CN115928122A - Nickel phosphide electrocatalytic material and preparation method thereof - Google Patents
Nickel phosphide electrocatalytic material and preparation method thereof Download PDFInfo
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- CN115928122A CN115928122A CN202211461217.3A CN202211461217A CN115928122A CN 115928122 A CN115928122 A CN 115928122A CN 202211461217 A CN202211461217 A CN 202211461217A CN 115928122 A CN115928122 A CN 115928122A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 17
- 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 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract 2
- 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 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 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 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Inert Electrodes (AREA)
Abstract
The invention relates to a nickel phosphide electrocatalytic composite material and a preparation method thereof, belonging to the technical field of electrocatalytic hydrogen production. The invention adopts an in-situ self-growth strategy and prepares nickel phosphide/nickel foam (Ni) with the characteristics of good substrate adhesion, mechanical stability, conductivity and the like by a simple two-step method of in-situ synthesis and low-temperature phosphorization 2 P/NF) electrocatalytic composite material. Under alkaline condition, ni prepared by the invention 2 The P/NF electrocatalytic composite material has the current density of 10 mA/cm 2 The overpotential of the capacitor is only 189mV, and the electric double layer capacitor (C) dl ) The value is as high as 30.68 mF/cm 2 Provides a new material design and synthesis technology for efficiently obtaining clean hydrogen energy.
Description
Technical Field
The invention relates to a nickel phosphide electrocatalytic composite material and a preparation method thereof, belonging to the technical field of electrocatalytic hydrogen production.
Background
The massive development of fossil fuels worldwide has led to serious energy crisis and environmental pollution, and there is an urgent need for clean, economically sustainable energy. The hydrogen energy is inexhaustible clean energy with wide source and high energy density, can gradually replace strategic performance source commodities such as petroleum, natural gas and the like, can ensure the safety and diversification of energy, is the only energy which can be coupled with a power grid, a heat grid and a gas grid, is an ideal energy class for forming a high-efficiency, safe and stable multi-energy complementary energy system, and plays an important role in realizing the goals of carbon peak reaching and carbon neutralization. The hydrogen production by water electrolysis is concerned by the characteristics of low energy consumption, less greenhouse gas emission in the whole preparation process, high purity of the prepared hydrogen, less impurity content and the like.
Currently, platinum (Pt) noble metals are the best performing Hydrogen Evolution (HER) electrocatalysts, but their large scale application is limited by the high price and scarce resources. Therefore, the preparation of low-cost, efficient and stable non-noble metal catalysts becomes one of the current research hotspots. Among them, transition metal compounds (including transition metal carbides, transition metal sulfides, transition metal nitrides, transition metal oxides, transition metal phosphides, and transition metal selenides) are receiving much attention due to their unique physicochemical properties, wide sources, low prices, and the like. However, most metals show poor hydrogen evolution performance because the acting force between the adsorbed hydrogen and the metal surface is too strong to desorb in the hydrogen production process by electrolyzing water. However, in the transition metal phosphide, P can enter the crystal lattice of the metal to "dilute" the metal atoms and maintain the electronic structure of the metal substantially unchanged, thereby reducing the free energy for hydrogen adsorption and facilitating hydrogen desorption. Meanwhile, P has high electronegativity and can capture electrons from metal elements, the P with negative charges can also be used as an active site for absorbing hydrogen, and the formed covalent bond (metal-phosphorus bond) can also improve the stability of metal phosphide.
Because nickel phosphide has various different component chemical formulas and catalytic mechanisms similar to hydrogenase, researchers at home and abroad have conducted many researches in the field. For example, CN 110512228A adopts a chemical plating method to prepare a nickel hydroxide/nickel foam precursor containing a nickel-phosphorus plating layer, and then a phosphating nickel/nickel foam self-supporting electrode is prepared by a phosphating method, the operation process is complex, a large amount of raw materials are used in the preparation process of the precursor, nickel sulfate is required to be additionally added as a nickel source, the bonding force between the formed precursor and a nickel foam substrate is not strong, and the prepared nickel phosphide/nickel foam self-supporting electrode has poor stability. Publication No. CN 113881964A discloses a preparation method of a sheet nickel phosphide array electrode material, firstly, cetyl trimethyl ammonium bromide and hydrogen peroxide are used for activating foamed nickel to obtain a sheet nickel hydroxide array/foamed nickel precursor, and then, the sheet nickel hydroxide array/foamed nickel precursor is subjected to phosphating at 400 ℃ for 1 hour to obtain a nickel phosphide/foamed nickel electrode. The preparation process does not need to add a nickel source, but has long preparation period and complex operation process and needs to use a surfactant.
In view of the above problems, it is important to prepare an efficient, stable, green and economical electrocatalytic composite material by a simple process.
The foam nickel used in the invention is directly Ni (OH) 2 The formation of (a) provides a nickel source without adding an additional nickel source. Therefore, the prepared precursor can be rooted in NF, has good substrate adhesion, conductivity and mechanical stability, and can still maintain the characteristics after low-temperature in-situ phosphorization.
Disclosure of Invention
The first technical problem solved by the present invention is to provide an electrocatalytic composite material prepared by a self-growth strategy, which has good substrate adhesion, electrical conductivity and mechanical stability.
The invention solves the second technical problem by providing a preparation method of an electrocatalytic composite material, which comprises the following steps:
a. taking urea (CO (NH) 2 ) 2 ) Ammonium fluoride (NH) 4 F) Dissolving in 70mL of deionized water, and uniformly stirring to obtain a mixed solution;
b. b, transferring the mixed solution obtained in the step a and the treated Nickel Foam (NF) sheet to a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into a drying oven for hydrothermal reaction, and cooling to room temperature after hydrothermal reaction is finishedWashing with deionized water and ethanol, and vacuum drying to obtain Ni (OH) 2 a/NF precursor;
c. with sodium hypophosphite (NaH) 2 PO 2 ·H 2 O) is used as a phosphorus source and is placed at the tail part of the quartz boat, the precursor obtained in the step b is placed at the top of the quartz boat, the quartz boat is transferred into a tube furnace with nitrogen atmosphere for heating and phosphorization, the temperature is reduced to room temperature, then deionized water and ethanol are used for cleaning, and drying is carried out to obtain Ni 2 P/NF electrocatalytic composite material.
In one embodiment, in step a, the urea concentration is 5 to 20mmol/L; preferably, the urea concentration is 15mmol/L.
In one embodiment, in step b, the hydrothermal temperature is 125 ℃ to 200 ℃; preferably, the hydrothermal temperature is 150 ℃.
In one embodiment, in step b, the hydrothermal time is 6-12 h; preferably, the hydrothermal time period is 8 hours.
In one embodiment, in step c, the amount of the phosphorus source is 8:1-16; preferably, the phosphorus source is used in an amount of 10.
In one embodiment, in step c, the heating rate is 1 ℃/min to 5 ℃/min; preferably, the rate of temperature rise is 1 deg.C/min.
In one embodiment, in step c, the heating temperature is 240 ℃ to 300 ℃; preferably, the incubation time is 290 ℃.
In one embodiment, in step c, the heating and holding time is 1 to 3 hours; preferably, the incubation time is 2h.
The third technical problem solved by the invention is to provide the application of the electrocatalytic composite material, and the electrocatalytic composite material is used for efficiently electrolyzing water to prepare hydrogen.
The invention has the beneficial effects that:
1. the electrocatalytic composite material utilizes NF as a Ni source and ammonium fluoride as an etching agent to enable the NF to release Ni ions, the Ni ions are slowly precipitated and react in situ to form Ni (OH) 2 The precursor, the self-growth strategy, increases the adhesion between the catalyst and the conductive substrate, and effectively improves the durability and stability of the material.
2. The invention adopts a low-cost hydrothermal method and a low-temperature phosphating method, and has the advantages of simple preparation method, mild conditions, wide raw material sources and low cost.
Drawings
FIG. 1 shows Ni obtained in example 1 2 XRD pattern of P/NF-8:1 electrocatalytic composite material.
FIG. 2 shows Ni obtained in example 1 2 LSV curve of P/NF-8:1 electrocatalytic composite material.
FIG. 3 shows Ni obtained in example 1 2 C of P/NF-8:1 electrocatalytic composite material dl Figure (a).
FIG. 4 shows Ni obtained in example 2 2 XRD pattern of P/NF-10
FIG. 5 shows Ni obtained in example 2 2 LSV curve of the P/NF-10.
FIG. 6 shows Ni obtained in example 2 2 P/NF-10 dl Drawing.
FIG. 7 shows Ni obtained in example 3 2 XRD pattern of P/NF-12.
FIG. 8 shows Ni obtained in example 3 2 LSV curve of the P/NF-12.
FIG. 9 shows Ni obtained in example 1 2 P/NF-12 dl Figure (a).
Detailed Description
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Electrocatalytic testing
The electrocatalytic hydrogen evolution reaction test is carried out in KOH solution with the concentration of 1M, ni 2 The size of the P/NF composite material is 1 × 1cm, a carbon rod is used as a counter electrode, hg/HgO is used as a reference electrode, and a glassy carbon electrode clamp is used for clamping Ni 2 The P/NF composite material is used as a working electrode, and the electrochemical performance test is carried out on an electrochemical workstation DH7000 (Donghua test).
Example 1
The synthesis process comprises the following steps:
a. 0.047g of urea (CO (NH) was taken 2 ) 2 ) 0.023g of ammonium fluoride (NH) 4 F) Dissolving in 70mL of deionized water, and uniformly stirring to obtain a mixed solution;
b. transferring the mixed solution obtained in the step a and a treated Nickel Foam (NF) sheet into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into an oven, keeping the temperature for 6 hours at 125 ℃, cooling to room temperature after hydrothermal is finished, washing with deionized water and ethanol, and drying in vacuum at 60 ℃ to obtain Ni (OH) 2 a/NF precursor;
c. sodium hypophosphite (NaH) in a mass ratio of 8:1 2 PO 2 ·H 2 O) is used as a phosphorus source and is placed at the tail part of the quartz boat, the precursor obtained in the step b is placed at the top of the quartz boat, the quartz boat is put into a tube furnace in nitrogen atmosphere, the temperature is raised to 300 ℃ at the speed of 2 ℃/min for phosphorization for 1h, the temperature is reduced to room temperature, deionized water and ethanol are used for cleaning, and drying is carried out to obtain Ni 2 P/NF-8:1 electrocatalytic composite material.
FIG. 1 shows Ni obtained in example 1 of the present invention 2 XRD pattern of P/NF-8:1 electrocatalytic composite material, as can be seen from FIG. 1, ni prepared in example 1 2 The XRD result of the P/NF-8:1 is consistent with the standard diffraction peak, no other impurities exist, and the success of phosphorization is proved.
FIG. 2 shows Ni obtained in example 1 of the present invention 2 LSV of P/NF-8:1 electrocatalytic composite material, as can be seen from FIG. 2, ni obtained in example 1 2 P/NF-8:1 electrocatalytic composite material with current density of 10mA cm -2 The overpotential in this case was 263mV.
FIG. 3 shows Ni obtained in example 1 of the present invention 2 C of P/NF-8:1 electrocatalytic composite material dl As can be seen from FIG. 3, ni obtained in example 1 2 C of P/NF-8:1 dl The value was 14.83mF/cm 2 。
Example 2
The synthesis process comprises the following steps:
a. 0.063g of urea (CO (NH) was taken 2 ) 2 ) 0.023g of ammonium fluoride (NH) 4 F) Dissolving in 70mL of deionized water, and uniformly stirring to obtain a mixed solution;
b. transferring the mixed solution obtained in the step a to a poly-Nickel Foam (NF) sheet together with the treated NF sheetPutting into a hydrothermal kettle with a tetrafluoroethylene lining, placing into an oven, keeping the temperature at 150 ℃ for 8h, cooling to room temperature after hydrothermal reaction, washing with deionized water and ethanol, and vacuum drying at 60 ℃ to obtain Ni (OH) 2 a/NF precursor;
c. sodium hypophosphite (NaH) in a mass ratio of 10 2 PO 2 ·H 2 O) is used as a phosphorus source and is placed at the tail part of the quartz boat, the precursor obtained in the step b is placed at the top of the quartz boat, the quartz boat is put into a tube furnace in nitrogen atmosphere, the temperature is raised to 290 ℃ at 1 ℃/min for phosphorization for 2h, the temperature is reduced to room temperature, deionized water and ethanol are used for cleaning, and drying is carried out to obtain Ni 2 P/NF-10.
FIG. 4 shows Ni obtained in example 2 of the present invention 2 XRD pattern of P/NF-10 2 The XRD result of the P/NF-10.
FIG. 5 shows Ni obtained in example 2 of the present invention 2 LSV of the P/NF-10 2 P/NF-10 -2 The overpotential was 189mV.
FIG. 6 shows Ni obtained in example 2 of the present invention 2 P/NF-10 dl As can be seen from FIG. 6, ni obtained in example 2 2 P/NF-10 dl The value was 30.18mF/cm 2 。
Example 3
The synthesis process comprises the following steps:
a. 0.084g of urea (CO (NH)) was taken 2 ) 2 ) 0.023g of ammonium fluoride (NH) 4 F) Dissolving in 70mL of deionized water, and uniformly stirring to obtain a mixed solution;
b. transferring the mixed solution obtained in the step a and a treated Nickel Foam (NF) sheet into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into an oven, keeping the temperature at 175 ℃ for 10h, cooling to room temperature after hydrothermal is finished, washing with deionized water and ethanol, and drying in vacuum at 60 ℃ to obtain Ni (OH) 2 a/NF precursor;
c. a sub-subunit of 12Sodium phosphate (NaH) 2 PO 2 ·H 2 O) is used as a phosphorus source and is placed at the tail part of the quartz boat, the precursor obtained in the step b is placed at the top of the quartz boat, the quartz boat is put into a tube furnace in nitrogen atmosphere, the temperature is raised to 280 ℃ at the speed of 5 ℃/min for phosphorization for 3h, the temperature is reduced to room temperature, deionized water and ethanol are used for cleaning, and drying is carried out to obtain Ni 2 P/NF-12.
FIG. 7 shows Ni obtained in example 3 of the present invention 2 XRD pattern of P/NF-12 2 The XRD result of the P/NF-12.
FIG. 8 is a LSV diagram of the Ni2P/NF-12 electrocatalytic composite material obtained in example 3 of the invention, and it can be seen from FIG. 8 that Ni obtained in example 3 is 2 P/NF-12 -2 The overpotential at this time was 216mV.
FIG. 9 shows Ni obtained in example 3 of the present invention 2 P/NF-12 dl As can be seen from FIG. 9, ni produced in example 3 2 P/NF-12 dl The value was 19.33mF/cm 2 。
Claims (10)
1. A nickel phosphide electrocatalytic composite material and a preparation method thereof are characterized in that: the invention adopts a self-growth strategy and prepares nickel phosphide/nickel foam (Ni) with the characteristics of good substrate adhesion, mechanical stability, conductivity and the like by a simple two-step method of in-situ synthesis and low-temperature phosphorization 2 P/NF) electrocatalytic composite material to realize excellent hydrogen production performance by electrocatalytic decomposition of water.
2. The nickel phosphide electrocatalytic composite material as set forth in claim 1 and the preparation method thereof, characterized by comprising the steps of:
a. taking urea (CO (NH) 2 ) 2 ) Ammonium fluoride (NH) 4 F) Dissolving in 70mL of deionized water, and uniformly stirring to obtain a mixed solution;
b. mixing the mixed solution obtained in the step a with treated foam Nickel (NF)) Transferring the slices into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into an oven for hydrothermal reaction, cooling to room temperature after hydrothermal reaction, washing with deionized water and ethanol, and vacuum drying to obtain Ni (OH) 2 a/NF precursor;
c. with sodium hypophosphite (NaH) 2 PO 2 ·H 2 O) is used as a phosphorus source and is placed at the tail part of the quartz boat, the precursor obtained in the step b is placed at the top of the quartz boat, the quartz boat is transferred into a tube furnace with nitrogen atmosphere for heating and phosphorization, the temperature is reduced to room temperature, then deionized water and ethanol are used for cleaning, and drying is carried out to obtain Ni 2 P/NF electrocatalytic composite material.
3. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step a, the concentration of the urea is 5-20 mmol/L.
4. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step b, the hydrothermal temperature is 125-200 ℃.
5. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step b, the hydrothermal time is 6-12 h.
6. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein the nickel phosphide electrocatalytic composite material comprises the following components in percentage by weight: in the step c, the dosage of the phosphorus source is 8:1-16 by mass ratio.
7. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step c, the heating rate is 1-5 ℃/min.
8. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step c, the heating temperature is 240-300 ℃.
9. The nickel phosphide electrocatalytic composite material and the preparation method thereof as claimed in claim 2, wherein: in the step c, the heating and heat preservation time is 1-3 h.
10. Use of a nickel phosphide electrocatalytic composite material as set forth in claim 1 or prepared by the preparation method as set forth in any one of claims 2 to 8 as an electrocatalytic water decomposition catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211461217.3A CN115928122B (en) | 2022-11-16 | 2022-11-16 | Nickel phosphide electrocatalytic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN114807996A (en) * | 2022-04-13 | 2022-07-29 | 北京工业大学 | Preparation method of monatomic platinum-loaded transition metal phosphide hydrogen evolution catalyst |
| CN114824180A (en) * | 2022-05-10 | 2022-07-29 | 北京航空航天大学 | Foam nickel with heterojunction nanosheet layer grown on surface and preparation method and application thereof |
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