CN111334821A - High-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under neutral condition and preparation method thereof - Google Patents
High-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under neutral condition and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 16
- 230000007935 neutral effect Effects 0.000 title claims abstract description 16
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000006260 foam Substances 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 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 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 description 5
- 235000011009 potassium phosphates Nutrition 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- 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
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- 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
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- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention provides a high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under a neutral condition and a preparation method thereof. The porous nickel foam then acts as a carrier to facilitate the deposition of nickel phosphide, during which very small amounts of platinum from the platinum sheet are deposited onto the porous nickel foam. The additive component provides a target element source for various doping, and plays a role in preparing hydrogen through concerted catalysis. The prepared catalytic electrode has better performance of hydrogen evolution by electrolyzing water.
Description
Technical Field
The invention belongs to the technical field of clean energy, in particular to the technical field of hydrogen production by water electrolysis, and discloses a high-efficiency nickel phosphide water electrolysis hydrogen evolution catalytic electrode under a neutral condition and a preparation method thereof.
Background
Energy and environment are two major problems in the world at present, and the construction of a safe green energy system is not slow. The hydrogen energy has attracted attention by the characteristic of no pollution and cleanness, and a plurality of methods for preparing the hydrogen are provided, wherein the hydrogen preparation by electrolyzing water becomes a research hotspot because the process is simple and clean and has no pollution. For preparing hydrogen by electrolyzing water, the most critical way is to design and prepare a more efficient catalytic material at present, so that the overpotential is further reduced, and the energy consumption is reduced.
At present, electrocatalytic hydrogen production catalysts can be roughly classified into three types according to the used elements: (1) noble metal platinum (Pt), a highly efficient hydrogen evolution catalyst; (2) transition metals mainly including iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), and tungsten (W); (3) non-metals, mainly including boron (B), carbon (C), nitrogen (N), phosphorus (P), sulfur (S), and selenium (Se). The noble metal platinum (Pt) has excellent hydrogen evolution catalytic performance, but the expensive price and low natural abundance limit the large-scale industrial application of the noble metal platinum. However, composite catalysts containing a very small amount of noble metal platinum still remain a major research direction because of their superior performance and their ability to be composited with other types of catalysts, such as catalysts having a dispersed noble metal supported thereon. Meanwhile, composite catalysts in which transition metals are combined with non-metals are also a research hotspot. In recent years, metallic nickel phosphide has attracted much attention in the field of catalytic hydrogen production, and has been studied extensively.
Another current situation of hydrogen production by water electrolysis is that the existing research is still that catalytic hydrogen production is more under acidic and alkaline conditions, and hydrogen production is more difficult under neutral conditions. Aiming at the current situation, the invention provides a preparation method of a high-efficiency nickel phosphide hydrogen evolution catalytic electrode by electrolyzing water under a neutral pH condition, wherein a very trace noble metal Pt is loaded on the surface of a catalyst by a simple electrodeposition method, and the prepared catalytic electrode has better hydrogen evolution performance by electrolyzing water under the condition of 0.1M low-concentration potassium phosphate.
Disclosure of Invention
The invention relates to a high-efficiency nickel phosphide hydrogen evolution catalytic electrode by water electrolysis under a neutral condition and a preparation method thereof.
The present invention achieves the above-described object by the following technical means.
A preparation method of a high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under a neutral condition is characterized by comprising the following steps:
(1) cleaning a matrix by using foamed nickel as the matrix;
(2) immersing a substrate serving as a working electrode in an electrolyte solution into the electrolyte solution; the metal platinum sheet is used as a counter electrode, namely an auxiliary electrode; performing three-electrode deposition by adopting an electrochemical workstation; the electrolyte is a mixed solution of sodium hypophosphite, nickel sulfate, sodium borate, sodium fluoride, ferrous chloride and cobalt chloride;
(3) and washing the deposited porous electrode with deionized water, and drying.
Further, a saturated calomel electrode or a silver chloride electrode is used as a reference electrode, and the height of the foam nickel matrix immersed in the electrolyte solution is 1 cm.
Furthermore, in the three-electrode deposition process, the deposition mode adopts CV scanning for 100 to 300 cycles, and the scanning speed is 2 mv/s.
Furthermore, the electrolyte contains 0.1-0.6mol/L sodium hypophosphite, 0.1-0.6mol/L nickel sulfate, 0.05-0.1mol/L sodium borate, 0.05-0.1mol/L sodium fluoride, 0.001-0.1mol/L ferrous chloride and 0.001-0.1mol/L cobalt chloride.
Further, the preparation method of the electrolyte comprises the following steps: respectively preparing a sodium hypophosphite solution and a nickel salt solution under the condition of continuous stirring, then mixing the sodium hypophosphite solution and the nickel salt solution under the stirring action, adding other components of the electrolyte, and continuously stirring to obtain the electrolyte.
The electrolyte adopted by the invention is as follows: 0.1-0.6mol/L sodium hypophosphite, 0.1-0.6mol/L nickel sulfate, 0.05-0.1mol/L sodium borate, 0.05-0.1mol/L sodium fluoride, 0.001-0.1mol/L ferrous chloride and 0.001-0.1mol/L cobalt chloride.
In the preparation method of the high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under the neutral condition, the electrolyte is a mixed solution of sodium hypophosphite, nickel sulfate, sodium borate, sodium fluoride, ferrous chloride and cobalt chloride, and the mechanism and the action of each component in the electrolyte are as follows:
the nickel salt in the electrolyte provides the nickel source required for deposition, the sodium hypophosphite provides the phosphorus source, and the platinum sheet naturally provides the platinum source during the anodic process. The porous nickel foam then acts as a carrier to facilitate the deposition of nickel phosphide, during which very small amounts of platinum from the platinum sheet are deposited onto the porous nickel foam. The additive component provides a target element source for various doping, and plays a role in preparing hydrogen through concerted catalysis.
After the electrode is prepared, an electrolytic water hydrogen evolution test is carried out in 0.1mol/L potassium phosphate solution, a CV test of 20 cycles is firstly carried out in a certain potential range, the scanning speed is 100mV/s, then an LSV test is carried out in the same range, the scanning speed is 2mV/s, and a plurality of LSV scans are carried out. The hydrogen overpotential at a density of 10mA was obtained and converted to the RHE potential.
The invention has the advantages that:
(1) the deposition of a trace amount of noble metal Pt in the catalyst is simply realized by a one-step method, and the result is deduced from the experimental effect. The contrast test shows that when the carbon rod is used as the counter electrode, the performance of the prepared catalytic electrode is very poor, and that when the metal Pt is used as the counter electrode, a trace amount of Pt enters the electrolyte in the anode process and loads the surface of the prepared catalytic electrode.
(2) The combination of various transition metal elements and non-metal phosphorus is directly realized by utilizing a one-step method, phosphide of the transition metal elements is formed, and the catalytic hydrogen evolution performance is improved by the synergistic catalytic action of the various transition metals.
(3) The electrode prepared by the invention has higher hydrogen evolution catalytic performance in 0.1M neutral potassium phosphate solution.
(4) The method has the advantages of stable and reliable process, simple adopted equipment, reaction at normal temperature, convenient operation and easy mastering.
Drawings
FIG. 1 is a schematic diagram of a porous nickel foam and a schematic diagram of a prepared electrode.
Figure 2 is an XRD pattern of the porous nickel foam and the prepared catalyst substrate.
In FIG. 3, (a) is a porous nickel foam image, (b) is a SEM image of the surface of the prepared catalytic electrode, and (c) is an EDS image of the surface of the catalytic electrode.
FIG. 4 is an AFM image of the catalytic electrode surface.
FIG. 5 is a graph of the polarization of a catalytic electrode in 0.1M potassium phosphate.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
(1) firstly, cutting commercial foam nickel purchased into a shape of 3.5cm x 1cm, washing with dilute hydrochloric acid, then respectively carrying out ultrasonic cleaning for 10-15 minutes by ethanol and 10-15 minutes by acetone, then carrying out ultrasonic cleaning for 2-3 times by deionized water for 10-15 minutes each time, and then drying in an oven at 30-40 ℃, wherein the substance is shown in (a) in figure 1.
(2) 0.1-0.6mol/L sodium hypophosphite, 0.1-0.6mol/L nickel sulfate, 0.05-0.1mol/L sodium borate, 0.05-0.1mol/L sodium fluoride, 0.001-0.1mol/L ferrous chloride and 0.001-0.1mol/L cobalt chloride, wherein a three-electrode system is adopted, porous foamed nickel is used as a working electrode, a 2cm × 2, 2cm × 0.2, 0.2cm foil is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a CHI electrochemical working station is adopted to carry out CV scanning for 200 cycles in the range of-0.3V to-1.5V, and the speed is 2 mv/s.
(3) And washing the prepared catalytic electrode with deionized water, and drying in an oven at 20-25 ℃.
FIG. 1(b) shows that a layer of material is obviously deposited on the porous nickel foam through electrodeposition. FIG. 2 XRD patterns before and after deposition of the porous nickel foam, research shows that no substance with a crystal structure is found on the surface of the porous nickel foam, but all characteristic peaks of the nickel matrix are weakened, possibly caused by the fact that the surface of the nickel matrix is covered by an amorphous layer. In fig. 3, (a), (b), and (c) are SEM images of the surface of the porous nickel foam, SEM images of the surface of the prepared catalytic electrode, and EDS images of the surface of the catalytic electrode, respectively. It is apparent from fig. 3 that the pore foam nickel surface is covered with a layer of loose material, indicating that the catalyst has been deposited on its surface. This is consistent with XRD results. The EDS chart shows that the deposited catalyst contains elements such as phosphorus, iron, cobalt and the like besides nickel, so that main elements in the electrolyte component also enter the catalyst, but the EDS does not find metal Pt, which is mainly because the content of Pt is very small, and the EDS cannot detect the metal Pt. FIG. 4 is an AFM image of the surface of a catalyst, which shows that the catalyst is in a micro-nano structure. The prepared sample was subjected to HER test, and the hydrogen evolution overpotential of fig. 5, a polarization curve of the catalyst surface in 0.1M potassium phosphate, was about 85mV, and the hydrogen evolution overpotential of the catalytic electrode prepared using a carbon rod as a counter electrode was about 168 mV.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (6)
1. A preparation method of a high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under a neutral condition is characterized by comprising the following steps:
(1) cleaning a matrix by using foamed nickel as the matrix;
(2) immersing a substrate serving as a working electrode in an electrolyte solution into the electrolyte solution; the metal platinum sheet is used as a counter electrode, namely an auxiliary electrode; performing three-electrode deposition by adopting an electrochemical workstation; the electrolyte is a mixed solution of sodium hypophosphite, nickel sulfate, sodium borate, sodium fluoride, ferrous chloride and cobalt chloride;
(3) and washing the deposited porous electrode with deionized water, and drying.
2. The method for preparing the high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under the neutral condition as claimed in claim 1, wherein a saturated calomel electrode or a silver chloride electrode is adopted as a reference electrode, and the height of the foam nickel matrix immersed in the electrolyte solution is 1 cm.
3. The method for preparing the high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under the neutral condition as claimed in claim 1, wherein in the deposition process of the three electrodes, the deposition mode adopts CV scanning for 100 to 300 cycles with the scanning speed of 2 mv/s.
4. The method for preparing the high-efficiency nickel phosphate electrode for the electrolysis of water and hydrogen evolution catalysis under the neutral condition according to claim 1, wherein the electrolyte contains 0.1-0.6mol/L sodium hypophosphite, 0.1-0.6mol/L nickel sulfate, 0.05-0.1mol/L sodium borate, 0.05-0.1mol/L sodium fluoride, 0.001-0.1mol/L ferrous chloride and 0.001-0.1mol/L cobalt chloride.
5. The method for preparing the high-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under the neutral condition as claimed in claim 1, wherein the preparation method of the electrolyte is as follows: respectively preparing a sodium hypophosphite solution and a nickel salt solution under the condition of continuous stirring, then mixing the sodium hypophosphite solution and the nickel salt solution under the stirring action, adding other components of the electrolyte, and continuously stirring to obtain the electrolyte.
6. The high efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode prepared by the method for preparing the high efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under neutral condition according to any one of claims 1 to 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458482A (en) * | 2020-11-18 | 2021-03-09 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4033837A (en) * | 1976-02-24 | 1977-07-05 | Olin Corporation | Plated metallic cathode |
| CN108172850A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of hydrogen-precipitating electrode and its preparation and application |
| CN108607586A (en) * | 2018-04-28 | 2018-10-02 | 重庆长安汽车股份有限公司 | A kind of method of nickel phosphide, preparation method and water electrolysis hydrogen production |
| CN109136982A (en) * | 2018-09-18 | 2019-01-04 | 温州大学 | By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst |
| CN110129826A (en) * | 2019-05-27 | 2019-08-16 | 浙江师范大学 | A kind of step electro-deposition prepares metal sulfide/metal elctro-catalyst universality method |
-
2020
- 2020-02-28 CN CN202010127301.6A patent/CN111334821A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4033837A (en) * | 1976-02-24 | 1977-07-05 | Olin Corporation | Plated metallic cathode |
| CN108172850A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of hydrogen-precipitating electrode and its preparation and application |
| CN108607586A (en) * | 2018-04-28 | 2018-10-02 | 重庆长安汽车股份有限公司 | A kind of method of nickel phosphide, preparation method and water electrolysis hydrogen production |
| CN109136982A (en) * | 2018-09-18 | 2019-01-04 | 温州大学 | By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst |
| CN110129826A (en) * | 2019-05-27 | 2019-08-16 | 浙江师范大学 | A kind of step electro-deposition prepares metal sulfide/metal elctro-catalyst universality method |
Non-Patent Citations (3)
| Title |
|---|
| RONG CHEN 等: "Use of platinum as the counter electrode to_study the activity of nonprecious metal catalysts for the hydrogen evolution_reaction", 《ACS ENERGY LETTERS》 * |
| 张允诚 等: "《电镀手册》", 31 December 2011, 国防工业出版社 * |
| 陈艳丽 等: "电沉积制备Ni-P非晶态催化电极上的析氢反应", 《过程工程学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458482A (en) * | 2020-11-18 | 2021-03-09 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN112458482B (en) * | 2020-11-18 | 2021-11-19 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113363411B (en) * | 2021-05-31 | 2022-07-15 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
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