CN114196983B - Preparation method of metal hydroxide composite electrocatalyst and product thereof - Google Patents

Preparation method of metal hydroxide composite electrocatalyst and product thereof Download PDF

Info

Publication number
CN114196983B
CN114196983B CN202111522301.7A CN202111522301A CN114196983B CN 114196983 B CN114196983 B CN 114196983B CN 202111522301 A CN202111522301 A CN 202111522301A CN 114196983 B CN114196983 B CN 114196983B
Authority
CN
China
Prior art keywords
conductive substrate
metal hydroxide
solution
composite electrocatalyst
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111522301.7A
Other languages
Chinese (zh)
Other versions
CN114196983A (en
Inventor
田忠良
李铮
周言根
程皓
郭春
汪滔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202111522301.7A priority Critical patent/CN114196983B/en
Publication of CN114196983A publication Critical patent/CN114196983A/en
Application granted granted Critical
Publication of CN114196983B publication Critical patent/CN114196983B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a metal hydroxide composite electrocatalyst and a product thereof, comprising the following steps: 1) At least one of metal salt A, metal salt B and metal salt C is placed in a solvent according to a set proportion, and is stirred and dissolved to obtain solution D; 2) Pretreating a conductive substrate Y, placing the pretreated conductive substrate Y into a solution D, adsorbing at a set temperature, and performing vacuum drying after the adsorption is finished to obtain a precursor; 3) And (3) placing the precursor into an alkaline solution for soaking, and obtaining the metal hydroxide composite electrocatalyst after the soaking is finished. The composite electrocatalyst provided by the invention has a nano porous structure, is rich in defects, large in specific surface area and good in conductivity, and has excellent charge transmission characteristics and stability. The current density of the catalyst with the best activity is 10mAcm under the conventional condition ‑2 Only 180mV overpotential was needed, and the system remained stable after 900h of reaction.

Description

Preparation method of metal hydroxide composite electrocatalyst and product thereof
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a metal hydroxide composite electrocatalyst and a product thereof.
Background
The development of renewable clean energy is receiving increasing attention due to the increasing exhaustion of fossil energy. However, after clean energy such as solar energy, water energy, wind energy and the like is vigorously developed, the instability of energy output and the storage and transportation become new problems. The water is electrochemically decomposedAn effective way to transfer unstable energy and produce sustainable high-efficiency hydrogen energy. Electrolytic water reactions include anodic Oxygen Evolution (OER) and cathodic Hydrogen Evolution (HER). The theoretical driving voltage of electrolyzed water is 1.23V, but the complex electron transfer mechanism and slow kinetics during the reaction increase the start-up energy threshold, thus requiring a higher overpotential. At present, noble metal materials with best performance, such as IrO for OER 2 And RuO (Ruo) 2 And Pt for HER, its scarcity and high price limit its widespread use. The high-efficiency and stable non-noble metal-based catalyst is a feasible catalyst for reducing cost and process complexity, and the difunctional monolithic water-splitting electrocatalyst is a better choice. While alkaline solutions are often used as ideal electrolytes due to their good stability to metal-based catalysts. Thus, there is a need to explore electrocatalysts with higher electrocatalytic activity towards OER and HER in alkaline electrolytes.
Metal hydroxides have attracted considerable attention from researchers because of their relatively high hydrogen/oxygen evolution properties and low cost. However, the metal hydroxide still has the disadvantages of lower activity and lower stability compared with the noble metal catalyst. So researchers prepare single/multi-metal hydroxides with high catalytic activity of hydrogen/oxygen evolution by electrolysis through the combination of various transition metal elements such as Co, mo, fe and the like. Meanwhile, nanometer metal-based metal hydroxide catalyst materials are prepared by different methods, such as an atomic deposition method, an electrochemical deposition method, a sol-gel method and the like. Li et al synthesized MoO as reported in the literature 3 Ni-NiO/CC catalyst, (adv. Mater.2020, 2003414). NiFe LDH-rGO was synthesized in two steps by Pang et al and used as an electrocatalyst for OER under alkaline conditions (J.Power Sources 2016,33,53-60). Although the preparation method has a great progress in hydrogen evolution/oxygen electrocatalytic activity, the preparation method still has the defects of complex process, high toxicity, easy residue and the like of the used medicaments, and is difficult to realize large-scale industrial production, or additives and conductive agents are required to be used in the preparation process, so that the binding force of the catalyst and a collective is reduced, and the stability of the catalyst is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a metal hydroxide composite electrocatalyst used in hydrogen/oxygen production reaction in a water decomposition process, which can be simply prepared in a large scale, and a product thereof; the preparation method adopts an in-situ growth mode, and the metal hydroxide is assembled on the conductive substrate material in a strong alkali solution to obtain the composite electrocatalyst with excellent activity and stability; the composite electrocatalyst prepared by the method has a porous structure, the catalyst active substance and the conductive matrix are tightly combined, and the mechanical stability is high.
The preparation method of the metal hydroxide composite electrocatalyst comprises the following steps:
1) At least one of metal salt A, metal salt B and metal salt C is placed in a solvent according to a set proportion, and is stirred and dissolved to obtain solution D;
2) Pretreating a conductive substrate Y, placing the pretreated conductive substrate Y into the solution D in the step 1), adsorbing at a set temperature, and performing vacuum drying after the adsorption is finished, so as to obtain a precursor;
3) And (3) placing the precursor in the step (2) into an alkaline solution for soaking, and obtaining the metal hydroxide composite electrocatalyst after the soaking is finished.
In the step 1), the metal salt A is at least one of acetylacetonate, citrate, acetate, chloride, nitrate, sulfate or phosphate corresponding to each element of iron, nickel, cobalt and manganese; the metal salt B is at least one of acetylacetone salt, citrate, acetate, chloride, nitrate, sulfate or phosphate corresponding to each element in vanadium, chromium, copper and zinc; the metal salt C is at least one of acetylacetone salt, citrate, acetate, chloride, nitrate, sulfate or phosphate corresponding to each element in ruthenium, gold, platinum and iridium; the mass setting ratio of the mixture of the metal salt A, the metal salt B and the metal salt C is (5-10): 0-4): 0-3.
Preferably, the metal salt A, the metal salt B and the metal salt C are one of chloride salt or nitrate.
In the step 1), the solvent is at least one of methanol, ethanol, glycol, isopropanol, N-dimethylformamide, carbon tetrachloride, dimethyl sulfoxide and deionized water, and different metal salts are selected to be suitable solvents, so that the dispersibility of the conductive substrate Y is improved; the temperature is 20-80 ℃ and the rotating speed is 10-1000 rpm during stirring; in the solution D, the total concentration of the metal salt is 0.5-20 mol/L.
In the step 2), the conductive substrate Y is one of foam metal, carbon paper and carbon cloth, and the foam metal is one of foam nickel, copper, titanium and iron; the thickness of the foam metal is 1.0-4.0 mm, and the porosity is 20-99%; the thickness of the carbon cloth is 0.1-0.3 mm, and the tensile strength is more than 4000Mpa; the thickness of the carbon paper is 0.1-0.3 mm, and the porosity is 20-99%; the high-porosity material with a certain thickness can effectively adsorb the reaction substances and improve the load of the active substances. If the thickness is too thin, the supporting performance of the material is reduced, and the material cannot be used as an electrode; if the thickness is too thick, the adsorption effect is affected, and the active substances are unevenly dispersed. The pretreatment of the conductive substrate Y comprises the following specific steps: conducting substrate Y was ultrasonically cleaned with 1mol/L hydrochloric acid solution to ph=7 (the concentration of hydrochloric acid used did not react with the substrate in order to remove surface oxides), and then placed at a temperature of 60-80 ℃ and 10% -2 ～10 -6 Drying for 6-24 h under Pa vacuum condition; the conductive substrate subjected to pretreatment cleaning is beneficial to removing greasy dirt and oxide on the surface.
In the step 2), 100-50000 uL of solution D is required to be added to each square centimeter of conductive substrate Y; setting the temperature to be 25-120 ℃, wherein the adsorption mode is one of standing adsorption, ultrasonic adsorption and suction filtration adsorption, and the reasonable adsorption mode can increase the load of the metal hydroxide on the conductive substrate Y, and the adsorption time is 30-600 min; the vacuum drying conditions are as follows: vacuum degree of 10 -2 ～10 -6 Pa, and drying time is 6-24 h.
In the step 3), the concentration of the alkaline solution is 1-10 mol/L, and the strong base is KOH, naOH, liOH and Ca (OH) 2 At least one of the solutions, preferably at least one of KOH and NaOH solution, the concentration is 1-4 mol/L, the reaction is smoothly carried out due to the too low concentration of alkali liquor, and the concentration is highToo high a degree causes serious agglomeration of materials; the soaking time is 1-3600 min, preferably 20-40 min.
The metal hydroxide composite electrocatalyst is prepared according to the preparation method.
The metal hydroxide composite electrocatalyst comprises a conductive substrate and metal hydroxide growing on the conductive substrate Y, wherein the structural general formula of the metal hydroxide composite electrocatalyst is M (OH) x Y, 1.ltoreq.x.ltoreq.5, Y representing the conductive substrate Y, M representing the metal, said M (OH) x At least one of nano-sheet, nano-wire, nano-rod or nano-cluster, the thickness is 10-100 nm, and the specific surface area is 150-250 cm 3 g -1 。
The invention has the beneficial effects that:
(1) The composite electrocatalyst provided by the invention has a nano porous structure, is rich in defects, large in specific surface area and good in conductivity, and has excellent charge transmission characteristics and stability. Shows excellent activity and stability when electrocatalytic water decomposition. Wherein the catalyst with the best activity is 1mol L -1 At room temperature, the current density was 10mAcm -2 Only 180mV overpotential was needed and the system remained stable after 900 hours of reaction.
(2) The preparation method disclosed by the invention is simple to operate, the required raw materials are cheap and easy to obtain, the preparation method has the advantages of rapid mass preparation, the industrial adaptability is good, the high catalytic activity of the metal hydroxide can be ensured, and the conductive substrate provides a good conductive network, so that the catalyst shows excellent conductivity, electron transmission characteristic and stability
(3) According to the preparation method, the electrode system with high activity and high stability is obtained by modulating the components, concentration, reaction temperature, reaction time and other parameters of the metal salt, so that different requirements on catalytic performance are met. Meanwhile, the in-situ preparation method is favorable for the tight combination between the catalyst and the conductive carrier, thereby improving the charge transmission characteristic and the mechanical stability of the catalyst and having higher industrial application prospect.
Drawings
FIG. 1 is an SEM image of an iron nickel hydroxide/carbon cloth of example 1 of the invention;
FIG. 2 is a graph showing the LSV of the oxygen evolution reaction of examples 1-3 of the present invention;
FIG. 3 is a Tafil curve of examples 1-3 of the present invention;
FIG. 4 is a graph showing the stability test of examples 1 to 3 of the present invention;
FIG. 5 shows the LSV curves of comparative examples 1 and 2 of the present invention
Detailed Description
Further description will be made by way of example for the purpose of more clearly illustrating the present invention. The following examples do not limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The oxygen precipitation activity test conditions used in the invention are: at 1.0mol L -1 KOH is used as electrolyte for oxygen precipitation, a three-electrode system is tested, a platinum sheet is used as a counter electrode, the purity is higher than 99.99%, saturated Ag/AgCl is used as a reference electrode, and a testing instrument is an electrochemical workstation of Gamry company in America. All the test voltage values are converted into voltage values for standard hydrogen electrodes
Example 1
Step (1): 500mg of ferric nitrate is weighed and dissolved in 10ml of ethanol solution, and the solution is fully dissolved by mechanical stirring at 200r/min to obtain solution D.
Step (2): cutting carbon cloth with thickness of 0.167mm and tensile strength of more than 4000MPa into 4X 3cm 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum conditions to obtain the treated carbon cloth. Placing the treated carbon in a glassware, dripping 3000 microliters of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-treating at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): and (3) putting the precursor into a KOH solution with the concentration of 1mol/L, and soaking for 0.5h to obtain FeOOH@CC.
Example 2
Step (1): 400mg of nickel nitrate and 100g of ferric nitrate are weighed and dissolved in 10ml of ethanol solution, and the solution is fully dissolved by mechanical stirring at 200r/min to obtain solution D.
Step (2): cutting carbon cloth with thickness of 0.167mm and tensile strength of more than 4000MPa into 4X 3cm 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum conditions to obtain the treated carbon cloth. Placing the treated carbon in a glassware, dripping 3000 microliters of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-treating at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): soaking the precursor in 1mol/L KOH solution for 0.5 hour to obtain NiFe X (OH) Y @CC。
Comparative example 1
Step (1): 400g of nickel nitrate and 100g of ferric nitrate are weighed and dissolved in 10ml of ethanol solution, and the solution is fully dissolved by mechanical stirring at 200r/min to obtain solution D.
Step (2): cutting carbon cloth with thickness of 0.167mm and tensile strength of more than 4000MPa into 4X 3cm 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum conditions to obtain the treated carbon cloth. Placing the treated carbon in a glassware, dripping 3000 microliters of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-treating at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): soaking the precursor in 0.2mol/L KOH solution for 0.5 hr to obtain NiFe X (OH) Y @CC。
Comparative example 2
Step (1): 5mL of 100mg aqueous solution of nickel nitrate a and 5mL of 400mg aqueous solution of nickel nitrate b were prepared.
Step (2): 28mL of a 0.2M aqueous urea solution c and 4mL of a 0.01M aqueous sodium citrate solution d were prepared.
Step (3): solution aB, c, d and an area of 4X 3cm 2 Carbon with a thickness of 0.167mm and a tensile strength of more than 4000MPa is arranged in a 100mL polytetrafluoroethylene bottle, and is subjected to hydrothermal reaction for 3 hours under the condition of 150 ℃.
Step (4): washing the carbon cloth after the hydrothermal reaction with ethanol and aqueous solution, and then carrying out vacuum degree of 10 -2 ～10 - 6 And under the conditions of Pa and drying temperature of 80 ℃, obtaining the NiFe-LDH.
Example 3
Step (1): 30g of nickel nitrate, 10g of ferric nitrate and 10g of ruthenium chloride are weighed and dissolved in 10ml of ethanol solution, and the solution is fully dissolved by mechanical stirring at 200r/min to obtain solution D.
Step (2): cutting carbon cloth with thickness of 0.167mm and tensile strength of more than 4000MPa into 4X 3cm 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum conditions to obtain the treated carbon cloth. Placing the treated carbon in a glassware, dripping 3000 microliters of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-treating at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): soaking the precursor in 1mol/L KOH solution for 0.5 hour to obtain NiFeRu X (OH) Y @CC。
FIG. 1 is an SEM image of the electrocatalyst prepared in example 2, as clearly seen in FIG. 1, niFe X (OH) Y The @ CC is formed by a plurality of nano sheets with very thin thickness, the nano sheets can obviously improve the specific surface area of the catalyst, and the active sites are increased, so that the reaction efficiency is improved.
FIG. 2 shows the results of the oxygen evolution activity measured in this example 1-3. FeOOH@CC, niFe X (OH) Y @CC and NiFeRu X (OH) Y At a current density of 10mA cm @ CC -2 The time overpotential was 260mV, 190mV and 180mV, respectively, and FIG. 3 shows the corresponding Tafil slopes of 102.1, 60.4 and 39.5dec for the oxygen evolution reaction -1 The stability was 20h, 600h and 900h, respectively. The corresponding catalyst thicknesses were 35, 48 and 64nm,specific surface areas of 200, 205 and 218cm 3 g -1 . At a current density of 10mA cm -2 At the same time, the overpotential in comparative example 1 was 452mV and the Tafil slope was 185dec -1 The electrocatalytic activity is poor. Comparative example 2, which was prepared by conventional hydrothermal method, had an overpotential of 280mV and a Tafil slope of 90dec -1 。
Example 4
Step (1): 40g of nickel nitrate and 10g of ferric nitrate are weighed and dissolved in 10ml of ethanol solution, and fully dissolved under 200r/min mechanical stirring to obtain solution D.
Step (2): foam nickel (50% porosity) with a thickness of 0.167mm was cut into 4X 3cm pieces 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum condition to obtain the treated foam nickel. Placing the treated foam nickel into a glassware, dripping 5000 microliters of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-maintaining at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): soaking the precursor in 4mol/L NaOH solution for 0.5 hour to obtain NiFe X (OH) Y @Ni Foam。
Example 5
Step (1): 40g of nickel nitrate and 10g of ferric nitrate are weighed and dissolved in 10ml of ethanol solution, and fully dissolved under 200r/min mechanical stirring to obtain solution D.
Step (2): copper foam (46% porosity) with a thickness of 3.5mm was cut into 4X 3cm pieces 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum condition to obtain the treated foam copper. Placing the treated foamy copper into a glassware, dripping 5000 microliter of solution D, standing at 25deg.C for adsorption for 180min, and vacuum-maintaining at 10 -2 ～10 -6 And (3) drying in vacuum for 12h at the Pa and the drying temperature of 80 ℃ to obtain the precursor.
Step (3): immersing the precursor in 4mol/L KOH solutionSoaking for 0.5 hr to obtain NiFe X (OH) Y @Cu Foam。
Example 6
Step (1): 40g of nickel nitrate and 10g of ferric nitrate are weighed and dissolved in 10ml of ethanol solution, and fully dissolved under 200r/min mechanical stirring to obtain solution D.
Step (2): foam iron (porosity 54%) with a thickness of 4mm was cut into 4X 3cm pieces 2 Then ultrasonically washed with 1mol/L hydrochloric acid solution to pH=7, and then placed at 60℃and 10% -2 ～10 -6 And (5) carrying out vacuum drying for 18h under Pa vacuum condition to obtain the treated foam iron. Placing the treated foam iron into a glassware, dripping 5000 microliters of solution D, standing at 25deg.C for 180min, and vacuum-absorbing to 10 -2 ～10 -6 Vacuum drying for 12h under Pa and drying temperature of 80 ℃ to obtain precursor
Step (3): soaking the precursor in 4mol/L KOH solution for 0.5 hour to obtain NiFe X (OH) Y @Fe Foam。
The catalyst prepared in examples 4-6 had a nanoporous material morphology, corresponding to catalyst thicknesses of 45, 48 and 44nm and specific surface areas of 204, 205 and 208cm 3 g -1 . The current density is 10mA cm -2 At an overpotential of 185mV for NiFe X (OH) Y Stability test was performed at current densities of 10, 50, 80 and 100mA cm @ Ni Foam -2 The test was performed for 300 hours and still stable.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (6)

1. A method for preparing a metal hydroxide composite electrocatalyst, comprising the following steps:
1) Placing ferric nitrate and nickel nitrate or ferric nitrate, nickel nitrate and ruthenium chloride in a solvent according to a set proportion, stirring and dissolving to obtain a solution D;
the solvent is at least one of methanol, ethanol, glycol and isopropanol; the temperature is 20-80 ℃ during stirring, and the rotating speed is 10-1000 revolutions per minute; in the solution D, the total concentration of the metal salt is 0.5-20 mol/L;
2) Pretreating a conductive substrate Y, placing the pretreated conductive substrate Y into the solution D in the step 1), adsorbing at a set temperature, and performing vacuum drying after the adsorption is finished, so as to obtain a precursor;
the conductive substrate Y is one of foam metal, carbon paper and carbon cloth;
the adsorption time is 30-600 min;
the vacuum drying conditions are as follows: vacuum degree of 10 -2 ～10 -6 Pa, and drying time is 6-24 h;
3) Soaking the precursor in the step 2) in an alkaline solution to obtain a metal hydroxide composite electrocatalyst after soaking;
the concentration of the alkaline solution is 1-10 mol/L, the alkaline solution is at least one of KOH, naOH, liOH solutions, and the soaking time is 1-3600 min.
2. The method for preparing a metal hydroxide composite electrocatalyst according to claim 1, wherein in step 2), the metal foam is one of nickel foam, copper foam, titanium foam, and iron foam; the thickness of the foam metal is 1.0-4.0 mm, and the porosity is 20-99%; the thickness of the carbon cloth is 0.1-0.3 mm, and the tensile strength is more than 4000Mpa; the thickness of the carbon paper is 0.1-0.3 mm, and the porosity is 20-99%.
3. The method for preparing a metal hydroxide composite electrocatalyst according to claim 1, wherein in step 2), the pretreatment of the conductive substrate Y comprises the specific steps of: conducting ultrasonic cleaning on the conductive substrate Y by using 1mol/L hydrochloric acid solution until the pH value is=7, and then placing the conductive substrate Y at the temperature of 60-80 ℃ and 10 -2 ～10 -6 And (5) drying for 6-24 hours under the Pa vacuum condition.
4. The method for preparing a metal hydroxide composite electrocatalyst according to claim 1, wherein in step 2), 100 to 50000ul of solution D is added per square centimeter of the conductive substrate Y; the adsorption mode is one of standing adsorption, ultrasonic adsorption and suction filtration adsorption, and the reasonable adsorption mode can increase the load of the metal hydroxide on the conductive substrate Y.
5. The method for preparing a metal hydroxide composite electrocatalyst according to claim 1, wherein the alkaline solution is at least one of KOH and NaOH, the concentration is 1 to 4mol/L, and the soaking time is 20 to 40 minutes.
6. The metal hydroxide composite electrocatalyst according to any one of claims 1 to 5, wherein the metal hydroxide composite electrocatalyst comprises a conductive substrate and a metal hydroxide grown on the conductive substrate Y and having a general structural formula M (OH) x Y, 1.ltoreq.x.ltoreq.5, Y representing the conductive substrate Y, M representing the metal, said M (OH) x The nano-rod-shaped nano-particle material is at least one of nano-sheet-shaped, nano-wire-shaped, nano-rod-shaped or nano-cluster-shaped, and the thickness is 10-100 nm.
CN202111522301.7A 2021-12-13 2021-12-13 Preparation method of metal hydroxide composite electrocatalyst and product thereof Active CN114196983B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111522301.7A CN114196983B (en) 2021-12-13 2021-12-13 Preparation method of metal hydroxide composite electrocatalyst and product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111522301.7A CN114196983B (en) 2021-12-13 2021-12-13 Preparation method of metal hydroxide composite electrocatalyst and product thereof

Publications (2)

Publication Number Publication Date
CN114196983A CN114196983A (en) 2022-03-18
CN114196983B true CN114196983B (en) 2023-07-11

Family

ID=80653247

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111522301.7A Active CN114196983B (en) 2021-12-13 2021-12-13 Preparation method of metal hydroxide composite electrocatalyst and product thereof

Country Status (1)

Country Link
CN (1) CN114196983B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115354357B (en) * 2022-08-18 2024-08-16 广东工业大学 Fe/Ni@FF catalyst and preparation method and application thereof
CN117127213B (en) * 2023-08-28 2024-10-01 西湖大学 Hybrid catalyst and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108199051B (en) * 2016-12-08 2020-09-22 中国科学院大连化学物理研究所 Oxygen precipitation electrode and preparation and application thereof
CN110743570A (en) * 2019-11-19 2020-02-04 宋学杰 Preparation method of catalyst containing porous structure base material and method for decomposing formaldehyde by using catalyst

Also Published As

Publication number Publication date
CN114196983A (en) 2022-03-18

Similar Documents

Publication Publication Date Title
Xu et al. Template-directed assembly of urchin-like CoS x/Co-MOF as an efficient bifunctional electrocatalyst for overall water and urea electrolysis
CN110838588B (en) Rechargeable zinc-air battery bifunctional catalyst and preparation method and application thereof
CN110479329B (en) Preparation and application of phosphorus-doped cobalt telluride nano material
CN114196983B (en) Preparation method of metal hydroxide composite electrocatalyst and product thereof
Xu et al. Hollow bimetallic selenide derived from a hierarchical MOF-based Prussian blue analogue for urea electrolysis
CN113481534B (en) Preparation method of zirconium-doped cobalt-iron layered double hydroxide with low crystallinity and application of zirconium-doped cobalt-iron layered double hydroxide in hydrogen production by water electrolysis
CN113437314B (en) Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof
Wang et al. Elaborately tailored NiCo 2 O 4 for highly efficient overall water splitting and urea electrolysis
CN114438545A (en) Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst
CN112647092A (en) Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof
CN113718270A (en) Carbon-supported NiO/NiFe2O4Preparation method and application of spinel type solid solution water electrolysis oxygen evolution catalyst
CN114875442A (en) Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof
CN110841658A (en) Preparation method of cobalt-based sulfide nanorod array
Yan et al. Controllable fabrication of a nickel–iridium alloy network by galvanic replacement engineering for high-efficiency electrocatalytic water splitting
CN110629248A (en) Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst
CN112921351B (en) Preparation method and application of self-supporting catalytic electrode
Zhao et al. Hollow spherical LaNiO3 perovskite with superior multifunctional performances and durability for urea-assisted Zn-air batteries
CN117230458A (en) High-entropy Ni-Co-Fe-N-M hydroxide composite material, preparation thereof and application thereof in electrocatalysis
CN111342065A (en) Air electrode material, preparation method thereof, air electrode and air battery
CN115478296A (en) Self-supporting oxygen evolution electrode and preparation method and application thereof
CN114807967A (en) Preparation method of Ir-modified Ni/NiO porous nanorod array full-hydrolysis catalyst
CN114318410A (en) Cobalt-based water electrolysis catalyst, preparation method thereof and application thereof in water electrolysis
CN113293407A (en) Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof
CN112501645A (en) Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof
Lu et al. An Fe 3+ induced etching and hydrolysis precipitation strategy affords an Fe–Co hydroxide nanotube array toward hybrid water electrolysis

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant