CN110607532A - Preparation method of Co-Ni-P/fs-Si material for hydrogen evolution by water electrolysis - Google Patents
Preparation method of Co-Ni-P/fs-Si material for hydrogen evolution by water electrolysis Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910018104 Ni-P Inorganic materials 0.000 title claims abstract description 29
- 229910018536 Ni—P Inorganic materials 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 13
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 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 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 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 5
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- -1 AgCl (saturated potassium chloride Chemical class 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 238000001816 cooling Methods 0.000 claims 3
- 239000001307 helium Substances 0.000 claims 2
- 229910052734 helium Inorganic materials 0.000 claims 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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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
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a preparation method of a Co-Ni-P/fs-Si material for electrolyzing water to generate hydrogen, belonging to the technical field of new energy material preparation. The invention comprises four steps: (1) etching silicon by adopting a femtosecond laser processing technology to obtain fs-Si with a certain morphology as a substrate; (2) preparing a cobalt-nickel precursor/fs-Si material by using fs-Si as a substrate and adopting a hydrothermal method; (3) carrying out phosphating treatment on the synthesized cobalt-nickel precursor/fs-Si material to obtain a Co-Ni-P/fs-Si material; (4) the prepared Co-Ni-P/fs-Si material is used as a self-supporting electrode and has excellent performance of hydrogen evolution by water electrolysis; at 0.5mol L‑1H2SO4In solution, 10mA cm‑2The required voltage was 69 mV. The method is simple and easy to operate, can be used for mass production, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of new energy material preparation, in particular to a preparation method of a Co-Ni-P/fs-Si material for hydrogen evolution by water electrolysis.
Background
With the rapid consumption of traditional fossil energy such as petroleum, coal, natural gas and the like, the problems of environmental pollution, large amount of greenhouse gas emission and the like caused by the combustion of the fossil energy become increasingly prominent. Therefore, the development of environment-friendly, clean and efficient alternative new energy is imperative. Hydrogen gas is expected to be a green energy source having a high energy density and a non-polluting combustion product, and is renewable, and is receiving wide attention in response to energy and environmental problems. The traditional industrial hydrogen production methods are mainly methane steam reforming and coal gasification, and the hydrogen produced by the two methods accounts for more than 90% of the total hydrogen production, but still needs a large amount of fossil energy as raw materials. The hydrogen production by electrolyzing water has the characteristics of simple device, pure product, high energy conversion rate and the like. Particularly, with the progress of the power generation technology of renewable energy sources such as wind energy, solar energy, tidal energy and the like, the convenience of hydrogen production by electrolysis is greatly improved, the cost is expected to be further reduced, and the hydrogen production by electrolysis is expected to become an important direction for the development of future energy sources.
In the process of electrolyzing water, two core reactions of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) exist, and the two reactions are limited by reaction kinetics, and both require high-efficiency catalysts to accelerate the reaction. At present, RuO2And Pt catalysts are the most efficient catalysts for OER and HER, but their use is limited due to their low inventory and high cost. For this reason, it has been the pursuit of researchers to prepare non-noble metal catalysts with high catalytic activity and low cost. Among them, cobalt and nickel are two metal elements commonly used in the preparation of the electrolytic water catalyst at present due to their abundant contents in the earth's crust and good catalytic activity, and are considered to be one of the materials most likely to replace noble metals as a material for constructing a novel electrocatalyst. Theoretically, the elementary cobalt and nickel should have the best electrocatalytic activity due to excellent metallicity and conductivity, but the elementary cobaltNickel is extremely unstable in an air environment and is easily oxidized, so that catalytic activity is reduced. Therefore, researchers can increase the exposed number of active sites by preparing cobalt and nickel catalysts with different shapes and structures; on the other hand, the catalyst is compounded with other non-noble metal elements to prevent oxidation and improve catalytic activity.
Transition metal catalysts, such as cobalt and nickel phosphide, have also been widely studied and developed in recent years. The Lizidona subject group takes ZIF-8@ ZIF-67 core-shell nano-particles as a template, and obtains a novel N-doped CoP nano-particle coated by a carbon nano-tube hollow polyhedron through continuous pyrolysis-oxidation-phosphorization processes. Due to the strong synergy of the CoP nanoparticles and the N-doped carbon nanotubes, the overpotential required for full water splitting is only 1.64V when the heterogeneous nanoparticles are used as cathode and anode. Furthermore, it also exhibits superior stability with continuous cycling for 36h without significant degradation. Jun Chen project group prepared a porous multi-layered Ni assembled by nanoparticles using a simple and economical template method2P hollow microspheres. Compared with pure nano particles and solid nanospheres, the multilayer porous multilayer hollow microsphere has more excellent catalytic hydrogen evolution performance under an alkaline condition. Husam n3Plasma technology converts NiCo hydroxide to NiCoP three-phase catalyst. The catalyst has excellent hydrogen evolution, oxygen evolution and full water decomposition performances. However, as far as we know, the research on improving the electrocatalytic performance of cobalt and nickel-based materials by combining a femtosecond processing substrate and cobalt nickel phosphide is not reported, and the preparation of the high-efficiency electrocatalytic hydrogen evolution material is still a valuable exploration topic.
Disclosure of Invention
The invention aims to solve the problems of high cost and scarcity of noble metal platinum as an electrocatalytic hydrogen evolution electrode material, and further provides a preparation method of a novel electrocatalytic hydrogen evolution electrode material.
The Co-Ni-P/fs-Si material prepared by the invention has the advantages of convenient preparation method, simple flow, low energy consumption, easily obtained raw materials and low overall cost. The method is realized by taking a femtosecond laser etched silicon chip as a novel self-supporting substrate, synthesizing a Co-Ni-P/fs-Si material by a method of firstly hydrothermal and then phosphorizing, wherein the material has a hierarchical micro-nano structure and exposes a plurality of active sites.
The preparation method of the Co-Ni-P/fs-Si material comprises the following specific steps:
the method comprises the following steps: treating the cleaned silicon wafer by a femtosecond laser processing technology to form a porous structure on the surface of the silicon wafer, and preparing fs-Si as a substrate;
step two: taking fs-Si prepared in the first step as a substrate, and synthesizing a cobalt-nickel precursor/fs-Si material by adopting a hydrothermal method under an acidic condition, wherein the hydrothermal temperature is 100-180 ℃ and the hydrothermal time is 5-24 hours;
step three: phosphorizing the cobalt-nickel precursor/fs-Si material synthesized in the step two, wherein a phosphorizing reagent is NaH2PO2Weighing 0.1-1.0 g of material, controlling the phosphating temperature to be 300-500 ℃, and heating for 1-4 hours in an inert atmosphere to obtain a Co-Ni-P/fs-Si material;
step four: and (4) testing by adopting a CHI660e electrochemical workstation at room temperature, and performing an electrolytic water hydrogen evolution performance test by taking the Co-Ni-P/fs-Si material synthesized in the step three as a self-supporting electrode.
Drawings
FIG. 1 is a 300-fold scanning electron microscope picture of a Co-Ni-P/fs-Si material;
FIG. 2 is a 900-fold scanning electron microscope picture of a Co-Ni-P/fs-Si material;
FIG. 3 is a 2300-fold scanning electron microscope picture of a Co-Ni-P/fs-Si material;
FIG. 4 is a polarization curve of Co-Ni-P/fs-Si material.
Detailed Description
Cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea, ammonium fluoride and sodium dihydrogen hypophosphite which are selected by the method are all commercially available analytical pure products, and deionized water is self-made by a laboratory; the glassware and equipment used are those commonly used in the laboratory.
The first embodiment is as follows: and cleaning a silicon wafer sold in the market by adopting alkaline cleaning, acid cleaning and ultrasonic cleaning. The preparation method of the alkaline washing liquid comprises the following steps: 20% concentrated ammonia water: 30% hydrogen peroxide: deionized water 1:1: 5; the preparation method of the pickling solution comprises the following steps: 25% concentrated hydrochloric acid: 30% hydrogen peroxide: washing with deionized water at a ratio of 1:1:6 at 60-80 ℃ for 10-20 minutes, washing with deionized water after alkaline washing and acid washing, performing ultrasonic cleaning for 10-20 minutes, and finally performing vacuum high-temperature drying; and (3) performing femtosecond laser etching on the cleaned silicon wafer to form a porous structure on the surface of the silicon wafer, thereby preparing the fs-Si substrate.
Adding cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea, ammonium fluoride and deionized water into a 50 ml beaker, and carrying out ultrasonic dissolution to obtain an orange pink solution, wherein the cobalt nitrate hexahydrate is used as a cobalt source, the weighed mass is 1.164 g, the nickel nitrate hexahydrate is used as a nickel source, the weighed mass is 0.582 g, the urea is used as a precipitator, the weighed mass is 0.6 g, the ammonium fluoride is used as a structure directing agent, the weighed mass is 0.185 g, and the added deionized water is 30 ml; transferring the obtained orange pink solution and the fs-Si substrate to a 50 ml reaction kettle, and carrying out hydrothermal treatment, wherein the hydrothermal temperature is 120 ℃, and the hydrothermal time is 5 hours; and washing and drying the product to obtain a pink cobalt-nickel precursor/fs-Si material.
Respectively placing the obtained cobalt-nickel precursor/fs-Si material and a phosphating reagent in two separated ceramic boats in a quartz tube, wherein the phosphating reagent is NaH2PO2Weighing 1.0 g; and NaH2PO2Is positioned at the upstream side of the tubular furnace, and the rate of temperature rise is 2 ℃ for min-1And the phosphating temperature is 350 ℃, the heating time is 2 hours under the inert atmosphere which is argon, and the Co-Ni-P/fs-Si material is finally obtained.
The second embodiment is as follows: this embodiment is different from the first embodiment in that the hydrothermal reaction time is 100 ℃, and the other steps are the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first embodiment in that the hydrothermal reaction time is 140 ℃, and the other steps are the same as the first embodiment.
The fourth concrete implementation mode: the difference between the experimental mode and the specific experimental mode is that cobalt nitrate hexahydrate is used as a cobalt source, the weighed mass is 0.582 g, nickel nitrate hexahydrate is used as a nickel source, the weighed mass is 1.164 g, and the rest is the same as that of the specific embodiment mode.
The fifth concrete implementation mode: the difference between the experimental mode and the specific experimental mode is that cobalt nitrate hexahydrate is used as a cobalt source, the weighed mass is 0.582 g, nickel nitrate hexahydrate is used as a nickel source, the weighed mass is 0.582 g, and the rest is the same as that of the specific embodiment mode.
The sixth specific implementation mode: the difference between the experimental mode and the specific experimental mode is that the hydrothermal reaction time is 12 hours; the rest is the same as the first embodiment.
The seventh embodiment: the difference between the experimental mode and the specific experimental mode is that the hydrothermal reaction time is 24 hours; the rest is the same as the first embodiment.
The materials were tested for hydrogen by electrowater desorption as follows:
the electrochemical measurement adopts CHI660e electrochemical workstation to test, the test temperature is room temperature, the electrode system is three-electrode configuration, respectively working electrode, auxiliary electrode and reference electrode, the working electrode is platinum sheet electrode sandwiching the sample to be tested, the auxiliary electrode is carbon rod, and the reference electrode is Ag/AgCl (saturated potassium chloride filled) or saturated calomel electrode; clamping the synthesized Co-Ni-P/fs-Si material by a platinum sheet electrode clamp, wherein the platinum sheet electrode clamp is not in contact with the electrolyte in the reaction tank, the area of the platinum sheet electrode clamp penetrating into the electrolyte is 0.02-0.1 square centimeter and is 0.5mol L-1H2SO4Recording linear sweep voltammetry in solution at a sweep rate of 5mV s-1(ii) a The Co-Ni-P/fs-Si material obtained in the first embodiment is used for carrying out an electrolytic water hydrogen evolution test, and the Co-Ni-P/fs-Si material prepared in the first embodiment has better electrolytic water hydrogen evolution performance at 0.5mol L-1H2SO4In solution, 10mA cm-2The required voltage was 69 mV.
The present invention may be embodied in other specific forms, and various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of a Co-Ni-P/fs-Si material for electrolyzing water to generate hydrogen is characterized by comprising the following preparation steps:
the method comprises the following steps: processing the cleaned silicon wafer by a femtosecond laser processing technology to form a porous structure on the surface of the silicon wafer to prepare fs-Si;
step two: taking fs-Si prepared in the first step as a substrate, and synthesizing a cobalt-nickel precursor/fs-Si material under an acidic condition by adopting a hydrothermal method;
step three: carrying out phosphating treatment on the cobalt-nickel precursor/fs-Si material synthesized in the step two to obtain a Co-Ni-P/fs-Si material;
step four: and (4) taking the Co-Ni-P/fs-Si material synthesized in the step three as a self-supporting electrode, and carrying out an electrolytic water hydrogen evolution performance test on the self-supporting electrode.
2. The preparation method of the Co-Ni-P/fs-Si material for hydrogen evolution by electrolysis of water, according to claim 1, is characterized in that in the step one, a silicon wafer sold in the market is cleaned, the cleaning method adopts alkaline cleaning, acid cleaning and ultrasonic cleaning, alkaline cleaning solution is prepared by concentrated ammonia water, hydrogen peroxide and deionized water, acid cleaning solution is prepared by concentrated hydrochloric acid, hydrogen peroxide and deionized water, the cleaning is carried out at 60-80 ℃ for 10-20 minutes, the cleaning is carried out by respectively washing with deionized water after the alkaline cleaning and the acid cleaning, then the ultrasonic cleaning is carried out for 10-20 minutes, and finally the vacuum high-temperature drying is carried out.
3. The method for preparing Co-Ni-P/fs-Si material for hydrogen evolution by electrolysis of water according to claim 1, wherein in the second step,
(1) adding a certain amount of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea, ammonium fluoride and deionized water into a beaker with the volume of 20-100 ml for ultrasonic dissolution to obtain an orange pink solution; cobalt nitrate hexahydrate is used as a cobalt source, the weighed mass is 0.5-1.5 g, nickel nitrate hexahydrate is used as a nickel source, the weighed mass is 0.5-2.0 g, urea is used as a precipitator, the weighed mass is 0.5-1.0 g, ammonium fluoride is used as a structure directing agent, and the weighed mass is 0.1-0.5 g;
(2) the solvent added in the step (1) is deionized water, 20-50 ml, the dissolving is carried out in an ultrasonic instrument, and the ultrasonic time is 1-10 minutes;
(3) transferring the orange pink solution obtained in the step (1) to a reaction kettle of 20-100 ml, and putting the reaction kettle into a blast drying oven for hydrothermal treatment, wherein the hydrothermal temperature is 100-180 ℃, and the hydrothermal time is 5-24 hours;
(4) and (4) after the step (3) is finished, cooling to room temperature, opening the reaction kettle, washing the sample, and drying in an oven at the drying temperature of 40-90 ℃ for 12-24 hours to obtain the cobalt-nickel precursor/fs-Si material with pink surface.
4. The preparation method of Co-Ni-P/fs-Si material for electrolysis of water for hydrogen evolution according to claim 1, characterized in that in the third step,
(1) in a tube furnace, the cobalt-nickel precursor/fs-Si material and the phosphating agent obtained in the step two are respectively arranged in two separated ceramic boats in a quartz tube, wherein the phosphating agent is NaH2PO2Weighing 0.1-1.0 g of the powder;
(2) in the above step (1), NaH2PO2Is positioned at the upstream side of the tubular furnace, and the rate of temperature rise is 1-5 ℃ for min-1The phosphating temperature is 300-500 ℃, the heating time is 1-4 hours under the inert atmosphere, and the inert atmosphere is argon, nitrogen, helium or the mixture gas of the argon, the nitrogen and the helium;
(3) after the step (2) is finished, cooling the tube furnace at the cooling rate of 1-5 ℃ for min-1Finally obtaining the Co-Ni-P/fs-Si material.
5. The method for preparing Co-Ni-P/fs-Si material for hydrogen evolution by electrolysis of water according to claim 1, wherein in the fourth step,
(1) the electrochemical measurement is carried out by adopting a CHI660e electrochemical workstation, the test temperature is room temperature, the electrode system is a three-electrode configuration and comprises a working electrode, an auxiliary electrode and a reference electrode, the working electrode is a platinum sheet electrode clamped with a Co-Ni-P/fs-Si material, the auxiliary electrode is a carbon rod, and the reference electrode is an Ag/AgCl (saturated potassium chloride filled) or saturated calomel electrode;
(2) and taking the Co-Ni-P/fs-Si material synthesized in the third step as a self-supporting electrode, clamping the self-supporting electrode by using a platinum sheet electrode clamp, wherein the platinum sheet electrode clamp is not in contact with the electrolyte in the reaction tank, and the area of the platinum sheet electrode clamp penetrating into the electrolyte is 0.02-0.1 square centimeter.
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