 /NF、 IrO 2 Linear scan voltammograms of nicu@ce precursor, niCuP/NF and NF materials. With noble metal IrO 2 In comparison, it can be seen that NiCuP@CeO 2 The electrochemical performance of/NF is better. When the current density is 10 mA cm -2 At the time of NiCuP@CeO 2 The overpotential of/NF was only 220 mV.
FIG. 5 is NiCuP@CeO 2 /NF、NiCuP@CeO 2 NF-1 and NiCuP@CeO 2 Linear sweep voltammogram of NF-2 material. As shown in the figure, niCuP@CeO 2 Electrochemical performance of/NF is superior to NiCuP@CeO 2 NF-1 and NiCuP@CeO 2 /NF-2。
FIG. 6 is NiCuP@CeO 2 /NF、IrO 2 Tafil slope plot of NiCu@Ce precursor, niCuP/NF and NF catalyst, niCuP@CeO can be seen 2 Tafil slope of/NF was minimal, indicating NiCuP@CeO 2 The NF activity was highest and the reaction rate was fastest.
FIG. 7 is NiCuP@CeO 2 /NF、IrO 2 Impedance diagrams of NiCu@Ce precursor, niCuP/NF and NF catalyst can clearly see NiCuP@CeO 2 The impedance of/NF is the smallest, indicating that it possesses the fastest electron transfer capability.
FIG. 8 is NiCuP@CeO 2 the/NF catalyst had a current density of 10 mA cm -2 The stability test below, which maintains a stable state of 15 or more h without performance degradation, shows that the catalyst has excellent stability.
Claims (10)
1. NiCuP@CeO 2 The preparation method of the NF oxygen evolution electrocatalyst is characterized by comprising the following steps:
(1) Respectively dissolving nickel nitrate hexahydrate, copper nitrate trihydrate and cerium nitrate hexahydrate in a methanol solution to form a uniform metal salt methanol solution;
(2) Respectively measuring different metal salt methanol solutions in the step (1), adding urea and the methanol solution, magnetically stirring until the solutions are uniformly mixed, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel reaction kettle, adding foam nickel NF, performing hydrothermal reaction, and after naturally cooling to room temperature, respectively washing the foam nickel with water and ethanol to obtain NiCu@Ce pre-reactor;
(3) Respectively placing the obtained NiCu@Ce pre-reactor and sodium hypophosphite into two porcelain boats, calcining in a tube furnace, cooling to room temperature to obtain NiCuP@CeO 2 a/NF catalyst.
2. A NiCuP@CeO according to claim 1 2 The preparation method of the NF oxygen evolution electrocatalyst is characterized in that the concentration of the nickel nitrate methanol solution in the step (1) is 0.5 mol/L, and the concentration of the copper nitrate methanol solution is highThe concentration of the cerium nitrate methanol solution is 0.5 mol/L.
3. A NiCuP@CeO according to claim 2 2 The preparation method of the NF oxygen evolution electrocatalyst is characterized in that in the step (2), the volume ratio of nickel nitrate methanol solution, copper nitrate methanol solution, cerium nitrate methanol solution and methanol solution is 80:1:0-2:64-66.
4. A NiCuP@CeO according to claim 1 2 The preparation method of the NF oxygen evolution electrocatalyst is characterized in that the volume mass ratio of the methanol solution to the urea in the step (2) is 64-66mL:3g; the mass ratio of urea in the step (2) to sodium hypophosphite in the step (3) is 6:1.
5. A NiCuP@CeO according to claim 1 2 A process for preparing NF oxygen evolution electrocatalyst, characterized in that the size of the nickel foam in step (2) is 2.2X3.5 cm 2 The temperature of the hydrothermal reaction in the step (2) is 120 ℃, and the reaction time is 10 hours.
6. A NiCuP@CeO according to claim 1 2 A process for preparing an oxygen evolution electrocatalyst, characterized in that the calcination in step (3) is carried out under Ar atmosphere, heating to 350 ℃ at a rate of 5 ℃/min and maintaining 1 h.
7. A nicup@ceo prepared by the preparation method according to any one of claims 1 to 6 2 Use of a/NF catalyst in the electrocatalytic oxygen evolution of electrolyzed water.
8. The use according to claim 7, characterized in that: niCuP@CeO 2 the/NF catalyst sample was cut to 1X 0.5 cm 2 Size, taking the electrode as a working electrode, testing by using an electrochemical workstation, and precious metal IrO 2 Mixing with naphthol solution to obtain mixed solution, and dripping onto 1×0.5. 0.5 cm 2 The test was performed on a large and small blank nickel foam NF.
9. The use according to claim 8, characterized in that: the concentration of naphthol solution was 5 Wt%, irO 2 The preparation method of the naphthol mixed solution comprises the following steps: 10 mg IrO 2 Placed in 1 mL 5 Wt% naphthol solution and sonicated for 30 min.
10. The use according to claim 8, characterized in that: the testing method adopts a three-electrode working system, takes Hg/HgO as a reference electrode, takes a carbon rod as a counter electrode, and takes potassium hydroxide solution as electrolyte under alkaline condition.
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