CN117468035A - Electrode for electrocatalytic water oxidation and preparation method thereof - Google Patents
Electrode for electrocatalytic water oxidation and preparation method thereof Download PDFInfo
- Publication number
- CN117468035A CN117468035A CN202311211000.1A CN202311211000A CN117468035A CN 117468035 A CN117468035 A CN 117468035A CN 202311211000 A CN202311211000 A CN 202311211000A CN 117468035 A CN117468035 A CN 117468035A
- Authority
- CN
- China
- Prior art keywords
- nickel
- bismuth
- electrode
- source
- hydroxide
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 47
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 168
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 71
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 65
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 49
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002110 nanocone Substances 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- 239000002243 precursor Substances 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 58
- 238000004070 electrodeposition Methods 0.000 claims description 56
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 50
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 35
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011530 conductive current collector Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002640 NiOOH Inorganic materials 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002484 cyclic voltammetry Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 70
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract 1
- 229910005578 NiBi Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GTGNGELJAJUYKF-UHFFFAOYSA-N O(O)O.[Ni]=O Chemical compound O(O)O.[Ni]=O GTGNGELJAJUYKF-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- -1 bismuth modified nickel Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000005406 washing 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
Abstract
The application discloses an electrode and a preparation method thereof, wherein the electrode has a structure of a self-supporting micro-nano cone array structure formed by secondary crosslinking and assembling of bismuth doped nickel (oxygen) hydroxide electrocatalyst nano sheets. The three-dimensional structure has excellent mass transfer and bubble transmission characteristics, good physical stability and structural stability, the catalytic activity of the three-dimensional structure is comparable to that of a nickel molten iron oxidation catalyst in an electrocatalytic water oxidation reaction, meanwhile, a nickel-bismuth catalyst system has more excellent stability, and the elution of bismuth species in a long-time catalysis process is almost negligible, so that the three-dimensional structure has obvious advantages compared with a typical nickel-iron system, and has an industrial application foundation.
Description
Technical Field
The application relates to an electrode for electrocatalytic water oxidation and a preparation method thereof, and belongs to the field of electrodes.
Background
The technology for producing hydrogen by electrolyzing water can realize the conversion and storage of renewable energy sources to hydrogen energy, is an effective way for solving the problems of energy sources and environment, and related researches are widely focused on all countries of the world. Among various water electrolysis hydrogen production technologies, the alkaline water electrolysis hydrogen production technology has a mature commercialization mode and can be realized by a non-noble metal electrocatalyst, and is one of ideal modes for preparing green hydrogen. The development of the low-cost, high-efficiency and stable water oxidation electrocatalyst is one of the cores of the alkaline water electrolysis hydrogen production technology, and the related research has important significance. The nickel-based metal oxide system has the advantages of alkali corrosion resistance, easiness in synthesis and modulation and the like, and has been widely applied to water electrolysis processes as an anode material of a commercial alkaline water electrolysis system. However, the anode material has poor alkaline oxygen evolution performance under the working condition of high current density, and the required overpotential is high, so that the energy consumption of the electrolyzed water is high. In order to further improve the hydrogen production efficiency of alkaline electrolyzed water and reduce energy consumption, it is important to develop a nickel-based catalytic system with excellent performance.
The multi-metal composite nickel-based oxide system coupling different metal components is an effective way to obtain a high-efficiency catalyst, such as NiFe (CN 106861699A; NC 202010202643.X; J.am. Chem. Soc.2013,135, 12329-12337), niCo (CN 110721749B; CN 112226780A), coV (ACS catalyst.2018, 8, 644-650) and other binary metal-based oxide catalysts, and research on the use of a multi-element alloy oxide catalyst represented by NiFeCo (CN 109423660B; CN114892207A; ACS catalyst.2016, 6,155-161;Adv.Energy Mater.2015,1402307) for catalyzing a water oxidation reaction is based on the design and regulation of a multi-element catalytic system. The early research results show that the design of the bimetallic or even more meta-metal-based oxide water oxidation catalyst not only can adjust the electronic property of the catalyst to improve the intrinsic activity, but also can influence the morphology and three-dimensional structural characteristics of the catalyst, and greatly increases the number of active sites to improve the overall catalytic performance of the catalyst. So far, although a number of multi-element nickel-based composite oxide catalyst systems have been designed and used in electrocatalytic water oxidation studies, the most representative and potential system is still a NiFe-based composite oxide catalyst. However, the catalyst system has serious Fe loss under the severe condition of working condition operation, which affects the working efficiency and the service life of the electrode system and restricts the further popularization and application of the electrode system (Chem 2017,2,590-597; angew.chem.int.ed.2018,57, 1616-1620). Therefore, to achieve a more efficient and stable water oxidation catalytic process, it is still necessary to develop a catalyst system that has properties comparable to NiFe-based catalysts and that is more stable.
The metal bismuth has the advantages of easy alloying, convenient formation of new Bi-based active centers, capability of modulating the adsorption characteristics of reaction intermediate species on the active sites of the original metal and the like to promote the activity of the catalyst, and meanwhile, the Bi is taken as a trace binary component to form a composite system, so that a more stable catalyst system can be obtained. Based on the advantages, the construction of the bismuth-doped nickel-based composite oxide catalyst system is expected to obtain an excellent electrocatalytic water oxidation catalyst system. The previous research result shows that the construction of a NiBi system by the bismuth modified nickel electrode can improve the glycerol oxidation and tetracycline degradation performance of the nickel-based electrode (ACS appl. Mater. Interfaces 2020,12,15095-15107; CN115432746A); meanwhile, the NiBi catalytic system also has alkaline hydrogen evolution performance (chemSus chem 2021,14,3074-3083; J.Mater.chem. A,2022,10, 808) superior to that of a pure Ni-based system, which shows that bismuth doping has a significant improvement effect on a nickel-based electrode system; in addition, bi doping has also been reported to be advantageous in the construction of high activity catalyst systems with spin-dependent symmetry break (nat. Commun.2022,13,4106). Therefore, on the basis, by reasonable design and construction, the development of the bismuth doped nickel (oxygen) hydroxide catalyst system with unique electronic characteristics and three-dimensional structure is expected to realize the efficient electrocatalytic water oxidation process.
Disclosure of Invention
According to one aspect of the application, an electrode for electrocatalytic water oxidation is provided, the electrode system is a self-supporting micro-nano cone array structure formed by secondarily crosslinking and assembling nano sheets, the three-dimensional structure has excellent mass transfer and bubble transmission characteristics, good physical stability and structural stability, the catalytic activity of the electrocatalytic catalyst in the electrocatalytic water oxidation reaction is comparable with that of a ferronickel water oxidation catalyst, meanwhile, the nickel bismuth catalyst system has more excellent stability, and the bismuth species is dissolved out almost negligible in the long-time catalysis process, so that the electrode system has obvious advantages compared with a typical ferronickel system, and has an industrial application basis.
The electrode for electrocatalytic water oxidation comprises a bismuth-doped nickel (oxygen) hydroxide electrocatalyst and a conductive current collector;
the bismuth doped nickel (oxy) hydroxide electrocatalyst comprises nickel-based hydroxide and nickel-based oxide;
the nickel-based hydroxide and the nickel-based oxide are doped with bismuth;
wherein bismuth is Bi 3+ In the form of nickel (oxy) hydroxide, nickel being present as Ni 2+ And Ni 3+ Is present in the nickel (oxy) hydroxide;
the bismuth doped nickel (oxy) hydroxide electrocatalyst is deposited on a conductive current collector;
the electrode is in a self-supporting micro-nano cone array structure.
Optionally, the self-supporting micro-nano cone array structure is formed by secondarily crosslinking and assembling bismuth-doped nickel (oxygen) hydroxide electrocatalyst nano sheets.
Alternatively, the crystalline phase of the bismuth doped nickel (oxy) hydroxide electrocatalyst comprises 4Ni (OH) 2 -NiOOH and hexagonal nickel-based hydrotalcite structures.
Alternatively, bismuth is in Bi 3+ Is uniformly distributed in the nickel (oxy) hydroxide.
Optionally, bismuth comprises 0.1at.% to 20at.% of the total metal content; preferably, bismuth comprises 0.1at.% to 10at.% of the total metal content; more preferably, bismuth comprises 3.5at.% of the total metal content.
Alternatively, the ratio of bismuth metal to total metal content is independently selected from any one of the values 0.1at.%, 1at.%, 2at.%, 3at.%, 4at.%, 5at.%, 10at.%, 20at.%, or a range of values for both.
At.% in this application refers to atomic percent.
Optionally, the bismuth doped nickel (oxy) hydroxide electrocatalyst is further modified with a third metal modifier; the third metal modifier is a metal-containing component other than bismuth and nickel.
Optionally, the non-bismuth and nickel containing metal-containing component is selected from any one or more of the Fe, co, W, mn, V, cr, sn, mo, ce, cu containing components.
Optionally, the conductive current collector is a nickel-based current collector.
In yet another aspect, the present application provides a method of preparing an electrode for electrocatalytic water oxidation, comprising: depositing and growing a bismuth doped nickel (oxygen) hydroxide electrocatalyst on the conductive current collector to obtain an electrode;
the deposition growth mode is deposition growth mode I and/or deposition growth mode II;
the deposition growth mode I sequentially comprises a low-temperature wet chemical method operation and an electrochemical deposition growth operation;
the deposition growth mode II sequentially comprises a hydrothermal operation, a high-temperature roasting operation and an electric traction growth operation.
Preferably, before deposition growth, a process of treating the conductive current collector is included, the process including:
the metallic nickel material is immersed in a reaction solution containing LiCl and phosphoric acid, and is treated.
Alternatively, the molar ratio of LiCl to phosphoric acid is (0.2-5): 1, a step of; preferably, the molar ratio of LiCl to phosphoric acid is (0.5-1.5): 1, a step of; more preferably, the molar ratio of LiCl to phosphoric acid is 1:1.
Alternatively, the total concentration of LiCl and phosphoric acid in the reaction solution is 0.2mol/L to 3mol/L; preferably, the total concentration of LiCl and phosphoric acid in the reaction solution is 1mol/L.
Optionally, the metallic nickel material is selected from any one of nickel mesh with mesh number of 20-1000 mesh, foam nickel with thickness of 0.1-0.5cm and nickel foil; preferably a nickel mesh with a mesh number of 20-1000 mesh.
Optionally, the conditions of the treatment are: the temperature is 90-200 ℃ and the time is 20-300min; preferably, the conditions of the treatment are: the temperature is 100-150 ℃ and the time is 100-150min; more preferably, the conditions of the treatment are: the temperature is 120 ℃ and the time is 120min.
In one embodiment, deposition growth regime I comprises:
and adopting an electrochemical deposition method, taking a conductive current collector as a carrier, and electrodepositing in a precursor aqueous solution I comprising a nickel source and a bismuth source to obtain the electrode in situ.
Alternatively, the electrodeposition mode is a two-electrode system or a three-electrode system.
Alternatively, the electrodeposition may employ any one or more of galvanostatic, potentiostatic, square wave pulse, cyclic voltammetry, or galvanostatic methods.
Optionally, the conditions of the electrodeposition are: the current density is-0.08 to-4A/cm 2 The electrodeposition time is 5-5000s or the voltage is-0.05 to-130V/cm 2 The electrodeposition time is 5-5000s.
Preferably, the current density is-0.08 to-2A/cm during electrodeposition 2 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the current density is-1.5A/cm at the time of electrodeposition 2 。
Alternatively, the current density is independently selected from-0.08A/cm upon electrodeposition 2 、-1A/cm 2 、-1.5A/cm 2 、-2A/cm 2 Either value or a range of both.
Preferably, the voltage is-0.05 to-5V/cm during electrodeposition 2 。
Alternatively, the voltage is independently selected from-0.05V/cm upon electrodeposition 2 、-1V/cm 2 、-2V/cm 2 、-5V/cm 2 Either value or a range of both.
Preferably, the electrodeposition time is 90-600s; more preferably, the electrodeposition time is 105s.
Alternatively, in electrodeposition, the electrodeposition time is independently selected from any one value or range of two values of 5s, 10s, 20s, 50s, 70s, 80s, 90s, 100s, 110s, 200s, 300s, 400s, 500s, 600s, 1000s, 2000s, 3000s, 4000s, 5000s.
In one embodiment, deposition growth regime ii comprises: and (3) taking reduced graphene oxide as a carrier, carrying out hydrothermal impregnation in a precursor aqueous solution II comprising a nickel source and a bismuth source to obtain a metal precursor, roasting to obtain a bismuth doped nickel (oxygen) hydroxide electrocatalyst, placing the electrocatalyst in an electric traction solution, and carrying out electric traction growth on a conductive current collector to obtain the electrode.
Optionally, the roasting temperature is 300-800 ℃; the roasting time is 0.5-10h; preferably, the firing temperature is 150 ℃; the roasting time is 2 hours.
Optionally, during the process of the electric traction growth, the concentration of the bismuth doped nickel (oxygen) hydroxide electrocatalyst in the electric traction solution is 0.1-0.8w/v; preferably, the concentration of bismuth doped nickel (oxy) hydroxide electrocatalyst in the electric traction solution is between 0.1 and 0.5w/v; more preferably, the concentration of bismuth doped nickel (oxy) hydroxide electrocatalyst in the electric traction solution is 0.2w/v.
Optionally, the concentration of the bismuth doped nickel (oxy) hydroxide electrocatalyst in the electric traction solution is at a value selected from any one of 0.1w/v, 0.2w/v, 0.34w/v, 0.5w/v, 0.8w/v, and ranges of both.
W/v in this application: the mass concentration w of the catalyst powder system per volume unit v in the electric traction fluid.
Optionally, the electric traction growth applies a voltage of-0.2 to-5V/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electric traction growth time is 60 s-3600 s.
Optionally, in the precursor aqueous solution I including a nickel source and a bismuth source and the precursor aqueous solution II including a nickel source and a bismuth source, each independently:
the nickel source and the bismuth source are selected from any one or more of acetylacetone salt, citrate, acetate, chloride, nitrate, sulfate and phosphate of corresponding metals.
Optionally, the total concentration of the metal source in the precursor aqueous solution I and the precursor aqueous solution II is independently 0.01-2mol/L, and the molar concentration ratio of the bismuth source to the nickel source is (0.01-0.2): 1.
preferably, the total concentration of the metal source in the precursor aqueous solution I and the precursor aqueous solution II is independently 1-2mol/L.
Preferably, the molar concentration ratio of bismuth source to nickel source is (0.01-0.1): 1, a step of; more preferably, the molar concentration ratio of bismuth source to nickel source is 0.05:1.
Optionally, the molar concentration ratio of bismuth source to nickel source is (0.01-0.1): 1.
alternatively, the molar ratio of bismuth source to nickel source is independently selected from 0.01: 1. values of any one of 0.05:1, 0.1:1, 0.2:1, and ranges of values for both.
Preferably, the aqueous precursor solution I and the aqueous precursor solution II further independently comprise a third component metal modifier.
Preferably, the third component metal modifier is selected from one or more of the Fe, co, W, mn, V, cr, sn, mo, ce, cu containing metal sources.
Preferably, the metal source is selected from any one or more of acetylacetonate, citrate, acetate, chloride, nitrate, sulfate, phosphate of the corresponding metal.
Optionally, the aqueous precursor solution I further comprises a base additive and/or a secondary electrolyte.
Optionally, the base additive is selected from any one or more of thiourea, urea, sodium ascorbate, PVP, P123.
Optionally, the concentration of the base additive in the aqueous electrodeposition precursor solution is 0-2mol/L.
Optionally, the concentration of the base additive in the aqueous electrodeposition precursor solution is 1-2mol/L.
Optionally, the auxiliary electrolyte is selected from any one or more of boric acid, acetic acid, ammonium chloride, lithium chloride, sodium chloride and sodium hypophosphite.
Optionally, the concentration of the auxiliary electrolyte in the aqueous electrodeposition precursor solution is 0-5mol/L.
Optionally, the concentration of the auxiliary electrolyte in the electrodeposition precursor aqueous solution is 1-5mol/L; the concentration of the auxiliary electrolyte in the electrodeposition precursor aqueous solution is 1-2mol/L.
The construction of the electrode is beneficial to improving the overall catalytic capacity of the catalyst, and meanwhile, the dispersity and the mass transfer characteristic of the electrode system can be improved, so that the catalytic performance is remarkably improved. This shows that in the bismuth doped nickel (oxy) hydroxide electrocatalyst material described in this application, there are regulatory and synergistic effects between the elemental compositions, which are important for improving the catalytic performance of the composite catalyst.
In addition, the nickel bismuth bimetallic (oxygen) hydroxide water oxidation electrocatalyst system is prepared by adopting a low-temperature wet chemical method-electrodeposition or hydrothermal-high-temperature roasting-electric traction growth method, has a self-supporting micro-nano cone array structure formed by secondary crosslinking and assembling of nano sheets, is favorable for mass transfer and bubble transmission, has good physical stability and structural stability, and shows excellent catalytic activity and stability in an electrocatalytic water oxidation reaction. It is worth mentioning that the Bi bimetallic catalyst dissolves out Bi species almost negligible during the catalytic water oxidation reaction, which is a significant advantage over typical NiFe systems.
The beneficial effects that this application can produce include:
(1) The electrode structure is a self-supporting micro-nano cone array structure formed by secondarily crosslinking and assembling nano sheets, and Bi 3+ Uniformly distributed to Ni (OH) x In the main structure, the catalyst system has high overall dispersity, large specific surface area, good conductivity and excellent charge transmission characteristic and stability. The excellent performance of a typical NiFe electrode is shown to be comparable when catalyzing alkaline water oxidation reactions.
Wherein, when the catalyst with the best activity is tested for oxygen evolution activity in a KOH solution with the concentration of 1mol/L, the current density is 100mA/cm 2 、500mA/cm 2 1000mA/cm 2 Only overpotential 248, 357 and 394mV are needed at that time (see fig. 6 in particular).
Under the working condition and operation condition, the catalyst can be used as a bifunctional catalyst to construct a full-water decomposition two-electrode system, and the current density is 10, 500 and 1000mA/cm 2 Only groove pressures of 1.48, 1.60 and 1.66V are required (see fig. 12 in particular).
Meanwhile, the catalyst has excellent long-term stability (example 11) and has a certain industrial application prospect. When a small amount of Fe is added into the catalyst system as a third component metal regulator, the performance of the catalyst system can be further improved, and the current density is 500mA/cm and 1000mA/cm 2 Only overpotential 290 and 325mV were needed (example 9).
(2) The bismuth doped nickel (oxygen) hydroxide water oxidation electrocatalyst is suitable for alkaline environments, the required raw materials are low in cost and easy to obtain, and the specific technical scheme has the advantage of rapid mass preparation and is good in industrial adaptability.
(3) The preparation method obtains the electrode system with high activity and high stability by modulating the components, concentration, reaction current, reaction temperature, reaction time and other parameters of the reaction solution, thereby meeting different requirements on catalytic performance.
Drawings
FIG. 1 is an XRD pattern of the samples prepared in examples 1-3;
FIGS. 2 (a) - (b) are high resolution XPS plots of Ni 2p and Bi 4f, respectively, for the samples prepared in examples 1-3;
FIGS. 3 (a) - (c) are HRTEM images of the samples prepared in examples 1, 2 and 3, respectively;
FIGS. 4 (a) - (d) are TEM (a-b) and SEM (c-d) images of samples prepared in examples 1-2, respectively;
FIGS. 5 (a) - (b) are graphs showing contact angle measurements of the samples prepared in examples 1-2, respectively;
FIG. 6 is a Linear Sweep Voltammetric (LSV) curve of the electrocatalyst prepared in examples 1-3 in a 1mol/L KOH solution;
FIG. 7 is a graph showing the activity data of the composite electrocatalyst according to example 6, wherein the proportions of Ni and Bi are different;
FIG. 8 is a graph of the activity data of the electrocatalyst obtained under different auxiliary additive conditions in example 7;
FIG. 9 is a graph of the activity data of the electrocatalyst obtained at various deposition times in example 8;
FIG. 10 is a diagram showing the result of Fe-NiBi (OH) obtained after adding the additive of the third metal component in example 9 x Activity data graph of samples;
FIG. 11 is a graph showing activity data of samples prepared by hydrothermal immersion-high temperature calcination-electric traction growth in example 10;
FIG. 12 (a) is Ni prepared in example 1 in example 11 97 Bi 3 (OH) x A Linear Sweep Voltammetry (LSV) curve of a two-electrode system constructed as a cathode and an anode under laboratory conditions (1 mol/L KOH, room temperature) and working conditions (30% KOH,80 ℃);
FIG. 12 (b) is a stability test chart of the two-electrode system in example 11.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain a required precursor which is named as E-Ni; thereafter, in a new electrodeposition precursor solution (the composition of the electrodeposition precursor solution is 0.95mol/L nickel sulfate+0.05 mol/L bismuth nitrate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea) with-1A/cm by adopting an electrochemical deposition manner and taking E-Ni as a conductive carrier and a catalyst carrier 2 In-situ to obtain NiBi-based (oxy) hydroxide water oxidation electrocatalyst electrode system, which was designated Ni based on actual metal component content measured by ICP 97 Bi 3 (OH) x 。
The catalytic system exhibited very excellent catalytic performance, as shown by the Linear Sweep Voltammetry (LSV) curve in fig. 6, with specific overpotential values listed in table 1. Wherein the test is performed in 1mol/L KOH solution and the test employs a three-electrode system: the conductive substrate loaded with the target catalyst is a working electrode; the carbon sheet is a counter electrode; the saturated calomel electrode is used as a reference electrode. The test used a sweep speed of 5mV/s.
FIG. 1 is an XRD pattern of the samples prepared in examples 1-3, showing that the oxygen evolution electrocatalyst prepared is less crystalline. Furthermore, the XRD spectrum peaks of example 1 have slightly lower angular offset compared to example 2, indicating successful incorporation of Bi into the Ni host.
FIGS. 2 (a) - (b) are high resolution XPS plots of Ni 2p and Bi 4f, respectively, for the samples prepared in examples 1-3. FIGS. 3 (a) - (c) are HRTEM diagrams of the samples prepared in examples 1, 2 and 3, respectively, wherein (a)
HRTEM images of samples prepared in example 2, (b) HRTEM images of samples prepared in example 1, and (c) HRTEM images of samples prepared in example 3.
XRD, XPS and HRTEM results indicate that the catalyst material obtained in example 1 has a predominant crystalline phase of 4Ni (OH) 2 -NiOOH and hexagonal nickel-based hydrotalcite structures. Bismuth (Bi) in Bi 3+ Is distributed in the nickel (oxy) hydroxide.
FIGS. 4 (a) - (d) are TEM (a-b) and SEM (c-d) images of the samples prepared in examples 1-2, respectively, wherein (a) is a TEM image of the sample prepared in example 2, (b) is a TEM image of the sample prepared in example 1, (c) is an SEM image of the sample prepared in example 2, and (d) is an SEM image of the sample prepared in example 1.
Fig. 5 (a) - (b) are respectively contact angle test patterns of the samples prepared in examples 1-2, wherein (a) the contact angle test pattern of the sample prepared in example 1 and (b) the contact angle test pattern of the sample prepared in example 2, and the results show that the introduction of Bi significantly improved the mass transfer characteristics of the water oxidation electrode.
SEM, TEM and contact angle test results show that the electrode structure obtained in the embodiment 1 is a micro-nano cone array structure formed by secondary crosslinking of small-size nano sheets, which is beneficial to mass transfer and bubble transmission.
Example 2
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain a required precursor which is named as E-Ni; thereafter, in an electrochemical deposition manner, E-Ni is used as a conductive carrier and a carrier of a catalyst in a newly prepared electrodeposition precursor solution (the composition of the electrodeposition precursor solution is 1mol/L nickel sulfate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea) at a concentration of-1A/cm 2 Is deposited 105s, in situ, to obtain an electrode system of the Ni-based mixed (oxy) hydroxide water oxidation electrocatalyst, which is denoted as Ni (OH) x 。
XRD, XPS and HRTEM results indicate the obtained Ni (OH) x The material is mainly 4Ni (OH) 2 NiOOH and mixed (oxy) hydroxides of hexagonal nickel-based hydrotalcite structure.
SEM, TEM and contact angle test results show that the obtained electrode structure is a three-dimensional structure formed by stacking nano sheets, and the mass transfer characteristic is required to be improved.
Example 3
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain a required precursor which is named as E-Ni; thereafter, in a new electrodeposition precursor solution (the composition of the electrodeposition precursor solution is 0.5mol/L bismuth nitrate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea) with E-Ni as a conductive carrier and a catalyst carrier by adopting an electrochemical deposition manner, the composition of the electrodeposition precursor solution is-1A/cm 2 Is in situ obtained for a Bi (oxy) hydroxide water oxidation electrocatalyst electrode system, designated Bi (OH) x 。
XRD and HRTEM results indicate the obtained Bi (OH) x The catalyst material mainly consists of metal Bi, bi (OH) 3 BiO (BiO) 2.33 The composition is formed.
Wherein the overpotential of the catalysts described in examples 1-3 is shown in table 1, the advantages of the nimi composite catalyst system are demonstrated.
Table 1: oxygen evolution peroxypotential meter of the catalyst systems described in examples 1-3
From the above table, it can be seen that the bismuth doped nickel (oxy) hydroxide catalyst systems developed in the present application exhibit very excellent water oxidation properties, whereas metal (oxy) hydroxide catalyst systems containing only Ni and Bi exhibit poor catalytic activity. These results indicate that there is a significant synergistic effect between the Ni and Bi metals in the catalyst system, and the coexistence of both can greatly improve the catalytic performance of the catalyst; in addition, the doping of Bi can improve the dispersity and mass transfer characteristic of the electrode system, thereby obviously improving the catalytic performance.
Example 4
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain an E-Ni precursor;thereafter, E-Ni is used as a conductive carrier and a catalyst carrier in an electrochemical deposition manner, and the composition of the electrodeposition precursor solution is 0.95mol/L nickel sulfate+0.05 mol/L bismuth nitrate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea in a newly prepared electrodeposition precursor solution of-2A/cm 2 Is deposited for 90s to obtain NiBi-based water oxidation electrocatalyst NiBi (OH) in situ x An electrode system.
Example 5
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain an E-Ni precursor; afterwards, an electrochemical deposition mode is adopted, E-Ni is used as a conductive carrier and a catalyst carrier, and an operating voltage of minus 2V is applied to a newly prepared electrodeposition precursor solution (the components of the electrodeposition precursor solution are 0.95mol/L nickel sulfate, 0.05mol/L bismuth nitrate, 0.4mol/L boric acid, 0.28mol/L ammonium chloride, 1mol/L thiourea and 1mol/L urea) for deposition for 600 seconds, so that the NiBi-based water oxidation electrocatalyst NiBi (OH) is obtained in situ x An electrode system.
Example 6
This example illustrates an example of the control of the proportion of metal components produced by a Bi-doped nickel (oxy) hydroxide oxygen evolution electrocatalyst system:
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain an E-Ni precursor; and then, taking E-Ni as a conductive carrier and a carrier of a catalyst, controlling 1mol/L nickel sulfate, 0.4mol/L boric acid, 0.28mol/L ammonium chloride, 1mol/L thiourea and 1mol/L urea in the electrodeposited precursor solution to be unchanged, changing the content of bismuth nitrate, and enabling the atomic ratio of metal components in the electrodeposited precursor solution to be 0.5 at%, 1 at%, 2 at%, 5 at%, 10 at%, 20 at%, 50 at%, and-1A/cm 2 In situ to obtain a series of water oxidation electrocatalyst electrode systems NiBi (OH) having different NiBi ratios x . The corresponding activity data for catalysts with different metal component content are shown in figure 7.
Analysis shows that the metal component proportion of the catalyst is closely related to the water oxidation performance of the catalyst, and the too low or too high Bi content is unfavorable for improving the catalytic performance of the catalyst.
Example 7
This example illustrates a control example of an auxiliary additive prepared by a nickel (oxy) hydroxide electrocatalytic system:
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain an E-Ni precursor; thereafter, using E-Ni as a conductive carrier and a catalyst carrier, controlling 1mol/L nickel sulfate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride in the electrodeposited precursor solution to remain unchanged, and adding 1mol/L thiourea, 1mol/L urea, 1mol/L sodium hypophosphite, any two of the three auxiliary additives, and-1A/cm 2 Is deposited 105s, in situ, to obtain a series of water oxidation electrocatalysts Ni (OH) with different auxiliary additives x The corresponding activity data of the obtained catalyst are shown in fig. 8.
Example 8
This example illustrates an example of control of deposition time for the preparation of Bi-doped Ni-based electrocatalyst system:
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain a required precursor which is named as E-Ni; thereafter, in a new electrodeposition precursor solution (the composition of the electrodeposition precursor solution is 0.95mol/L nickel sulfate+0.05 mol/L bismuth nitrate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea) with-1A/cm by adopting an electrochemical deposition manner and taking E-Ni as a conductive carrier and a catalyst carrier 2 Respectively depositing 75, 90, 105, 120, 135 and 150s, and obtaining a series of NiBi-based water oxidation electrocatalyst electrode systems with different deposition times in situ. The corresponding activity data for the catalysts obtained at different deposition times are shown in figure 9.
Example 9
This example illustrates an example of the addition of a modifier for a third metal component prepared by a Bi-doped nickel-based electrocatalysis system:
60mL (the rest is water) of a reaction solution consisting of LiCl and phosphoric acid in a molar ratio of 1:1 (wherein the LiCl is used in an amount of 2.54g and the phosphoric acid is used in an amount of 4.1 mL) is adopted, and a 40-mesh metal nickel screen is treated for 2 hours at 120 ℃ to obtain a required precursor which is named as E-Ni; thereafter, E-Ni is used as a conductive carrier and a catalyst carrier in an electrochemical deposition manner, and the composition of the electrodeposition precursor solution is 0.95mol/L nickel sulfate+0.05 mol/L bismuth nitrate+0.05 mol/L ferrous sulfate+0.4 mol/L boric acid+0.28 mol/L ammonium chloride+1 mol/L thiourea+1 mol/L urea in a newly prepared electrodeposition precursor solution of-1A/cm 2 The current density deposition of 120s, in situ, resulted in a Fe modified NiBi electrode system, the performance data of which are shown in fig. 10.
Example 10
This example illustrates a Bi-doped nickel (oxy) hydroxide oxygen evolution electrocatalytic system prepared by hydrothermal preparation-high temperature reduction:
the method comprises the steps of adopting hydrothermal preparation, high-temperature reduction and electric traction growth, taking reduced graphene oxide as a carrier, and carrying out hydrothermal soaking for 2 hours at 150 ℃ in a precursor solution containing a nickel source and a bismuth source in a proportion of 9:1 (wherein the nickel source is nickel sulfate, the adding amount is 0.2mol/L, and the bismuth source is bismuth nitrate), so as to obtain a dipping metal precursor. And washing and drying the obtained precursor, and roasting at 600 ℃ for 2 hours to obtain the bismuth doped nickel (oxygen) hydroxide powder catalyst. The resulting powdered catalyst was placed in an electric traction solution containing a 1M urea+1M sodium ascorbate solution, wherein the concentration of the catalyst powder was 0.1, 0.2, 0.34 and 0.5w/v (w/v: the mass concentration w of powdered catalyst per volume unit v in the electric traction solution), respectively. Under the action of electrostatic adsorption, voltage of-5V is applied to the nickel current collector for electric traction growth for 90s to obtain a series of NiBi catalysts, and the performance data graph of the series of NiBi catalysts is shown in FIG. 11.
Example 11
This example illustrates the water electrolysis performance of a Bi-doped nickel (oxy) hydroxide oxygen evolution electrocatalyst assembled two electrode system under laboratory conditions and operating conditions.
Ni was prepared as in example 1 97 Bi 3 (OH) x Catalyst system as cathode for electrolysis of waterAnd the anode and the cathode are constructed to obtain a two-electrode water decomposition system, and the electrolysis water performance of the system is tested under laboratory conditions (1 mol/L KOH,25 ℃) and working condition running conditions (30% KOH,80 ℃), respectively. The two-electrode system exhibited excellent water splitting properties, as shown by the Linear Sweep Voltammetry (LSV) curve in FIG. 12a, with a current density of 100mA/cm under laboratory conditions 2 And 500mA/cm 2 When the groove pressure is required to be 1.65V and 1.79V, under the working condition, 100mA/cm and 500mA/cm can be obtained under the groove pressure of 1.52V and 1.60V 2 Is used for the current density of the battery. At the same time, the two-electrode system is at 500mA/cm 2 The electrolysis time at a current density of about 500h still maintains its water splitting properties as shown in FIG. 12 b.
The application provides a bismuth doped nickel (oxygen) hydroxide electrocatalyst electrode for electrocatalytic water oxidation and a preparation method thereof. The bismuth doped nickel (oxygen) hydroxide electrocatalyst is prepared by a low-temperature wet chemical method-electrodeposition or a hydrothermal-high-temperature roasting-electric traction growth method. Wherein, the metal Bi in the NiBi electrocatalyst is Bi 3+ In the form of 0.1% -10% of the metal component, ni being Ni 2+ And Ni 3+ In a mixed form, the total proportion of which is 90% to 99.9%. The prepared electrode system is a self-supporting micro-nano cone array structure formed by secondarily crosslinking and assembling nano sheets through Bi, the three-dimensional structure has excellent mass transfer and bubble transmission characteristics and good physical stability and structural stability, the catalytic activity of the electrode system is comparable with that of a nickel molten iron oxidation catalyst in an electrocatalytic water oxidation reaction, meanwhile, the nickel-bismuth catalyst system has more excellent stability, and the bismuth species can be dissolved out almost negligible in a long-time catalysis process, so that the electrode system has obvious advantages compared with a typical nickel-iron system, and has an industrial application foundation.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. An electrode for electrocatalytic water oxidation, characterized in that the electrode comprises a bismuth doped nickel (oxy) hydroxide electrocatalyst and an electrically conductive current collector;
the bismuth doped nickel (oxy) hydroxide electrocatalyst comprises nickel-based hydroxide and nickel-based oxide;
the nickel-based hydroxide and the nickel-based oxide are doped with bismuth;
wherein bismuth is Bi 3+ In the form of nickel (oxy) hydroxide, nickel being present as Ni 2+ And Ni 3+ Is present in the nickel (oxy) hydroxide;
the bismuth doped nickel (oxy) hydroxide electrocatalyst is deposited on a conductive current collector;
the electrode is in a self-supporting micro-nano cone array structure.
2. The electrode for electrocatalytic water oxidation according to claim 1, wherein the crystalline phase of the bismuth doped nickel (oxy) hydroxide electrocatalyst comprises 4Ni (OH) 2 -NiOOH and hexagonal nickel-based hydrotalcite structure;
preferably, the self-supporting micro-nano cone array structure is formed by secondarily crosslinking and assembling bismuth-doped nickel (oxygen) hydroxide electrocatalyst nano sheets.
3. The electrode for electrocatalytic water oxidation according to claim 1, wherein bismuth comprises 0.1at.% to 20at.% of the total metal content;
preferably, bismuth comprises 0.1at.% to 10at.% of the total metal content.
4. The electrode for electrocatalytic water oxidation according to claim 1, wherein the bismuth doped nickel (oxy) hydroxide electrocatalyst is further modified with a third metal modifier;
the third metal modifier is a metal-containing component other than bismuth and nickel;
preferably, the non-bismuth and nickel containing metal-containing component is selected from any one or more of the Fe, co, W, mn, V, cr, sn, mo, ce, cu containing components;
preferably, the conductive current collector is a nickel-based current collector.
5. A method of preparing an electrode for electrocatalytic water oxidation according to any one of claims 1-4, comprising: depositing and growing a bismuth doped nickel (oxygen) hydroxide electrocatalyst on the conductive current collector to obtain an electrode;
the deposition growth mode is deposition growth mode I and/or deposition growth mode II;
the deposition growth mode I sequentially comprises a low-temperature wet chemical method operation and an electrochemical deposition growth operation;
the deposition growth mode II sequentially comprises a hydrothermal operation, a high-temperature roasting operation and an electric traction growth operation;
preferably, before deposition growth, a process of treating the conductive current collector is included, the process including:
immersing a metallic nickel material in a reaction solution containing LiCl and phosphoric acid, and treating;
the conditions of the treatment include: the temperature is 90-200 ℃ and the time is 20-300min;
preferably, the conditions of the treatment include: the temperature is 100-150deg.C, and the time is 100-150min.
6. The method of preparing an electrode for electrocatalytic water oxidation according to claim 5, wherein the deposition growth regime i comprises:
adopting an electrochemical deposition method, taking a conductive current collector as a carrier, and electrodepositing in a precursor aqueous solution I comprising a nickel source and a bismuth source to obtain an electrode in situ;
preferably, the electrodeposition mode is a two-electrode system or a three-electrode system;
preferably, the electrodeposition is performed by any one or more of a constant current method, a constant potential method, a square wave pulse method, a cyclic voltammetry method and a constant electric quantity method;
preferably, the conditions of the electrodeposition are: the current density is-0.08 to-4A/cm 2 The electrodeposition time is 5-5000s or the voltage is-0.05 to-130V/cm 2 The electrodeposition time is 5-5000s;
preferably, the current density is-0.08 to-2A/cm during electrodeposition 2 ；
Preferably, the electrodeposition time is 90-600s.
7. The method of preparing an electrode for electrocatalytic water oxidation according to claim 5, wherein the deposition growth regime ii comprises: and (3) taking reduced graphene oxide as a carrier, carrying out hydrothermal impregnation in a precursor aqueous solution II comprising a nickel source and a bismuth source to obtain a metal precursor, roasting to obtain a bismuth doped nickel (oxygen) hydroxide electrocatalyst, placing the electrocatalyst in an electric traction solution, and carrying out electric traction growth on a conductive current collector to obtain the electrode.
8. The method for preparing an electrode for electrocatalytic water oxidation according to claim 7, wherein the firing temperature is 300-800 ℃; the roasting time is 0.5-10h;
preferably, the concentration of the bismuth doped nickel (oxygen) hydroxide electrocatalyst in the electrotraction solution during the electrotraction growth is between 0.1 and 0.8w/v;
preferably, the concentration of bismuth doped nickel (oxy) hydroxide electrocatalyst in the electric traction solution is between 0.1 and 0.5w/v;
preferably, the electric traction growth applies a voltage of-0.2 to-5V/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electric traction growth time is 60 s-3600 s.
9. The method for preparing an electrode for electrocatalytic water oxidation according to claim 6 or 7, wherein in the precursor aqueous solution I including a nickel source, a bismuth source and the precursor aqueous solution II including a nickel source, a bismuth source, each independently:
the nickel source and the bismuth source are selected from any one or more of acetylacetone salts, citrate salts, acetate salts, chloride salts, nitrate salts, sulfate salts and phosphate salts of corresponding metals;
preferably, the total concentration of the metal source in the precursor aqueous solution I and the precursor aqueous solution II is independently 0.01-2mol/L, and the molar concentration ratio of the bismuth source to the nickel source is (0.01-0.2): 1, a step of;
preferably, the molar concentration ratio of bismuth source to nickel source is (0.01-0.1): 1, a step of;
preferably, the aqueous precursor solution I and the aqueous precursor solution II further independently comprise a third component metal modifier;
preferably, the third component metal modifier is selected from one or more of the Fe, co, W, mn, V, cr, sn, mo, ce, cu containing metal sources;
preferably, the metal source is selected from any one or more of acetylacetonate, citrate, acetate, chloride, nitrate, sulfate, phosphate of the corresponding metal.
10. The method for the preparation of an electrode for electrocatalytic water oxidation according to claim 6, wherein the aqueous precursor solution I further comprises a base additive and/or a secondary electrolyte;
preferably, the base additive is selected from any one or more of thiourea, urea, sodium ascorbate, PVP, P123;
preferably, the concentration of the basic additive in the electrodeposition precursor aqueous solution is 0-2mol/L, and the concentration does not include 0;
preferably, the auxiliary electrolyte is selected from any one or more of boric acid, acetic acid, ammonium chloride, lithium chloride, sodium chloride and sodium hypophosphite;
preferably, the concentration of the auxiliary electrolyte in the electrodeposition precursor aqueous solution is 0-5mol/L, and the concentration does not include 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311211000.1A CN117468035A (en) | 2023-09-19 | 2023-09-19 | Electrode for electrocatalytic water oxidation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311211000.1A CN117468035A (en) | 2023-09-19 | 2023-09-19 | Electrode for electrocatalytic water oxidation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117468035A true CN117468035A (en) | 2024-01-30 |
Family
ID=89632070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311211000.1A Pending CN117468035A (en) | 2023-09-19 | 2023-09-19 | Electrode for electrocatalytic water oxidation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117468035A (en) |
-
2023
- 2023-09-19 CN CN202311211000.1A patent/CN117468035A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109201060B (en) | Preparation method of foamed nickel-nickel iron oxide composite oxygen evolution catalyst | |
| CN111001427B (en) | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof | |
| CN112133932A (en) | Three-metal-based Ni-Co-Zn-N Co-doped porous carbon catalyst and preparation method and application thereof | |
| CN106967997B (en) | A kind of efficient self-supporting catalysis electrode and its preparation method and application | |
| CN110484934B (en) | Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN109277104B (en) | Sulfur-rich vanadium-modified NiS2Electrocatalyst and method of making | |
| CN111933961B (en) | Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof | |
| CN113512737B (en) | Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof | |
| CN109898097A (en) | Monatomic iron-the carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method and applications | |
| CN111701607A (en) | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof | |
| CN111001414A (en) | Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof | |
| CN115692746A (en) | Method for preparing ORR and OER dual-function catalyst by one-step deposition | |
| CN113529120B (en) | Transition metal sulfide composite electrode, preparation method and application thereof | |
| CN111640953A (en) | Air electrode catalyst of aluminum-air battery and preparation method thereof | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN114300276B (en) | Ni-Fe-S@NiCo 2 O 4 Nano-NF composite material and preparation method and application thereof | |
| CN117468035A (en) | Electrode for electrocatalytic water oxidation and preparation method thereof | |
| CN110797206A (en) | Co-Mn-S composite material and preparation method and application thereof | |
| US20240117512A1 (en) | Water electrolysis catalyst with core-shell structure and method for preparing same | |
| CN113089019B (en) | Preparation method of high-efficiency catalyst Ni/Fe/Cr-based composite material for oxygen evolution reaction | |
| KR102586625B1 (en) | Anode for alkaline water electrolysis and method for manufacturing the same | |
| CN117026257B (en) | Preparation method of zinc-nitrate radical battery based on high-entropy oxide | |
| CN115224293B (en) | ORR and OER dual-function catalyst and preparation method and application thereof | |
| CN116613330A (en) | Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof |
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 |