CN114134536B - Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof - Google Patents
Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114134536B CN114134536B CN202111447503.XA CN202111447503A CN114134536B CN 114134536 B CN114134536 B CN 114134536B CN 202111447503 A CN202111447503 A CN 202111447503A CN 114134536 B CN114134536 B CN 114134536B
- Authority
- CN
- China
- Prior art keywords
- nicop
- nio
- sea urchin
- electrode material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 145
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910017855 NH 4 F Inorganic materials 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000013535 sea water Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920006389 polyphenyl polymer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 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 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 241000257465 Echinoidea Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000010355 oscillation Effects 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
- 239000011574 phosphorus Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sea urchin-shaped Ni@Ni 2 A P@NiCoP electrode material, a preparation method and application thereof relate to the technical field of preparation of transition metal phosphide electrode materials, and the preparation method comprises the following steps: placing foam nickel in a bath containing divalent nickel salt and K 2 S 2 O 8 In the aqueous solution of (2), carrying out hydrothermal reaction, cooling, washing, drying and thermal annealing treatment to obtain a Ni@NiO material; divalent Nickel salt, divalent cobalt salt, NH 4 F and urea are dissolved in deionized water, stirred, then mixed solution of DMF and DMSO is added, ni@NiO material is added, hydrothermal reaction is carried out, washing and drying are carried out, and Ni@NiO@NiCo (OH) is obtained x A precursor; in a tube furnace, ni@NiO@NiCo (OH) x Carrying out high-temperature phosphating treatment on the precursor, and cooling to obtain sea urchin-shaped Ni@Ni 2 P@NiCoP. The electrode material prepared by the invention can expose more active sites, has high HER catalytic activity, and can obtain catalytic efficiency comparable to that of commercial Pt/C.
Description
Technical Field
The invention relates to the technical field of preparation of transition metal phosphide electrode materials, in particular to a sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and a preparation method and application thereof.
Background
Seawater is one of the most abundant natural resources on earth. The electrolysis of seawater is not only a promising method for generating clean hydrogen energy, but also has important significance for seawater desalination. The implementation of seawater electrolysis requires a powerful and effective electrocatalyst, and transition metal phosphide has a great specific surface area and thermodynamic stability, excellent conductivity, and unique advantages in terms of total decomposition of seawater, so that extensive researches are made. Unlike traditional hydrogen producing process with high power consumption, low production efficiency, etc., the electrocatalytic sea water decomposing hydrogen producing process is simple, low in cost and environment friendly.
At present, the research on transition metal phosphide mainly realizes the improvement of the catalytic activity of the material from the design and controllable synthesis of the material by regulating the morphology and the component structure of the material.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material, and preparation method and application thereof.
The invention provides a sea urchin-shaped Ni@Ni 2 The preparation method of the P@NiCoP electrode material comprises the following steps:
s1, pretreatment of foam nickel: cutting foam nickel into proper size and cleaning;
s2, synthesizing Ni@NiO: placing the cut foam nickel in a bath containing divalent nickel salt and K 2 S 2 O 8 Heating to perform hydrothermal reaction, cooling, washing, drying, and performing thermal annealing treatment in air atmosphere to obtain Ni@NiO material;
S3、Ni@NiO@NiCo(OH) x synthesizing a precursor: divalent Nickel salt, divalent cobalt salt, NH 4 F and urea are dissolved in deionized water, stirred and mixed, then mixed solution of DMF and DMSO is added, the mixture is stirred, ni@NiO material is added, heating is carried out for hydrothermal reaction, washing and drying are carried out, and Ni@NiO@NiCo (OH) is obtained x A precursor; wherein, the volume ratio of DMF to DMSO is 2:1, a step of;
S4、Ni@Ni 2 synthesis of P@NiCoP: ni@NiO@NiCo (OH) x Transferring the precursor into a tubular furnace, placing hypophosphite at an upper air port of an air path of the tubular furnace, introducing inert gas for high-temperature phosphating treatment, and cooling to obtain sea urchin-shaped Ni@Ni 2 P@NiCoP。
Preferably, the divalent nickel salt is one of nickel nitrate, nickel chloride and nickel acetate; the bivalent cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt acetate.
Preferably, in S2, the divalent nickel salt and K are contained 2 S 2 O 8 Ni in the divalent Ni salt 2+ The molar concentration of K is 0.04-0.05mol/L 2 S 2 O 8 The molar concentration of (C) is 0.01-0.02mol/L.
Preferably, in S2, heating to 145-155 ℃ and maintaining for 9-11h to perform hydrothermal reaction; and carrying out thermal annealing treatment for 1-3h at 380-420 ℃.
Preferably, in S3, ni in the divalent nickel salt after dissolution in deionized water 2+ And Co in a divalent cobalt salt 2+ The molar ratio of (2) is 1:2, the total molar concentration of metal ions is 0.08-0.15mol/L, NH 4 F has a molar concentration of 0.08-0.15mol/L and urea has a molar concentration of 0.25-0.30mol/L.
Preferably, in S3, after the mixed solution of DMF and DMSO is added, the volume percentage of the mixed solution in the system is 8-12vt percent.
Preferably, in S3, the hydrothermal reaction is carried out by heating to 100-110℃for 9-11 hours.
Preferably, in S4, the high temperature phosphating is carried out at 340-360 ℃ for 1.5-2.5 hours.
The invention also provides the sea urchin-shaped Ni@Ni prepared by adopting the method 2 P@NiCoP electrode material.
The invention also provides the sea urchin-shaped Ni@Ni 2 The application of the P@NiCoP electrode material in catalyzing alkaline electrolysis water hydrogen evolution reaction.
The invention also provides the sea urchin-shaped Ni@Ni 2 Application of P@NiCoP electrode material in catalyzing alkaline seawater full hydrolysis.
The beneficial effects are that: according to the invention, niO nano-sheets are grown on a foam nickel substrate by a hydrothermal method and heat treatment, and thenIn a three solvent system (H 2 O/DMF/DMSO), depositing a NiCo (OH) x precursor on the NiO nanosheet skeleton by a hydrothermal method to form a hierarchical heterogeneous nanostructure, and finally performing high-temperature phosphating treatment to successfully prepare the sea urchin-shaped Ni@Ni2P@NiCoP electrode material. According to the invention, the NiO nano-sheet synthesized in the first hydrothermal process is utilized to provide a growth site for the cluster nano-needle grown in the second hydrothermal process, and the structure can fully contact with electrolyte to expose the active site and enhance the HER performance of the catalyst. In addition, by adding the surface structure regulator DMF and DMSO in the hydrothermal process and regulating the proportion of the DMF and DMSO, a nano spherical structure similar to sea urchins is obtained, compared with the method of adding only one MSO or DMF, the nano spherical structure has more excellent catalytic activity, and the changed morphology benefits from large active area, high surface activity and favorable ion and gas diffusion channels, and has excellent HER activity. The electrode material prepared by the invention can obtain catalytic efficiency comparable to commercial Pt/C, and has high HER catalytic activity.
Drawings
FIG. 1 is a diagram of sea urchin-like Ni@Ni according to the present invention 2 A synthetic schematic diagram of the P@NiCoP electrode material;
FIG. 2 is a sea urchin-like Ni@Ni prepared in example 1 of the present invention 2 SEM images of p@nicop electrode material;
FIG. 3 is an XRD pattern of the material prepared in example 1 of the present invention; wherein a is Ni@NiO, b is Ni@NO@NCO, c is Ni@NP@NCP (H), d is Ni@NP@NCP (F), e is Ni@NP@NCP (SO), and F is Ni@NP@NCP (F/SO);
FIG. 4 is a chart showing the sea urchin-like Ni@Ni prepared in example 1 of the present invention 2 XPS diagram of P@NiCoP electrode material;
FIG. 5 is an LSV plot of the material prepared in example 1 of the present invention;
FIG. 6 is a Tafil slope plot of the material prepared in example 1 of the present invention;
FIG. 7 is a LSV graph of the material prepared in example 1 of the present invention in seawater;
FIG. 8 is an EIS diagram of the material prepared in example 1 of the present invention;
FIG. 9 is a sea urchin-like Ni@Ni prepared in example 1 of the present invention 2 P@NLSV plot of water total decomposition of iCoP electrode material in different electrolytes;
FIG. 10 is a chart showing the sea urchin-like Ni@Ni prepared in example 1 of the present invention 2 P@NiCoP electrode material is used as a timing potential v-t curve of the catalyst for full decomposition of water.
Detailed Description
As shown in FIG. 1, is sea urchin-like Ni@Ni 2 Schematic diagram of the synthesis process of the P@NiCoP nanostructure composite material. Firstly, synthesizing NiO nano-sheets on a foam nickel substrate by adopting a hydrothermal method; then in a three solvent system (H 2 In O/DMF/DMSO) NiCo (OH) was further prepared by hydrothermal method x The precursor is deposited on the NiO nanosheet skeleton to form a hierarchical heterogeneous nanostructure; finally, carrying out high-temperature phosphating treatment on the heterostructure composite material in inert atmosphere to successfully prepare the sea urchin-shaped Ni@Ni 2 P@NiCoP nanostructured catalyst.
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Sea urchin-shaped Ni@Ni 2 The preparation method of the P@NiCoP electrode material comprises the following steps:
(1) Pretreatment of foam nickel: the cut foam nickel NF (3X 2.5 cm) 2 ) Respectively ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, and drying for standby.
(2) Synthesis of Ni@NiO: the washed foam nickel was transferred to a polyphenyl (PPL) lined stainless steel autoclave (50 ml) containing homogeneous Ni (NO) 3 ) 2 ·6H 2 O (380 mg) and K 2 S 2 O 8 (100 mg) dissolved in 30ml H 2 Solution in O. Thereafter, the autoclave was sealed and kept at 150℃for 10 hours. After the reaction vessel cooled to room temperature, the sample was removed and washed several times with deionized water and ethanol and dried overnight at 60 ℃ under vacuum. And then carrying out thermal annealing on the base material for 2 hours in air at 400 ℃ to obtain the Ni@NiO material.
(3)Ni@NiO@NiCo(OH) x Synthesizing a precursor: typically, 1m is weighedM Ni(NO 3 ) 2 ·6H 2 O、2mM Co(NO 3 ) 2 ·6H 2 O、3mM NH 4 F and 7.5mM urea were dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then 2mL of DMF and 1mL of DMSO mixed solution were slowly added and stirring was continued for 10 minutes. After the solution was homogeneous, transfer to a 50mL teflon lined steel autoclave with ni@nio. After hydrothermal reaction for 11 hours at 100 ℃, washing with deionized water to obtain Ni@NiO@NiCo (OH) x The precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni 2 Synthesis of P@NiCoP: placing 0.75g NaH upstream of the porcelain boat 2 PO 2 ·H 2 O powder, ni@NiO@NiCo (OH) was placed downstream x Precursor sample, at N 2 Heated to 350 ℃ in a tube furnace under atmosphere and maintained for 2 hours. When the temperature naturally cools to room temperature, sea urchin-shaped Ni@Ni is obtained 2 P@NiCoP composite material.
Example 2
Sea urchin-shaped Ni@Ni 2 The preparation method of the P@NiCoP electrode material comprises the following steps:
(1) Pretreatment of foam nickel: the cut foam nickel NF (3X 2.5 cm) 2 ) Respectively ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, and drying for standby.
(2) Synthesis of Ni@NiO: the washed foam nickel was transferred to a polyphenyl (PPL) lined stainless steel autoclave (50 ml) containing homogeneous Ni (NO) 3 ) 2 ·6H 2 O (350 mg) and K 2 S 2 O 8 (85 mg) dissolved in 30ml H 2 Solution in O. Thereafter, the autoclave was sealed and maintained at 145℃for 11 hours. After the reaction vessel cooled to room temperature, the sample was removed and washed several times with deionized water and ethanol and dried overnight at 60 ℃ under vacuum. And then carrying out thermal annealing on the base material for 3 hours in air at 380 ℃ to obtain the Ni@NiO material.
(3)Ni@NiO@NiCo(OH) x Synthesizing a precursor: typically, 0.8mM Ni (NO 3 ) 2 ·6H 2 O、1.6mM Co(NO 3 ) 2 ·6H 2 O、2.5mM NH 4 F and 7mM urea were dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then 1.6mL of DMF and 0.8mL of DMSO mixed solution were slowly added and stirring was continued for 10 minutes. After the solution was homogeneous, transfer to a 50mL teflon lined steel autoclave with ni@nio. After hydrothermal reaction for 11 hours at 100 ℃, washing with deionized water to obtain Ni@NiO@NiCo (OH) x The precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni 2 Synthesis of P@NiCoP: placing 0.75g NaH upstream of the porcelain boat 2 PO 2 ·H 2 O powder, ni@NiO@NiCo (OH) was placed downstream x Precursor sample, at N 2 The tube furnace was heated to 340℃under an atmosphere and held for 2.5h. When the temperature naturally cools to room temperature, sea urchin-shaped Ni@Ni is obtained 2 P@NiCoP composite material.
Example 3
Sea urchin-shaped Ni@Ni 2 The preparation method of the P@NiCoP electrode material comprises the following steps:
(1) Pretreatment of foam nickel: the cut foam nickel NF (3X 2.5 cm) 2 ) Respectively ultrasonic washing in acetone, hydrochloric acid, deionized water and ethanol to remove impurities and oxide layers on the surface, washing with deionized water to neutrality, and drying for standby.
(2) Synthesis of Ni@NiO: the washed foam nickel was transferred to a polyphenyl (PPL) lined stainless steel autoclave (50 ml) containing homogeneous Ni (NO) 3 ) 2 ·6H 2 O (420 mg) and K 2 S 2 O 8 (150 mg) dissolved in 30ml H 2 Solution in O. Thereafter, the autoclave was sealed and kept at 155℃for 9 hours. After the reaction vessel cooled to room temperature, the sample was removed and washed several times with deionized water and ethanol and dried overnight at 60 ℃ under vacuum. And then carrying out thermal annealing on the base material for 1h in the air at 420 ℃ to obtain the Ni@NiO material.
(3)Ni@NiO@NiCo(OH) x Synthesizing a precursor: typically, 1.2mM Ni (NO 3 ) 2 ·6H 2 O、2.4mM Co(NO 3 ) 2 ·6H 2 O、4mM NH 4 F and 8mM urea was dissolved in 27mL deionized water and stirred at room temperature for 10 minutes. Then a mixed solution of 2.4mL DMF and 1.2mL DMSO was slowly added and stirring continued for 10 minutes. After the solution was homogeneous, transfer to a 50mL teflon lined steel autoclave with ni@nio. After hydrothermal reaction for 9 hours at 110 ℃, washing with deionized water to obtain Ni@NiO@NiCo (OH) x The precursor was then dried in an oven at 60 ℃.
(4)Ni@Ni 2 Synthesis of P@NiCoP: placing 0.75g NaH upstream of the porcelain boat 2 PO 2 ·H 2 O powder, ni@NiO@NiCo (OH) was placed downstream x Precursor sample, at N 2 The tube furnace was heated to 360℃under an atmosphere and held for 2.5h. When the temperature naturally cools to room temperature, sea urchin-shaped Ni@Ni is obtained 2 P@NiCoP composite material.
For the sea urchin-shaped Ni@Ni prepared in the embodiment of the invention 2 The P@NiCoP composite material is subjected to characterization and performance test.
The following substances, such as Ni@NiO, ni@NO@NCO, ni@NP@NCP (H), ni@NP@NCP (F), ni@NP@NCP (SO), ni@NP@NCP (F/SO), and the like, were prepared as follows:
Ni@NiO: the sea urchin-like Ni@Ni of example 1 was used 2 The P@NiCoP electrode material is prepared by the steps (1) and (2);
Ni@NO@NCO: the sea urchin-like Ni@Ni of example 1 was used 2 Steps (1), (2) and (3) of the preparation method of the P@NiCoP electrode material, and then obtaining Ni@NiO@NiCo (OH) x The precursor is arranged in N 2 Heating to 350 ℃ in a tube furnace under atmosphere, maintaining for 2 hours, and naturally cooling to room temperature to obtain the product;
Ni@NP@NCP (H): and sea urchin-like Ni@Ni in example 1 2 The preparation of the P@NiCoP electrode material only differs in that: in the step (3), 2mL of DMF and 1mL of DMSO mixed solution are replaced by 3mL of deionized water;
Ni@NP@NCP (F): and sea urchin-like Ni@Ni in example 1 2 The preparation of the P@NiCoP electrode material only differs in that: in the step (3), 2mL of DMF and 1mL of DMSO mixed solution are replaced by 3mL of DMF;
Ni@NP@NCP (SO): and sea urchin-like Ni@Ni in example 1 2 P@NiCoP electricThe preparation of the pole material differs only in that: in the step (3), 2mL of DMF and 1mL of DMSO mixed solution are replaced by 3mL of DMSO;
Ni@NP@NCP (F/SO): ni@Ni prepared for example 1 of the present invention 2 P@NiCoP composite material.
Characterization (one)
Sem characterization:
FIG. 2 is Ni@Ni 2 As can be seen from the SEM image of the P@NiCoP electrode material, the morphology of the composite material is greatly changed by adding DMF/DMSO, and Ni@Ni 2 The structure of the P@NiCoP is a nanosphere like a sea urchin, but the surface is still covered with uniform and compact cluster-shaped nano needles, and the sea urchin-shaped structure can further increase the surface area of the composite material and promote the electrocatalytic performance of the composite material.
XRD characterization
The chemical composition of the resulting composite was investigated by XRD. Typical XRD patterns are shown in FIG. 3, and diffraction peaks at 44.6, 52.0 and 76.6 are found in all diffraction patterns, which can be attributed to NF, corresponding to the (111), (200) and (220) crystal planes of the Ni phase (JCDF No. 70-0989). Peaks in curve a at 2θ=37.3 °, 43.4 ° and 63.0 ° can be assigned to the (111), (200) and (220) planes of NiO (JCPDF No. 73-1519). In addition to the NiO peaks, diffraction peaks at 31.1 °, 36.7 °, 59.1 ° and 65.0 ° were found in curve b, and they were ascribed to NiCo 2 O 4 The (220), (311), (511) and (440) crystal planes of the (JCDF No. 20-0781) species. Thus, the sample corresponding to curve b can be identified as Ni@NiO@NiCo 2 O 4 . Diffraction peaks of equal intensity at positions observed in curve c, d, e, f after phosphating, which are located at 41.0 °, 47.6 ° and 54.4 °, are compared with Ni 2 The (111), (210) and (300) planes of P (JCDF No. 74-1385) and NiCoP (JCDF No. 71-2336) are completely coincident. Peaks at 54.7 ° and 55.3 ° correspond to the (002), (211) crystal planes of NiCoP. Thus, it can be seen that the addition of DMSO and DMF only changes the microscopic morphology of the catalyst, no reaction occurs to produce new species, and all phosphatized samples can be defined as Ni@Ni 2 P@NiCoP。
XPS characterization
Further XPS measurements were used to probe Ni@Ni 2 Surface composition and oxidation state of P@NiCoP. From the survey spectrum (fig. 4 a) it can be seen that the electrode surface is present with Ni, co, P, O, C elements. Elemental C (C1 s,284.6 ev) is mainly from environmental pollution and is used as a reference for calibration of XPS spectra obtained. Ni@Ni 2 Ni2p of P@NiCoP 3/2 The core energy spectrum (FIG. 4 b) shows three peaks with binding energies 853.0, 856.8 and 861.9eV, respectively, which should be comparable to Ni-P, ni-PO, respectively x Associated with satellite peaks. Here, the binding energy of 853.0 is very close to that of metallic Ni (852.6 eV), indicating the presence of partially charged Ni species (Ni δ+ δ may be close to 0). Similarly, due to Co-P formation, the converted Ni@Ni 2 Co 2p of P@NiCoP 3/2 The fragment (FIG. 4 c) has a new peak at 778.4eV, which is also found to be slightly higher than the metal Co (778.2 eV), indicating that Co carries a partial positive charge (Co δ+ ). The peak at 781.8eV can be attributed to the Co oxidation state, which is the same as Co-PO x And (5) correlation. While the 786.1eV peak is associated with a satellite oscillation peak (sat.). FIG. 4d shows the P2P region, wherein two bimodals are observed, with main peak binding energies of 129.9 and 134.5eV, respectively. The former can be classified as reduced phosphorus in the form of metal phosphides with a binding energy of 129.9eV slightly lower than that of element P (130.0 eV), indicating that the P moiety is negatively charged (P δ- ). Thus, P can capture positively charged protons as a base during electrocatalysis. The latter are classified as phosphate substances (P) 5+ ) This is mainly from P on the surface 2 O 5 And PO (PO) 4 3- Is formed by the steps of (a). In fact, the O-P peak gives the same result at 531.5eV of the O1s spectrum (FIG. 4 e). Additional peaks at 532.8eV are associated with surface mass adsorption of water.
(II) electrochemical Performance test
1. HER Activity in 1mol/L KOH electrolyte
We first evaluated the HER activity of the prepared electrode material in a 1mol/LKOH electrolyte in a three-electrode system at room temperature (25 ℃). A Linear Scan Voltammogram (LSV) of Ni@NiO, ni@NO@NCO, ni@NP@NCP (H), ni@NP@NCP (F), ni@NP@NCP (SO), ni@NP@NCP (F/SO) nanostructures and commercial Pt/C is shown in FIG. 5. And Ni@NiO%258.7, 352.2 and 380.5 mV), ni@NO@NCO (156.7, 261.2 and 303 mV), ni@NP@NCP (H) (93.2, 173.2 and 221.2 mV), ni@NP@NCP (SO) (107.2, 200.2 and 250.2 mV), ni@NP@NCP (F) (74.2, 157.7 and 201.2 mV) nanostructures providing 10, 100 and 300mA cm at low overpotential of 68.2, 139.2 and 185.7mV, respectively -2 HER performance exceeded commercial Pt/C catalysts even at 193.2mV overpotential.
The Tafel slope of the prepared nanostructure was also calculated from the LSV curve to accurately explore HER dynamics. As shown in FIG. 6, the catalyst was bonded to Ni@NiO (104.05 mV dec -1 )、Ni@NO@NCO(92.95mV dec -1 )，Ni@NP@NCP(H)(79.92mV dec -1 )、Ni@NP@NCP(SO)(83.32mV dec -1 )、Ni@NP@NCP(F)(79.4mV dec -1 ) In contrast, the Ni@NP@NCP (F/SO) nanostructure showed a smaller Tafel slope of 71.64mV dec -1 Only slightly higher than commercial Pt/C, indicating rapid HER reaction kinetics.
2. Alkaline mimicking HER activity in seawater electrolyte (1M KOH+0.5M NaCl)
Then, we studied HER activity in alkaline simulated seawater electrolyte (1M koh+0.5m NaCl). As shown in FIG. 7, the Ni@NP@NCP (F/SO) nanostructured catalysts still exhibited excellent HER catalytic activity, requiring 80.2, 155.7 and 198.9mV overpotentials to achieve 10, 100 and 300mAcm, respectively -2 Is used for the current density of the battery. This performance is very similar to that in 1M KOH electrolyte, indicating that nf@np@ncp (F/SO) nanostructures still have good HER performance in alkaline conditioned brine.
To gain a deeper understanding of HER response kinetics, EIS tests were also performed (fig. 8). The ni@np@ncp (F/SO) nanostructure showed a minimum transfer resistance (Rct) of 0.3 Ω compared to ni@nio (2.2 Ω), ni@no@nco (1.52 Ω), ni@np@ncp (H) (0.93 Ω), ni@np@ncp (SO) (1.24 Ω), ni@np@ncp (F) (0.44 Ω), demonstrating the fastest electron transfer rate and lowest electrical impedance contributing to its excellent HER activity.
3. Full hydrolysis Performance test
Inspired by the excellent HER performance of the catalyst, the Ni@NP@NCP (F/SO) nanostructures are assembled into a bipolar alkalineThe cathode and anode in the cell (without membrane or film) were further investigated for overall seawater decomposition performance. Impressive, powerful catalytic performance is achieved by synthetic ni@np@ncp (F/SO) electrodes. And, the electrolytic cell exhibits excellent overall water-decomposing activity in both an alkaline solvent and an alkaline pseudo-seawater electrolyte. As shown in FIG. 9, 100mA cm was produced in 1M KOH and 1M KOH+0.5M NaCl at room temperature (25 ℃) -2 The cell voltages required for current densities are as low as 1.697 and 1.724V, respectively. In particular, our electrolyzer can produce 300mA cm in 1M KOH+0.5M NaCl electrolyte at a voltage of 1.822V -2 The high current density of (2) meets the requirement of realizing the high current density required by industry under low voltage.
Operational durability is also a very important indicator for evaluating the performance of an electrolytic cell. As shown in FIG. 10, the cell was used in an alkaline solvent and an alkaline simulated seawater electrolyte at 200mA cm -2 The constant current density of the seawater desalination device is operated for 24 hours, and the excellent overall seawater decomposition performance can be maintained, and the working voltage is not obviously changed, so that the seawater desalination device has great potential in large-scale application.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. Sea urchin-shaped Ni@Ni 2 The preparation method of the P@NiCoP electrode material is characterized by comprising the following steps of:
s1, pretreatment of foam nickel: cutting foam nickel into proper size and cleaning;
s2, synthesizing Ni@NiO: placing the cut foam nickel in a bath containing divalent nickel salt and K 2 S 2 O 8 Heating to perform hydrothermal reaction, cooling, washing, drying, and performing thermal annealing treatment in air atmosphere to obtain Ni@NiO material;
S3、Ni@NiO@NiCo(OH) x synthesizing a precursor: divalent Nickel salt, divalent cobalt salt, NH 4 F and urea are dissolved in deionized water, stirred and mixed, then mixed solution of DMF and DMSO is added, the mixture is stirred, ni@NiO material is added, heating is carried out for hydrothermal reaction, washing and drying are carried out, and Ni@NiO@NiCo (OH) is obtained x A precursor; wherein, the volume ratio of DMF to DMSO is 2:1, a step of;
S4、Ni@Ni 2 synthesis of P@NiCoP: ni@NiO@NiCo (OH) x Transferring the precursor into a tubular furnace, placing hypophosphite at an upper air port of an air path of the tubular furnace, introducing inert gas for high-temperature phosphating treatment, and cooling to obtain sea urchin-shaped Ni@Ni 2 P@NiCoP；
S2 comprises divalent nickel salt and K 2 S 2 O 8 Ni in the divalent Ni salt 2+ The molar concentration of K is 0.04-0.05mol/L 2 S 2 O 8 The molar concentration of (2) is 0.01-0.02mol/L;
s3, after being dissolved in deionized water, ni in bivalent nickel salt 2+ And Co in a divalent cobalt salt 2+ The molar ratio of (2) is 1:2, the total molar concentration of metal ions is 0.08-0.15mol/L, NH 4 F has a molar concentration of 0.08-0.15mol/L and urea has a molar concentration of 0.25-0.30mol/L; after adding the mixed solution of DMF and DMSO, the volume percentage of the mixed solution in the system is 8-12vt percent.
2. Sea urchin-like ni@ni according to claim 1 2 The preparation method of the P@NiCoP electrode material is characterized in that the divalent nickel salt is one of nickel nitrate, nickel chloride and nickel acetate; the bivalent cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt acetate.
3. Sea urchin-like ni@ni according to claim 1 2 The preparation method of the P@NiCoP electrode material is characterized by comprising the steps of heating to 145-155 ℃ in S2, and keeping for 9-11h for hydrothermal reaction; and carrying out thermal annealing treatment for 1-3h at 380-420 ℃.
4. Sea urchin-like ni@ni according to claim 1 2 P@NiCoP electrodeThe preparation method of the material is characterized in that in S3, the material is heated to 100-110 ℃ and kept for 9-11h for hydrothermal reaction.
5. Sea urchin-like ni@ni according to claim 1 2 The preparation method of the P@NiCoP electrode material is characterized in that in S4, the high-temperature phosphating treatment is carried out for 1.5-2.5 hours at 340-360 ℃.
6. Sea urchin-like Ni@Ni prepared by the method as claimed in any one of claims 1-5 2 P@NiCoP electrode material.
7. Sea urchin-like Ni@Ni as claimed in claim 6 2 The application of the P@NiCoP electrode material in catalyzing alkaline electrolysis water hydrogen evolution reaction.
8. Sea urchin-like Ni@Ni as claimed in claim 7 2 Application of P@NiCoP electrode material in catalyzing alkaline seawater full hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111447503.XA CN114134536B (en) | 2021-11-30 | 2021-11-30 | Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111447503.XA CN114134536B (en) | 2021-11-30 | 2021-11-30 | Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114134536A CN114134536A (en) | 2022-03-04 |
| CN114134536B true CN114134536B (en) | 2023-10-24 |
Family
ID=80386329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111447503.XA Active CN114134536B (en) | 2021-11-30 | 2021-11-30 | Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114134536B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323392B (en) * | 2022-08-12 | 2024-05-14 | 青岛理工大学 | Preparation of efficient Co/NiCoP/CC heterogeneous nanoparticle hydrogen evolution reaction electrocatalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017091955A1 (en) * | 2015-11-30 | 2017-06-08 | South University Of Science And Technology Of China | Bifunctional electrocatalyst for water splitting and preparation method thereof |
| CN112156798A (en) * | 2020-09-25 | 2021-01-01 | 河南师范大学 | NiCoP/NiCo-DH @ NF composite material, preparation method and application |
| CN112916028A (en) * | 2021-01-12 | 2021-06-08 | 安徽理工大学 | Benzene ring structure-like bimetal composite material and preparation and application thereof |
| CN112941559A (en) * | 2021-01-12 | 2021-06-11 | 安徽理工大学 | Fe-Co bimetal phosphide electrode material and preparation and application thereof |
| CN113130214A (en) * | 2021-03-17 | 2021-07-16 | 上海应用技术大学 | NF @ molybdenum oxide @ nickel cobalt-LDH composite material and preparation method and application thereof |
-
2021
- 2021-11-30 CN CN202111447503.XA patent/CN114134536B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017091955A1 (en) * | 2015-11-30 | 2017-06-08 | South University Of Science And Technology Of China | Bifunctional electrocatalyst for water splitting and preparation method thereof |
| CN112156798A (en) * | 2020-09-25 | 2021-01-01 | 河南师范大学 | NiCoP/NiCo-DH @ NF composite material, preparation method and application |
| CN112916028A (en) * | 2021-01-12 | 2021-06-08 | 安徽理工大学 | Benzene ring structure-like bimetal composite material and preparation and application thereof |
| CN112941559A (en) * | 2021-01-12 | 2021-06-11 | 安徽理工大学 | Fe-Co bimetal phosphide electrode material and preparation and application thereof |
| CN113130214A (en) * | 2021-03-17 | 2021-07-16 | 上海应用技术大学 | NF @ molybdenum oxide @ nickel cobalt-LDH composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "In situ surface engineering of nickel inverse opal for enhanced overall electrocatalytic water splitting";Zhou, Qingwen等;《JOURNAL OF MATERIALS CHEMISTRY A》;第5卷(第28期);第14873-14880页 * |
| "NiCoP self-supporting electrode with the sea urchin-like microstructure for the synchronous reaction of hydrogen evolution and contaminant degradation";Zhang, Shengnan等;《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》;第891卷;文献号 115273 * |
| "Synthesis of Urchin-like Ni@NP@NCP Composites with Three Solvothermal Systems for Highly Efficient Overall Seawater Splitting";Yang, Ping等;《LANGMUIR》;第39卷(第17期);第6240-6248页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114134536A (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A self-supported Ni–Co perselenide nanorod array as a high-activity bifunctional electrode for a hydrogen-producing hydrazine fuel cell | |
| Fang et al. | Nickel promoted cobalt disulfide nanowire array supported on carbon cloth: an efficient and stable bifunctional electrocatalyst for full water splitting | |
| Jayabalan et al. | Enhancing biohydrogen production from sugar industry wastewater using metal oxide/graphene nanocomposite catalysts in microbial electrolysis cell | |
| Li et al. | From water reduction to oxidation: Janus Co-Ni-P nanowires as high-efficiency and ultrastable electrocatalysts for over 3000 h water splitting | |
| Chen et al. | Hierarchical porous NiFe-P@ NC as an efficient electrocatalyst for alkaline hydrogen production and seawater electrolysis at high current density | |
| Huang et al. | Flexible cobalt phosphide network electrocatalyst for hydrogen evolution at all pH values | |
| Zhang et al. | Hydrolysis assisted in-situ growth of 3D hierarchical FeS/NiS/nickel foam electrode for overall water splitting | |
| US20220349066A1 (en) | Non-Noble Metal-Nitride Based Electrocatalysts for High-Performance Seawater Splitting | |
| CN109954503B (en) | Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application | |
| CN113005469B (en) | Ruthenium-loaded amorphous nickel hydroxide/nickel phosphide composite electrode and preparation method and application thereof | |
| US11459664B2 (en) | Multi-metal catalysts and devices and methods of use thereof | |
| CN112941559A (en) | Fe-Co bimetal phosphide electrode material and preparation and application thereof | |
| Jayabalan et al. | NiCo2O4-graphene nanocomposites in sugar industry wastewater fed microbial electrolysis cell for enhanced biohydrogen production | |
| CN111111707A (en) | Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof | |
| Gao et al. | Surface reconstructing hierarchical structures as robust sulfion oxidation catalysts to produce hydrogen with ultralow energy consumption | |
| CN111883367A (en) | Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof | |
| Guo et al. | Co/Cu-modified NiO film grown on nickel foam as a highly active and stable electrocatalyst for overall water splitting | |
| Devi et al. | Spatially dispersed one-dimensional carbon architecture on oxide framework for oxygen electrochemistry | |
| Ma et al. | In situ construction and post-electrolysis structural study of porous Ni 2 P@ C nanosheet arrays for efficient water splitting | |
| CN113637997A (en) | Co2P/CuP2Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst | |
| CN113275027A (en) | Preparation and application of bimetallic phosphide derived from prussian blue analogue as template and growing on foamed nickel | |
| Wang et al. | Corrosive engineering assisted in situ construction of an Fe–Ni-based compound for industrial overall water-splitting under large-current density in alkaline freshwater and seawater media | |
| Trivedi et al. | Self-supported Cr–Cu2S nanoflakes for hydrogen production from seawater | |
| CN114134536B (en) | Sea urchin-shaped Ni@Ni 2 P@NiCoP electrode material and preparation method and application thereof | |
| Wang et al. | Ni2P (O)–Fe2P (O)/CeOx as high effective bifunctional catalyst for overall water splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |