CN115710712A - Modification method of electrolytic water catalyst - Google Patents
Modification method of electrolytic water catalyst Download PDFInfo
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- CN115710712A CN115710712A CN202211435175.6A CN202211435175A CN115710712A CN 115710712 A CN115710712 A CN 115710712A CN 202211435175 A CN202211435175 A CN 202211435175A CN 115710712 A CN115710712 A CN 115710712A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002715 modification method Methods 0.000 title claims abstract description 21
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 abstract description 40
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 37
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 37
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 20
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 53
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 150000002815 nickel Chemical class 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 21
- 150000002471 indium Chemical class 0.000 claims description 18
- 159000000003 magnesium salts Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- -1 siCl 4 Chemical compound 0.000 claims description 5
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical group O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910018916 CoOOH Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YLZGECKKLOSBPL-UHFFFAOYSA-N indium nickel Chemical compound [Ni].[In] YLZGECKKLOSBPL-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to a modification method of an electrolyzed water catalyst. A modification method of an electrolytic water catalyst comprises the following steps: and (2) putting the metal oxyhydroxide or the hydrotalcite into a cyclohexane solution, uniformly stirring, dropwise adding silicon tetrachloride, stirring at room temperature for 22-26h, drying and grinding. According to the modification method of the electrolytic water catalyst, silicon tetrachloride is added into hydrotalcite, so that the morphology of the electrolytic water catalyst can be regulated, the surface active sites of the electrolytic water catalyst are increased, and the electrocatalytic activity can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a modification method of an electrolyzed water catalyst.
Background
Energy is an important foundation for the survival and development of human society, and is an important guarantee for the development of modern industry and economy. However, with the rapid growth of the world population and the rapid development of the global economy, the energy demand is increasing, and the use of traditional energy resources such as coal, oil, natural gas and the like will face serious environmental pollution and ecological damage. Therefore, there is an urgent need to develop an alternative clean energy source which is pollution-free, carbon-free and continuously renewable, and hydrogen energy becomes an excellent fossil energy source substitute due to its high calorific value, pollution-free and other characteristics.
The preparation of hydrogen energy has a plurality of ways, wherein the hydrogen production by electrocatalysis water decomposition is an important hydrogen production means at present because the technology is mature, the equipment is simple, no pollution is caused, the purity of the obtained hydrogen is high, the impurity content is low, and the hydrogen is suitable for various occasions. Common water electrolysis catalysts include hydrotalcite materials, metal oxyhydroxides, and the like.
However, pure hydrotalcite materials and metal oxyhydroxides have poor performance, and in recent years, some researchers have generally modified hydrotalcite and metal oxyhydroxides to improve their catalytic activity, for example, by means of forming vacancies, defects, ion doping, and the like.
In view of the above, the invention provides a novel method for modifying an electrolytic water catalyst, which comprises adding silicon tetrachloride into hydrotalcite and a metal oxyhydroxide, and utilizing the reaction of the silicon tetrachloride with the hydrotalcite and the metal oxyhydroxide to generate hydrochloric acid to etch the surface of the catalyst, so as to increase the surface active sites of the catalyst, thereby facilitating the catalytic activity of the catalyst in the electrocatalytic decomposition of water.
Disclosure of Invention
The invention aims to provide a modification method of an electrolyzed water catalyst, silicon tetrachloride is added into the electrolyzed water catalyst to perform peeling modification on the catalyst, the modified catalyst has a large number of surface active sites, and the preparation process is simple and clear.
In order to realize the purpose, the adopted technical scheme is as follows:
a modification method of an electrolytic water catalyst comprises the following steps: and (2) putting the metal oxyhydroxide or the hydrotalcite into a cyclohexane solution, uniformly stirring, then dropwise adding silicon tetrachloride, stirring at room temperature for 22-26h, drying and grinding.
Further, the metal oxyhydroxide or hydrotalcite, siCl 4 、C 6 H 12 The mass ratio of (1): 12-18:50-70.
Still further, the metal oxyhydroxide or hydrotalcite, siCl 4 、C 6 H 12 The mass ratio of (1): 15:60.
further, the preparation method of the hydrotalcite comprises the following steps: under the stirring of 75-85 ℃, formamide solution and sodium hydroxide solution are simultaneously dripped into the metal salt solution until the pH of the solution is 9-10, the solution is cooled to room temperature after reaction, and hydrotalcite is obtained after centrifugal washing, drying and grinding; the metal salt solution contains two of nickel salt, indium salt and magnesium salt;
the preparation method of the metal oxyhydroxide comprises the following steps: under the stirring of 75-85 ℃, formamide solution and sodium hydroxide solution are simultaneously dripped into metal salt solution containing cobalt salt and sylvite until the pH of the solution is 9-10, the solution is cooled to room temperature after reaction, and then the metal hydroxide is obtained after centrifugal washing, drying and grinding.
Further, the nickel salt is nickel nitrate hexahydrate, the indium salt is indium nitrate hydrate, and the magnesium salt is magnesium nitrate;
the cobalt salt is cobalt chloride, and the potassium salt is potassium persulfate.
Still further, in the preparation method of hydrotalcite, the metal salt solution contains nickel salt and indium salt, and the molar weight ratio of nickel salt to indium salt is 2.5-3.5:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 45-55:1;
the molar weight ratio of the cobalt salt to the potassium salt is 15-25.
Still further, in the preparation method of hydrotalcite, the metal salt solution contains nickel salt and indium salt, and the molar weight ratio of nickel salt to indium salt is 3:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 40:1;
the molar weight ratio of the cobalt salt to the potassium salt is 20.
Further, the stirring temperature is 80 ℃;
the volume fraction of the formamide solution is 20-26%;
the centrifugal washing was performed using a mixture of ethanol and water mixed at a volume ratio of 2.
Still further, the formamide solution has a volume fraction of 23%.
The invention also aims to provide a modified hydrotalcite electrocatalyst prepared by the preparation method, and the catalyst has a large number of surface active sites and excellent electrocatalytic performance.
Compared with the prior art, the invention has the advantages that:
1. from the raw material aspect, the silicon tetrachloride belongs to an industrial byproduct, and improper treatment can cause certain harm to the surrounding environment and the health. According to the invention, silicon tetrachloride is added into the electrolyzed water catalyst, so that waste utilization is realized while the electrolyzed water catalyst is modified.
2. The invention relates to a new morphology regulation method for an electrolytic water catalyst, which secondarily applies a silicon tetrachloride industrial byproduct to a technology for preparing new energy, and carries out means for cleaning raw materials and the technology in front and at back, and the obtained catalyst has excellent electrocatalysis performance.
Drawings
FIG. 1 is the LSV curve of the HER of NiIn-LDH and Si-NiIn-LDH tested in example 2;
FIG. 2 is the LSV curve for the OER of the NiIn-LDH and Si-NiIn-LDH tested in example 2;
FIG. 3 is a graph of the total hydrolysis of NiIn-LDH versus Si-NiIn-LDH tested in example 2.
Detailed Description
In order to further illustrate the method for modifying an electrolyzed water catalyst of the present invention to achieve the desired objects, the following embodiments are provided to describe the method for modifying an electrolyzed water catalyst according to the present invention, and the specific implementation, structure, features and effects thereof. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The method for modifying an electrolytic water catalyst according to the present invention will be described in further detail with reference to the following specific examples:
the invention provides a modification method of an electrolyzed water catalyst. The modification method comprises the following steps: putting an aqueous solution containing two metal salts into a beaker, and simultaneously dropwise adding a formamide solution and a sodium hydroxide solution under magnetic stirring at 80 ℃, and keeping the pH of the solution at 9-10. And after the reaction, cooling the solution to room temperature, washing, centrifuging, drying and grinding the solution to obtain an electrolyzed water catalyst, then putting the electrolyzed water catalyst into a cyclohexane solution, magnetically stirring for 20min, slowly dripping silicon tetrachloride into a beaker, sealing the opening of the beaker by using a safety film, stirring for 24h at room temperature, and then drying and grinding to obtain the silicon-doped electrolyzed water catalyst. The technical scheme of the invention is as follows:
a modification method of an electrolytic water catalyst comprises the following steps: and (2) putting the metal oxyhydroxide or the hydrotalcite into a cyclohexane solution, uniformly stirring, dropwise adding silicon tetrachloride, stirring at room temperature for 22-26h, drying and grinding.
Preferably, the metal oxyhydroxide or hydrotalcite, siCl 4 、C 6 H 12 The mass ratio of (1): 12-18:50-70.
More preferably, the metal oxyhydroxide, hydrotalcite or SiCl is 4 、C 6 H 12 The mass ratio of (1): 15:60.
preferably, the preparation method of the hydrotalcite comprises the following steps: under the stirring of 75-85 ℃, formamide solution and sodium hydroxide solution are simultaneously dripped into the metal salt solution until the pH of the solution is 9-10, the solution is cooled to room temperature after reaction, and hydrotalcite is obtained after centrifugal washing, drying and grinding; the metal salt solution contains two of nickel salt, indium salt and magnesium salt;
the preparation method of the metal oxyhydroxide comprises the following steps: under the stirring of 75-85 ℃, formamide solution and sodium hydroxide solution are simultaneously dripped into metal salt solution containing cobalt salt and sylvite until the pH of the solution is 9-10, the solution is cooled to room temperature after reaction, and then the metal hydroxide is obtained after centrifugal washing, drying and grinding.
The formamide is utilized to obtain a single-layer electrolyzed water catalyst, which is more beneficial to the subsequent modification treatment of the silicon tetrachloride.
Further preferably, the nickel salt is nickel nitrate hexahydrate, the indium salt is indium nitrate hydrate, and the magnesium salt is magnesium nitrate;
the cobalt salt is cobalt chloride, and the potassium salt is potassium persulfate.
Further preferably, in the method for preparing hydrotalcite, the metal salt solution contains nickel salt and indium salt, and the molar ratio of nickel salt to indium salt is 2.5-3.5:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 45-55:1;
the molar weight ratio of the cobalt salt to the potassium salt is 15-25.
Further preferably, in the method for preparing hydrotalcite, the metal salt solution contains a nickel salt and an indium salt, and the molar ratio of the nickel salt to the indium salt is 3:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 40:1;
the molar weight ratio of the cobalt salt to the potassium salt is 20.
Further preferably, the stirring temperature is 80 ℃;
the volume fraction of the formamide solution is 20-26%;
the centrifugal washing was performed using a mixture of ethanol and water mixed at a volume ratio of 2.
Further preferably, the formamide solution has a volume fraction of 23%.
The principle of the invention is as follows: the silicon tetrachloride reacts with hydroxyl in the water electrolysis catalyst to realize targeted and fixed-point doping, and the formed Si-O-Me bond can promote the generation of an intermediate and reduce the adsorption energy of adsorption functional molecules; and meanwhile, the hydrotalcite is sheared (immediately etched), so that the specific surface area of the hydrotalcite is enlarged, more active sites are obtained, and hydrogen production by water electrolysis is facilitated.
Example 1:
(1) Preparation of NiIn-LDH:
under magnetic stirring at 80 deg.C, the alloy will contain 75mmol of Ni (NO) 3 ) 2 ·6H 2 O and 25mmol of In Ni (NO) 3 ) 3 ·H 2 O, dissolved in 10mL of an aqueous solution, was added dropwise to 20mL of a formamide solution (23 vol%) (monolayer nickel indium hydrotalcite was obtained using formamide). Simultaneously, 0.25mol of sodium hydroxide was added dropwise to the solution to bring the pH to 9-10. The reaction was completed within 10 min. After cooling to room temperature, the product was collected by centrifugation, washed several times with a mixture of ethanol and water (volume 2.
(2) Preparation of Si-nin-LDH catalyst:
NiIn-LDH (0.2 g) prepared as described above was placed in a 50mL beaker, and a predetermined amount of cyclohexane (15.4 mL) was added thereto and stirred for 20min. Then 2mL of silicon tetrachloride solution was added dropwise to the mixture, the beaker mouth was closed with a safety film and stirred at room temperature for 24h. Finally, the solid was dried at 80 ℃ for 12h. And finely grinding the obtained solid, sealing and bottling to obtain the Si-NiIn-LDH electrocatalyst.
Example 2: evaluation of electrocatalytic performance of catalyst Si-NiIn-LDH
The catalyst prepared in example 1 was used for electrolytic water reaction, and the prepared catalyst was coated on a washed nickel mesh (1 x 1 cm) 2 ) In the above, the working electrode, the silver chloride electrode and the platinum sheet electrode are combined into a three-electrode system, and the reaction is performed in 1M potassium hydroxide electrolyte, and the results of the electrochemical test are shown in fig. 1.
FIGS. 1-3 are graphs of the performance of NiIn-LDH versus Si-NiIn-LDH, 1 (a) the LSV curve for HER, 2 (b) the LSV curve for OER, and 3 (c) the total hydrolysis curve. As can be seen from the figure, the performance of the hydrotalcite catalyst modified by the silicon tetrachloride is obviously better than that of the unmodified hydrotalcite catalyst.
Example 3.
(1) Preparation of NiIn-LDH:
under magnetic stirring at 85 ℃, the solution containing 75mmol of Ni (C)NO 3 ) 2 ·6H 2 O and 35mmol of In Ni (NO) 3 ) 3 ·H 2 O, dissolved in 20mL of an aqueous solution, was added dropwise to 20mL of a formamide solution (26 vol%). Simultaneously, 0.25mol of sodium hydroxide was added dropwise to the solution to bring the pH to 9-10. The reaction was completed within 10 min. After cooling to room temperature, the product was collected by centrifugation, washed several times with a mixture of ethanol and water (volume 2.
(2) Preparation of Si-nin-LDH catalyst:
NiIn-LDH (0.2 g) prepared as described above was placed in a 50mL beaker, and a predetermined amount of cyclohexane (17.7 mL) was added and stirred for 20min. Then 2.4mL of silicon tetrachloride solution was added dropwise to the mixture, the beaker mouth was closed with a safety film and stirred at room temperature for 26h. Finally, the solid was dried at 80 ℃ for 12h. The solid obtained is finely ground, sealed and bottled.
Example 4.
(1) Preparation of NiIn-LDH:
under magnetic stirring at 75 ℃, 70mmol of Ni (NO) is added 3 ) 2 ·6H 2 O and 20mmol of In Ni (NO) 3 ) 3 ·H 2 O, dissolved in 20mL of an aqueous solution, was added dropwise to 20mL of a formamide solution (20 vol%). Simultaneously, 0.25mol of sodium hydroxide was added dropwise to the solution to bring the pH to 9-10. The reaction was completed within 10 min. After cooling to room temperature, the product was collected by centrifugation, washed several times with a mixture of ethanol and water (volume 2.
(2) Preparation of Si-nin-LDH catalyst:
NiIn-LDH (0.2 g) prepared as described above was placed in a 50mL beaker, and a predetermined amount of cyclohexane (12.7 mL) was added and stirred for 20min. Then 1.62mL of silicon tetrachloride solution was added dropwise to the mixture, the beaker mouth was closed with a safety film and stirred at room temperature for 22h. Finally, the solid was dried at 80 ℃ for 12h. The solid obtained is finely ground, sealed and bottled.
Example 5:
(1) Preparation of NiMg-LDH: mixing Ni (NO) 3 ) 2 ·6H 2 O(1.454g，5mmol)、Mg(NO 3 ) 2 ·6H 2 O (25.6 mg, 0.1mmol) and 2-methylimidazole (0.411g, 5 mmol) were added to methanol (15 mL) in this order and vigorously stirred to form a homogeneous solution in a 20mL Teflon stainless steel autoclave. The resulting mixture was heated at 80 ℃ for 4h. The final light green product was collected by centrifugation, washed three times with methanol and dried in a vacuum oven at 80 ℃ for 6h to give NiMg-LDH.
(2) Preparation of Si-NiMg-LDH catalyst: niMg-LDH (0.2 g) prepared above was placed in a 50mL beaker. A certain mass of cyclohexane (15.4 mL) was added thereto and stirred for 20min. Then, an appropriate amount of silicon tetrachloride solution was added dropwise to the mixture, and the beaker mouth was closed with a safety film and stirred at room temperature for 24 hours. Finally, the solid was dried at 80 ℃ for 12h. The solid obtained is finely ground, sealed and bottled.
Example 6.
The procedure of example 6 is the same as example 5, except that: ni (NO) 3 ) 2 ·6H 2 O(1.309g，4.5mmol)、Mg(NO 3 ) 2 ·6H 2 O(25.6mg，0.1mmol)。
Example 7.
The procedure of example 7 is the same as example 5, except that: ni (NO) 3 ) 2 ·6H 2 O(1.599g，5.5mmol)、Mg(NO 3 ) 2 ·6H 2 O(25.6mg，0.1mmol)。
Example 8:
(1) Preparation of CoOOH spheres: a typical method is as follows: the metal salt was dissolved in deionized water (40 mL) to prepare a solution containing cobalt chloride (20 mmol) and K 2 S 2 O 8 (270.3mg, 1mmol) in water. After sonication, the vial (50 mL) was placed in a sealed blue-capped vial (100 mL) and 2mL of concentrated ammonium hydroxide solution was added. After diffusion at room temperature for 12h, centrifugation with deionized water (9000 rmin) -1 5 min) 2 washes and dries at room temperature.
(2) Preparation of Si-CoOOH catalyst: coOOH spheres (0.2 g) prepared as described above were placed in a 50mL beaker. A certain mass of cyclohexane (15.4 mL) was added thereto and stirred for 20min. Then, an appropriate amount of silicon tetrachloride solution was added dropwise to the mixture, and the beaker mouth was closed with a safety film and stirred at room temperature for 24 hours. Finally, the solid was dried at 80 ℃ for 12h. The solid obtained is finely ground, sealed and bottled.
Example 9.
The procedure of example 9 is the same as that of example 8 except that: cobalt chloride (15 mmol) and K 2 S 2 O 8 (1mmol)。
Example 10.
The procedure of example 10 is the same as example 8 except that: cobalt chloride (25 mmol) and K 2 S 2 O 8 (1mmol)。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A modification method of an electrolyzed water catalyst is characterized by comprising the following steps: and (2) putting the metal oxyhydroxide or the hydrotalcite into a cyclohexane solution, uniformly stirring, dropwise adding silicon tetrachloride, stirring at room temperature for 22-26h, drying and grinding.
2. The modification method according to claim 1,
the metal oxyhydroxide or hydrotalcite, siCl 4 、C 6 H 12 The mass ratio of (1): 12-18:50-70.
3. The modification method according to claim 2,
the metal oxyhydroxide or hydrotalcite, siCl 4 、C 6 H 12 The mass ratio of (1): 15:60.
4. the modification method according to claim 1,
the preparation method of the hydrotalcite comprises the following steps: under the stirring of 75-85 ℃, formamide solution and sodium hydroxide solution are simultaneously dripped into the metal salt solution until the pH of the solution is 9-10, the solution is cooled to room temperature after reaction, and hydrotalcite is obtained after centrifugal washing, drying and grinding; the metal salt solution contains two of nickel salt, indium salt and magnesium salt;
the preparation method of the metal oxyhydroxide comprises the following steps: under the stirring of 75-85 ℃, simultaneously dripping formamide solution and sodium hydroxide solution into metal salt solution containing cobalt salt and potassium salt until the pH of the solution is 9-10, cooling to room temperature after reaction, centrifugally washing, drying and grinding to obtain the metal oxyhydroxide.
5. The modification method according to claim 4,
the nickel salt is nickel nitrate hexahydrate, the indium salt is indium nitrate hydrate, and the magnesium salt is magnesium nitrate;
the cobalt salt is cobalt chloride, and the potassium salt is potassium persulfate.
6. The modification method according to claim 1,
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and indium salt, and the molar weight ratio of the nickel salt to the indium salt is 2.5-3.5:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 45-55:1;
the molar weight ratio of the cobalt salt to the potassium salt is 15-25.
7. The modification method according to claim 6,
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and indium salt, and the molar weight ratio of the nickel salt to the indium salt is 3:1;
in the preparation method of the hydrotalcite, the metal salt solution contains nickel salt and magnesium salt, and the molar weight ratio of the nickel salt to the magnesium salt is 40:1;
the molar weight ratio of the cobalt salt to the potassium salt is 20.
8. The modification method according to claim 4,
the stirring temperature is 80 ℃;
the volume fraction of the formamide solution is 20-26%;
the centrifugal washing was performed using a mixture of ethanol and water mixed at a volume ratio of 2.
9. The modification method according to claim 8,
the formamide solution has a volume fraction of 23%.
10. An electrolyzed water catalyst, characterized by being prepared by the modification method according to any one of claims 1 to 9.
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