CN113249747A - Chemical plating method for preparing metal sulfide by efficiently electrolyzing water to prepare hydrogen - Google Patents
Chemical plating method for preparing metal sulfide by efficiently electrolyzing water to prepare hydrogen Download PDFInfo
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- CN113249747A CN113249747A CN202110386911.2A CN202110386911A CN113249747A CN 113249747 A CN113249747 A CN 113249747A CN 202110386911 A CN202110386911 A CN 202110386911A CN 113249747 A CN113249747 A CN 113249747A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
Abstract
The invention discloses a chemical plating method for preparing a metal sulfide by efficiently electrolyzing water to produce hydrogen, which comprises the following steps: the electrochemical electrode sulfur-based material with good catalytic activity, greenness and low price is prepared by a mild and simple chemical plating method, and the application of the electrochemical electrode sulfur-based material in the hydrogen production by water electrolysis is realized. The invention overcomes the defect that the traditional high-temperature and high-pressure hydrothermal method is used for preparing the sulfur-based catalytic material, and adopts a one-step chemical plating method to prepare the catalytic electrode of the univalent metal sulfide, the binary metal sulfide and the multivariate metal sulfide with good hydrogen evolution function on different substrates (paper sheets, carbon cloth, sponge, titanium sheets, foamed nickel and the like). According to the invention, the catalytic electrode material has good catalytic hydrogen production effect, low overpotential of reaction, high stability and low requirements on environment and equipment in the preparation and test processes.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of a chemical plating method for realizing efficient water electrolysis hydrogen production by metal sulfides.
Background
The hydrogen as a clean, pollution-free and efficient renewable energy source provides great possibility for replacing the traditional fossil energy source in the future, has high heat value, and the combustion product of the hydrogen is water, so that the hydrogen has no pollution to the environment and can be continuously recycled and regenerated. The industrial preparation of hydrogen usually adopts the methods of chlor-alkali industry, coal and heavy oil cracking, two-stage conversion of natural gas and the like, but the purity of the hydrogen prepared by the methods is relatively low, and the other method for preparing high-purity hydrogen is hydrogen production by water electrolysis. Water electrolysis is a technology widely applied in the fields of sewage treatment, hydrogen production, oxygen production, seawater desalination and the like, and plays an important role in modern industrial production. The sewage treatment plays a key role in constructing a good ecological environment, the seawater desalination has important significance in treating and utilizing a large amount of seawater, and the hydrogen production by electrolyzing water is one of industrial technologies for preparing high-purity hydrogen, so that the method has a wide application prospect in the aspect of producing green clean hydrogen energy.
The process of electrolyzing water needs electrolyte, ion exchange membrane, anode reaction electrode and cathode reaction electrode. Under the standard state, the theoretical voltage value required for electrolyzing water is 1.23V, however, due to the polarization phenomenon of the electrode surface, the actual voltage value applied is far higher than the theoretical voltage value, and the part higher than the theoretical voltage value is called overpotential, and the overpotential increases the energy consumption during water electrolysis, thus causing unnecessary energy waste. According to estimation, the energy value of hundreds of millions of yuan RMB can be saved every year when the actual voltage of the water electrolysis hydrogen production equipment used in China is reduced by 250 mV. The electrochemical overpotential relates to a plurality of steps in the reaction process, and needs higher activation energy to break through higher energy barriers to promote the reaction to occur, so that energy is wasted.
At present, materials for preparing catalytic electrodes can be roughly divided into three types, the first type is a catalyst represented by noble metals such as platinum, iridium, ruthenium and the like, and has excellent catalytic performance, but the catalyst has higher cost and limited storage capacity and is difficult to be applied in a large scale; the second category is catalytic materials represented by transition metals such as nickel, iron, cobalt, manganese and the like, which are cheap and easy to prepare, but have low overall catalytic performance; the third type is a composite electrode using nonmetal and transition metal as catalytic materials, and the nonmetal is represented by elements such as sulfur, phosphorus, boron and the like, and the composite electrode has the characteristics of low cost, strong operability, good catalytic performance and the like. The Chinese invention patent 201810963621.8 relates to the preparation of a transition metal sulfide composite nano material, and the method adopts a step-by-step hydrothermal method to prepare NiCo2S by taking nickel nitrate hexahydrate, ZIF-67, thioacetamide, sodium molybdate and the like as precursor materials4@MoS2The nano material has the advantages of good core-shell structure, high specific surface area and the like, and shows good pseudo-capacitance characteristics and cycle stability in a voltage range of 0-0.5V when being used as an electrode material of a super capacitor. The Chinese patent 201811193515.2 relates to the preparation of a nano transition metal boride catalytic material, which is prepared by a solid phase replacement method and calcining. The Chinese invention patent 201310320738.1 uses cheap raw materials and a simple preparation method, takes nickel as a matrix, and prepares Ni/Ni by sulfurizing metallic nickel through hydrothermal reaction (temperature 140-3S2/Ni(OH)2A composite electrode that achieves high current density at ultra-low electrolyzed water overpotentials. Through literature study and experimental research, it can be found that the metal sulfide has good catalytic activity, electrochemical activity and higher conductivity, and is applied to the fields of hydrogen production by water electrolysis, supercapacitors, batteries and the likeThe method usually needs certain pressure equipment and specific temperature input (100-.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the chemical plating method for realizing the efficient hydrogen production by electrolyzing water by using the metal sulfide, the catalytic electrode material has good catalytic hydrogen production effect, the overpotential of the reaction is low, the stability is high, and the requirements of the preparation and test processes on the environment and equipment are low. To achieve the above objects and other advantages in accordance with the present invention, there is provided a method for preparing a metal sulfide by electroless plating for efficient hydrogen production by electrolysis of water, comprising the steps of:
s1, pretreatment of the substrate material: soaking a substrate material in an acid solution, sequentially cleaning the substrate material with deionized water and ethanol to remove surface impurities, activating the substrate material with a metal salt solution and a borohydride solution, putting the substrate material into a constant-temperature drying box, and drying the substrate material for later use;
s2, preparing a metal sulfide chemical plating solution: mixing and dissolving a metal salt compound precursor, a reducing agent, a buffering agent and a complexing agent in proportion into deionized water to obtain a chemical plating solution;
s3, chemical plating: and (4) putting the pretreated substrate material in the step S1 into the chemical plating solution in the step S2, taking out the substrate material after chemical plating reaction, washing with deionized water and ethanol, and drying to obtain the catalytic electrode loaded with the metal sulfide.
Preferably, the substrate material in step S1 includes paper sheet, titanium sheet, foamed nickel, carbon cloth, and sponge.
Preferably, the salt solution for activation in step S1 includes nickel sulfate, cobalt sulfate, ammonium ferrous sulfate, and copper sulfate, and the borohydride solution includes sodium borohydride, amine borane, potassium borohydride, or an amine borane compound.
Preferably, the acid in the acidic solution in step S1 includes hydrochloric acid, oxalic acid, sulfuric acid or nitric acid, the volume concentration of the acid is 2-20%, the temperature of the acid solution is 15-40 ℃, and the treatment time is 1-10 min.
Preferably, in step S2, the metal salt includes bismuth nitrate, cobalt sulfate, nickel sulfate, ammonium ferrous sulfate or copper sulfate, and the concentration is 0.01-1M, and the reducing agent includes sodium thiosulfate, thiourea or thioacetamide, and the concentration is 0.01-2M.
Preferably, the complexing agent in step S2 is a compound capable of complexing with a metal salt, and the compound includes ammonia, amine, sodium citrate, sodium acetate, sodium lactate, and sodium malonate; buffers include sodium acetate, boric acid, ammonium chloride or sodium sulfate.
Preferably, the electroless plating reaction temperature in the step S3 is 10-80 ℃, and the reaction time is 0.5-24 h.
Compared with the prior art, the invention has the beneficial effects that: the metal sulfide conductive material has good catalytic activity, conductivity and chemical stability, the bonding process of the metal sulfide material and the substrate material is simple, the bonding is firm, the service life is long, the metal sulfide conductive material is green, energy-saving and environment-friendly, and compared with the existing metal sulfide electrode, the metal sulfide conductive material can be prepared by a chemical plating method under mild and simple conditions. The metal sulfide catalytic material prepared by the method has wide application prospect in the water electrolysis process of hydrogen evolution industry, sewage treatment, chlor-alkali industry and large-scale industry.
Drawings
FIG. 1 is an SEM image of a Ni-S @ paper catalytic electrode for a chemical plating process for efficient hydrogen production by electrolysis of water using metal sulfides in accordance with the present invention;
FIG. 2 is a diagram showing the hydrogen evolution reaction performance of the Ni-S @ paper catalytic electrode for electrolyzing water according to the chemical plating method for efficiently electrolyzing water to produce hydrogen by using metal sulfides of the present invention;
FIG. 3 is a photo (a) and a hydrogen evolution reaction performance (b) of a Co-S @ paper catalytic electrode prepared by the electroless plating method for efficiently electrolyzing water to produce hydrogen by using metal sulfide according to the present invention;
FIG. 4 is a photograph (a) and a hydrogen evolution reaction performance diagram (b) of a Co-S @ chlorine catalytic electrode prepared by the electroless plating method for efficiently electrolyzing water to produce hydrogen by using metal sulfide according to the present invention;
FIG. 5 is a photo (a) and a hydrogen evolution reaction performance (b) of a Ni-Co-S @ Ni foam catalytic electrode prepared by the electroless plating method for efficiently electrolyzing water to produce hydrogen by using metal sulfide according to the present invention;
FIG. 6 is a schematic diagram of a large area of a Ni-S/Paper catalytic electrode of the electroless plating method for efficiently electrolyzing water to produce hydrogen by using metal sulfide according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-6, a preparation method of an electroless plating method for realizing efficient water electrolysis hydrogen production by metal sulfide comprises the following steps: s1, pretreatment of the substrate material: soaking a substrate material in an acid solution, sequentially cleaning the substrate material with deionized water and ethanol to remove surface impurities, activating the substrate material with a metal salt solution and a borohydride solution, putting the substrate material into a constant-temperature drying box, and drying the substrate material for later use;
s2, preparing a metal sulfide chemical plating solution: mixing and dissolving a metal salt compound precursor, a reducing agent, a buffering agent and a complexing agent in proportion into deionized water to obtain a chemical plating solution;
s3, chemical plating: and (4) putting the pretreated substrate material in the step S1 into the chemical plating solution in the step S2, taking out the substrate material after chemical plating reaction, washing with deionized water and ethanol, and drying to obtain the catalytic electrode loaded with the metal sulfide.
Further, the substrate material in the step S1 includes paper, titanium sheet, foamed nickel, carbon cloth, and sponge.
Further, the salt solution for activation in step S1 includes nickel sulfate, cobalt sulfate, ammonium ferrous sulfate, and copper sulfate, and the borohydride solution includes sodium borohydride, amine borane, potassium borohydride, or an amine borane compound.
Further, the acid in the acidic solution in the step S1 includes hydrochloric acid, oxalic acid, sulfuric acid or nitric acid, the volume concentration of the acid is 2-20%, the temperature of the acid solution is 15-40 ℃, and the treatment time is 1-10 min.
Further, in the step S2, the metal salt includes bismuth nitrate, cobalt sulfate, nickel sulfate, ammonium ferrous sulfate or copper sulfate, and the concentration is 0.01-1M, and the reducing agent includes sodium thiosulfate, thiourea or thioacetamide, and the concentration is 0.01-2M.
Further, the preparation method of the electroless plating method for realizing efficient hydrogen production by electrolyzing water with metal sulfide as claimed in claim 1, wherein the complexing agent in the step S2 is a compound capable of coordinating with metal salt, the compound includes ammonia, amine, sodium citrate, sodium acetate, sodium lactate and sodium malonate; buffers include sodium acetate, boric acid, ammonium chloride or sodium sulfate.
Further, in the step S3, the electroless plating reaction temperature is 10-80 ℃, and the reaction time is 0.5-24 h.
EXAMPLE preparation of Ni-S @ paper catalytic electrode Material
(1) Paper sheet base material pretreatment:
soaking a paper sheet substrate material in a dilute nitric acid solution, sequentially washing with deionized water and ethanol for 3 times to remove impurities such as surface oxides, and rapidly (2s) activating the paper sheet by using a 0.2M nickel sulfate solution and a sodium borohydride solution to excite a growth site of the substrate material for later use;
(2) preparing the chemical plating solution containing Ni-S, wherein the amount ratio and the experimental conditions of each substance are shown in the following table:
immersing the pretreated paper substrate into the solution, and performing chemical deposition for 1-6h at 50 ℃; catalytic electrode materials with different deposition thicknesses can be obtained, and the catalytic electrode materials are alternately washed for 3 times by deionized water and ethanol and dried to obtain the electrode. The electrode photographs and SEM images and element distributions are shown in FIG. 1;
(3) testing the electrochemical hydrogen evolution performance;
the electrochemical test adopts a three-electrode system, a carbon rod electrode is taken as a counter electrode, a saturated mercury chloride electrode is taken as a reference electrode, a prepared Ni-S @ paper electrode is taken as a working electrode, and a 1M KOH solution is taken as an electrolyte solution. Hydrogen Evolution Reaction (HER) performance tests were performed in a laboratory environment at 25 ℃ using an electrochemical workstation (CHI760E) as the detection device. The test results for this material and the activated paper sheet are shown in figure 2.
EXAMPLE preparation of Co-S @ paper catalytic electrode Material
(1) Paper sheet base material pretreatment:
soaking a paper sheet substrate material in a dilute nitric acid solution, sequentially washing with deionized water and ethanol for 3 times to remove impurities such as surface grease, oxides and the like, carrying out (2s) activation operation on the substrate material by using a 0.2M nickel sulfate solution and a sodium borohydride solution, exciting growth sites of the substrate material, and drying for later use;
(2) preparing a chemical plating solution containing Co-S, wherein the quantity ratio and the experimental conditions of each substance are shown in the following table:
immersing the pretreated paper substrate into the solution, and performing chemical deposition for 3 hours at 50 ℃; the catalytic electrode material with deposition thickness can be obtained, and the electrode is prepared by alternately washing with deionized water and ethanol for 3 times and drying. The electrode photograph and SEM image are shown in FIG. 3 (a);
(3) testing the electrochemical hydrogen evolution performance;
the electrochemical test adopts a three-electrode system, a carbon rod electrode is taken as a counter electrode, a saturated mercury chloride electrode is taken as a reference electrode, a prepared Co-S @ paper electrode is taken as a working electrode, and a 1M KOH solution is taken as an electrolyte solution. Hydrogen Evolution Reaction (HER) performance tests were performed in a laboratory environment at 25 ℃ using an electrochemical workstation (CHI760E) as the detection device. The test results for this material and the activated paper sheet are shown in FIG. 3 (b).
EXAMPLE preparation of a Co-S/cloth catalyzed electrode Material
(1) Pretreating a carbon cloth substrate material:
soaking a carbon cloth substrate material in a dilute nitric acid solution, sequentially cleaning with deionized water and ethanol for 3 times to remove impurities such as surface grease, oxides and the like, alternately using a 0.2M nickel sulfate solution and a sodium borohydride solution to activate the substrate material, exciting growth sites of the substrate material, and drying for later use;
(2) preparing a chemical plating solution containing Co-S, wherein the quantity ratio and the experimental conditions of each substance are shown in the following table:
immersing the pretreated paper substrate into the solution, and performing chemical deposition for 3 hours at 50 ℃; the catalytic electrode material with deposition thickness can be obtained, and the electrode is prepared by alternately washing with deionized water and ethanol for 3 times and drying. The electrode photograph and SEM image are shown in FIG. 4 (a);
(3) testing the electrochemical hydrogen evolution performance;
the electrochemical test adopts a three-electrode system, a carbon rod electrode is taken as a counter electrode, a saturated mercury chloride electrode is taken as a reference electrode, the prepared Co-S @ cloth electrode is taken as a working electrode, and a 1M KOH solution is taken as an electrolyte solution. Hydrogen Evolution Reaction (HER) performance tests were performed in a laboratory environment at 25 ℃ using an electrochemical workstation (CHI760E) as the detection device. The test results of the material and the activated carbon cloth are shown in fig. 4 (b).
EXAMPLE preparation of a TetraNi-Co-S @ Ni foam catalytic electrode Material
(1) Pretreating a foam nickel substrate material:
soaking a Ni foam substrate material in a dilute nitric acid solution, sequentially cleaning the substrate material with deionized water and ethanol for 3 times to remove impurities such as surface grease, oxides and the like, alternately using a 0.2M nickel sulfate solution and a sodium borohydride solution to activate the substrate material, exciting growth sites of the substrate material, cleaning the substrate material with the deionized water and the ethanol for 3 times, then placing the substrate material into a constant-temperature drying box at 50 ℃ for 5min, and drying the substrate material for later use;
(2) preparing a chemical plating solution containing Ni-Co-S, wherein the quantity ratio and the experimental conditions of each substance are shown in the following table:
immersing the pretreated Ni foam substrate into the solution, and performing chemical deposition for 3h at 50 ℃; and (3) obtaining a catalytic electrode material with deposition thickness, alternately washing with deionized water and ethanol for 3 times, and drying to obtain the electrode. The electrode photograph and SEM image are shown in FIG. 5 (a);
(3) testing the electrochemical hydrogen evolution performance;
the electrochemical test adopts a three-electrode system, a carbon rod electrode is taken as a counter electrode, a saturated mercury chloride electrode is taken as a reference electrode, a prepared Ni-Co-S @ Ni foam electrode is taken as a working electrode, and a 1M KOH solution is taken as an electrolyte solution. Hydrogen Evolution Reaction (HER) performance tests were performed in a laboratory environment at 25 ℃ using an electrochemical workstation (CHI760E) as the detection device. The test results for this material and the activated paper sheet are shown in FIG. 5 (b).
The number of devices and the scale of the processes described herein are intended to simplify the description of the invention, and applications, modifications and variations of the invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (7)
1. A preparation method of a chemical plating method for realizing efficient water electrolysis hydrogen production by metal sulfide is characterized by comprising the following steps:
s1, pretreatment of the substrate material: soaking a substrate material in an acid solution, sequentially cleaning the substrate material with deionized water and ethanol to remove surface impurities, activating the substrate material with a metal salt solution and a borohydride solution, putting the substrate material into a constant-temperature drying box, and drying the substrate material for later use;
s2, preparing a metal sulfide chemical plating solution: mixing and dissolving a metal salt compound precursor, a reducing agent, a buffering agent and a complexing agent in proportion into deionized water to obtain a chemical plating solution;
s3, chemical plating: and (4) putting the pretreated substrate material in the step S1 into the chemical plating solution in the step S2, taking out the substrate material after chemical plating reaction, washing with deionized water and ethanol, and drying to obtain the catalytic electrode loaded with the metal sulfide.
2. The preparation method of claim 1, wherein the substrate material in step S1 comprises paper, titanium, nickel foam, carbon cloth, and sponge.
3. The preparation method of claim 1, wherein the salt solution for activation in step S1 comprises nickel sulfate, cobalt sulfate, ferrous ammonium sulfate, and copper sulfate, and the borohydride solution comprises sodium borohydride, amine borane, potassium borohydride, or an amine borane compound.
4. The preparation method of claim 1, wherein the acid in the acidic solution in step S1 comprises hydrochloric acid, oxalic acid, sulfuric acid or nitric acid, the volume concentration of the acid is 2-20%, the temperature of the acid solution is 15-40 ℃, and the treatment time is 1-10 min.
5. The preparation method of claim 1, wherein in step S2, the metal salt comprises bismuth nitrate, cobalt sulfate, nickel sulfate, ferrous ammonium sulfate or copper sulfate, and the concentration is 0.01-1M, and the reducing agent comprises sodium thiosulfate, thiourea or thioacetamide, and the concentration is 0.01-2M.
6. The preparation method of claim 1, wherein the complexing agent in step S2 is a compound capable of coordinating with a metal salt, the compound comprising ammonia, an amine, sodium citrate, sodium acetate, sodium lactate, and sodium malonate; buffers include sodium acetate, boric acid, ammonium chloride or sodium sulfate.
7. The preparation method of claim 1, wherein the electroless plating reaction temperature in step S3 is 10-80 ℃ and the reaction time is 0.5-24 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113638005A (en) * | 2021-08-20 | 2021-11-12 | 中国科学院过程工程研究所 | Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst |
| CN113684493A (en) * | 2021-08-20 | 2021-11-23 | 中国科学院过程工程研究所 | Method for preparing efficient electrolytic water hydrogen evolution catalyst by chemical plating method |
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| CN111809196A (en) * | 2020-06-23 | 2020-10-23 | 复旦大学 | Hollow foam autocatalytic electrode and preparation method thereof |
| CN113832491A (en) * | 2021-09-26 | 2021-12-24 | 上海理工大学 | Preparation method capable of realizing bismuth-boron-based flexible catalytic electrode in organic phase |
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| CN107988617A (en) * | 2017-11-24 | 2018-05-04 | 复旦大学 | Water electrolysis efficiently, double-function catalyzing electrode and preparation method thereof |
| CN111809196A (en) * | 2020-06-23 | 2020-10-23 | 复旦大学 | Hollow foam autocatalytic electrode and preparation method thereof |
| CN113832491A (en) * | 2021-09-26 | 2021-12-24 | 上海理工大学 | Preparation method capable of realizing bismuth-boron-based flexible catalytic electrode in organic phase |
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| CN113638005A (en) * | 2021-08-20 | 2021-11-12 | 中国科学院过程工程研究所 | Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst |
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