CN110512234A - A kind of preparation method for the composite nanometer film producing hydrogen for electro-catalysis - Google Patents

A kind of preparation method for the composite nanometer film producing hydrogen for electro-catalysis Download PDF

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Publication number
CN110512234A
CN110512234A CN201910891212.6A CN201910891212A CN110512234A CN 110512234 A CN110512234 A CN 110512234A CN 201910891212 A CN201910891212 A CN 201910891212A CN 110512234 A CN110512234 A CN 110512234A
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sulfonated
poly
nanometer film
composite nanometer
sulfone
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王宁
潘大为
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Yantai Institute of Coastal Zone Research of CAS
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Yantai Institute of Coastal Zone Research of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention relates to a kind of preparation method of composite nanometer film for producing hydrogen for electro-catalysis, which has excellent electro-catalysis hydrogen capacity and resistance to acid and alkali.The composite nanometer film is made of multilayered structure, including supporting layer and nano-catalytic oxidant layer.Supporting layer is macromolecule proton exchange membrane, and nano-catalytic oxidant layer is inorganic nano material, wherein 100 microns~1000 microns of supporting layer thickness, 0.1 micron~100 microns of nanocatalyst thickness degree.A kind of preparation method of electro-catalysis hydrogen manufacturing composite nanometer film provided by the invention, has many advantages, such as that method is simple, efficient.The composite nanometer film of preparation is overall structure, and the removing of nanocatalyst application process kind is avoided to fall off；Gained composite nanometer film is porous structure, is conducive to electrocatalytic reaction.

Description

A kind of preparation method for the composite nanometer film producing hydrogen for electro-catalysis
Technical field
The present invention relates to a kind of preparation methods of composite nanometer film that hydrogen is produced for electro-catalysis, can be used for catalytic electrolysis water system Standby hydrogen.
Background technique
Hydrogen molecule can remove interior free yl, have good therapeutic effect to aging and chronic disease.The life of the mankind It is be unable to do without water, is most reasonable manner by drinking the drinking water rich in hydrogen molecule.Currently, water electrolysis hydrogen production molecule is before most having The hydrogen manufacturing mode of scape a, significant process of the Hydrogen evolving reaction as electrolysis water, has caused the extensive concern of scholar.Water first Electrode reaction occurs in anode, oxygen and hydrogen ion are generated, wherein only hydrogen ion and water can be reached by proton exchange membrane Cathode generates hydrogen molecule after obtaining electronics, and oxygen can not be by proton exchange membrane, to prepare purified hydrogen molecule.Currently, Proton exchange membrane used is generally the Nafion membrane of DuPont Corporation's production, and structure is polytetrafluoroethylene (PTFE) With perfluor -3,6- diepoxy -4- methyl -7- decene-sulfuric acid copolymer.Due to the presence of sulfonic acid group, film has very strong Seepage of water and proton exchange ability.However, Nafion membrane fancy price limits large-scale practical application.Therefore, it studies The proton exchange membrane of exploitation Cheap highly effective is one of the key scientific problems of the inexpensive water electrolysis hydrogen production of realization, and the neck at present The emphasis and hot spot of domain research.It is various to contain sulfonic copolymer since its unique proton exchange ability is by common concern.
In addition to proton exchange membrane, the inorganic nano material being attached in proton exchange membrane is for accelerating electrolysis water to prepare hydrogen It is also essential (Small, 2018,14,1800667).Using platinum, nickel, cobalt, iron, manganese, iridium, molybdenum and ruthenium as the metal of representative And its sulfide, selenides, phosphide, carbide, nitride and oxide, overpotential can be effectively reduced, improve energy benefit With rate, realize that efficient catalytic produces hydrogen.
Therefore, compound by the inexpensive proton exchange membrane and elctro-catalyst progress that will synthesize, preparation electro-catalysis hydrogen manufacturing is multiple Nanometer film is closed, low-cost high-efficiency hydrogen manufacturing is expected to, there is important research significance and real value.
Summary of the invention
The present invention aiming at the problems existing in the prior art, provides a kind of system of composite nanometer film for electro-catalysis hydrogen manufacturing Preparation Method.
To achieve the goals above, technical scheme is as follows:
A kind of preparation method for the composite nanometer film producing hydrogen for electro-catalysis, which is characterized in that
(a) with the multilayered structure of supporting layer and nano-catalytic oxidant layer.
(b) supporting layer described in plays proton exchange.
(c) composite nanometer film is with a thickness of 100 microns~1100 microns；Wherein supporting layer is micro- with a thickness of 100 microns~1000 Rice, accounts for the 50.0%~99.9% of composite Nano film thickness；Nanocatalyst layer is with a thickness of 0.1 micron~100 microns, Zhan Fuhe The 0.1~50.0% of nanometer film thickness.
(d) composite nanometer film is plate membrane.
Composite nanometer film, supporting layer are high molecular material, including sulfonated polystyrene block copolymer, sulfonated polysulfone block Copolymer, sulfonated polyphenyl sulfone block copolymer and sulfonation polyvinylidene fluoride alkene block copolymer；Nano-catalytic oxidant layer is inorganic nano Material is made of metal or metal sulfide, selenides, phosphide, carbide and nitride, metal include platinum, nickel, cobalt, iron, Manganese, iridium, molybdenum and ruthenium.
The preparation step of composite nanometer film includes:
(a) high molecular material is prepared into proton exchange membrane by the tape casting film forming.
(b) in the preparation process of composite nanometer film, using adhesive, by being coated with method or cement-dipping method for inorganic nano material It is adhered in proton exchange membrane, then obtains composite nanometer film in 40~60 DEG C of vacuum drying treatments.
The high molecular material, wherein sulfonated polystyrene block copolymer includes poly- (the 4- ethylene of sulfonated polystyrene-b- Yl pyridines), sulfonated polystyrene-b- poly- (2- vinylpyridine), sulfonated polystyrene-b- polyoxyethylene, sulfonated polystyrene- B- poly- (polymethylacrylic acid dimethylaminoethyl)；Wherein sulfonated polysulfone block copolymer includes poly- (the 4- ethylene of sulfonated polysulfone-b- Yl pyridines), sulfonated polysulfone-b- poly- (2- vinylpyridine), sulfonated polysulfone-b- polyoxyethylene, poly- (the poly- methyl of sulfonated polysulfone-b- Dimethylaminoethyl acrylate), sulfonated polyether sulfone-b- P4VP, poly- (the 2- vinylpyridine of sulfonated polyether sulfone-b- Pyridine), sulfonated polyether sulfone-b- polyoxyethylene, sulfonated polyether sulfone-b- poly- (polymethylacrylic acid dimethylaminoethyl)；Wherein, sulfonation Polyphenylsulfone block copolymer includes sulfonated polyphenyl sulfone-b- P4VP, poly- (the 2- vinylpyridine of sulfonated polyphenyl sulfone-b- Pyridine), sulfonated polyphenyl sulfone-b- polyoxyethylene, sulfonated polyphenyl sulfone-b- poly- (polymethylacrylic acid dimethylaminoethyl)；Wherein sulfonation Polyvinylidene fluoride alkene block copolymer includes sulfonation Kynoar-b- P4VP, and sulfonation Kynoar-b- is poly- (2- vinylpyridine), Kynoar-b- polyoxyethylene, poly- (the polymethylacrylic acid dimethylamino second of Kynoar-b- Ester).
The macromolecule solvent and adhesive is selected from n-methyl-2-pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, four Methyl sulfoxide, sulfolane, diphenyl sulfone tetramethylurea, dimethyl acetamide, dimethylformamide, acetone, methyl ethyl ketone, tricresyl phosphate Methyl esters and gamma-butyrolacton.
Specific embodiment
In order to deepen the understanding of the present invention and recognize, the present invention is made further With reference to embodiment Illustrate and introduces.
Embodiment 1-4:
Sulfonation Kynoar based block copolymer Polymer Solution is prepared into proton exchange membrane supporting layer by the tape casting； Inorganic nano material is dispersed in adhesive, inorganic material is adhered in proton exchange membrane by cement-dipping method, then 40 DEG C vacuum drying treatment obtains nano composite membrane.By taking nano composite membrane prepared by embodiment 4 as an example, nano composite membrane shows excellent Different electrocatalytic hydrogen evolution performance, in 10mA/cm2Current density under, overpotential is only 90mV, and continues 48 hours liberations of hydrogen After reaction, electric current decline is only 1.5%.
Embodiment 5-12:
Sulfonated polysulfone based block copolymer solution is prepared into proton exchange membrane by the tape casting；Inorganic nano material is dispersed In adhesive, inorganic material is adhered in proton exchange membrane by cement-dipping method.Then it is obtained in 50 DEG C of vacuum drying treatments Nano composite membrane.
Embodiment 13-16:
Sulfonated polyphenyl sulfone based block copolymer solution is prepared into proton exchange membrane supporting layer by the tape casting；By inorganic nano Material is dispersed in adhesive, and inorganic material is adhered in proton exchange membrane by being coated with method, is then dried in vacuo at 60 DEG C Processing obtains nano composite membrane.
Embodiment 17-20:
Sulfonated polystyrene based block copolymer solution is prepared into proton exchange membrane supporting layer by the tape casting；It is received inorganic Rice material is dispersed in adhesive, and inorganic material is adhered in proton exchange membrane by being coated with method, then dry in 60 DEG C of vacuum Dry processing obtains nano composite membrane.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no guarantors for the purpose of limiting the invention Range is protected, the equivalent substitution or substitution made based on the above technical solution all belongs to the scope of protection of the present invention, Protection scope of the present invention is subject to claims.

Claims (5)

1. a kind of preparation method for the composite nanometer film for producing hydrogen for electro-catalysis, which is characterized in that
(a) with the multilayered structure of supporting layer and nano-catalytic oxidant layer.
(b) supporting layer described in plays proton exchange.
(c) composite nanometer film is with a thickness of 100 microns~1100 microns；Wherein supporting layer accounts for a thickness of 100 microns~1000 microns The 50.0%~99.9% of composite Nano film thickness；Nanocatalyst layer accounts for composite Nano with a thickness of 0.1 micron~100 microns The 0.1~50.0% of film thickness.
(d) composite nanometer film is plate membrane.
2. composite nanometer film according to claim 1, supporting layer is high molecular material, including sulfonated polystyrene block is total to Polymers, sulfonated polysulfone block copolymer, sulfonated polyphenyl sulfone block copolymer and sulfonation polyvinylidene fluoride alkene block copolymer；Nanometer is urged Agent layer is inorganic nano material, is made of metal or metal sulfide, selenides, phosphide, carbide and nitride, metal Including platinum, nickel, cobalt, iron, manganese, iridium, molybdenum and ruthenium.
3. composite nanometer film according to claims 1 and 2, preparation step include:
(a) high molecular material is dissolved in solvent through the tape casting film forming and prepares proton exchange membrane.
(b) in the preparation process of composite nanometer film, using adhesive, inorganic nano material is glued by being coated with method or cement-dipping method It invests in proton exchange membrane, then obtains composite nanometer film in 40~60 DEG C of vacuum drying treatments.
4. high molecular material according to claim 2, wherein sulfonated polystyrene block copolymer includes sulfonated polyphenyl second Alkene-b- P4VP, sulfonated polystyrene-b- poly- (2- vinylpyridine), sulfonated polystyrene-b- polyoxy second Alkene, sulfonated polystyrene-b- poly- (polymethylacrylic acid dimethylaminoethyl)；Wherein sulfonated polysulfone block copolymer includes sulfonation Polysulfones-b- P4VP, sulfonated polysulfone-b- poly- (2- vinylpyridine), sulfonated polysulfone-b- polyoxyethylene, sulfonation Polysulfones-b- poly- (polymethylacrylic acid dimethylaminoethyl), sulfonated polyether sulfone-b- P4VP, sulfonated polyether sulfone- B- poly- (2- vinylpyridine), sulfonated polyether sulfone-b- polyoxyethylene, poly- (the polymethylacrylic acid dimethylamino of sulfonated polyether sulfone-b- Ethyl ester)；Wherein sulfonated polyphenyl sulfone block copolymer includes sulfonated polyphenyl sulfone-b- P4VP, sulfonated polyphenyl sulfone-b- Poly- (2- vinylpyridine), sulfonated polyphenyl sulfone-b- polyoxyethylene, poly- (the polymethylacrylic acid dimethylamino second of sulfonated polyphenyl sulfone-b- Ester)；Wherein sulfonation polyvinylidene fluoride alkene block copolymer includes sulfonation Kynoar-b- P4VP, and sulfonation is poly- Vinylidene-b- poly- (2- vinylpyridine), Kynoar-b- polyoxyethylene, the poly- (polymethyl of Kynoar-b- Sour dimethylaminoethyl).
5. solvent according to claim 3 and adhesive, sub- selected from n-methyl-2-pyrrolidone, tetrahydrofuran, dimethyl Sulfone, tetramethyl sulfoxide, sulfolane, diphenyl sulfone tetramethylurea, dimethyl acetamide, dimethylformamide, acetone, methyl ethyl ketone, Trimethyl phosphate and gamma-butyrolacton.
CN201910891212.6A 2019-06-05 2019-09-19 A kind of preparation method for the composite nanometer film producing hydrogen for electro-catalysis Pending CN110512234A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415888A (en) * 1993-04-26 1995-05-16 E. I. Du Pont De Nemours And Company Method of imprinting catalytically active particles on membrane
CN101250713A (en) * 2007-11-30 2008-08-27 清华大学 Method for manufacturing solid electrolyte membrane electrode
CN101463487A (en) * 2007-12-17 2009-06-24 中国电子科技集团公司第十八研究所 Preparation of proton exchange membrane electrode for electrolyzing water
CN101942672A (en) * 2010-09-16 2011-01-12 清华大学 Preparation method of polymer electrolyte membrane electrode
CN108273400A (en) * 2018-01-04 2018-07-13 中国科学院烟台海岸带研究所 A kind of preparation method of seperation film for ferro element separation
CN109037712A (en) * 2018-07-23 2018-12-18 成都新柯力化工科技有限公司 A kind of nitridation catalyst with base of molybdenum being used to prepare fuel cell hydrogen and preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415888A (en) * 1993-04-26 1995-05-16 E. I. Du Pont De Nemours And Company Method of imprinting catalytically active particles on membrane
CN101250713A (en) * 2007-11-30 2008-08-27 清华大学 Method for manufacturing solid electrolyte membrane electrode
CN101463487A (en) * 2007-12-17 2009-06-24 中国电子科技集团公司第十八研究所 Preparation of proton exchange membrane electrode for electrolyzing water
CN101942672A (en) * 2010-09-16 2011-01-12 清华大学 Preparation method of polymer electrolyte membrane electrode
CN108273400A (en) * 2018-01-04 2018-07-13 中国科学院烟台海岸带研究所 A kind of preparation method of seperation film for ferro element separation
CN109037712A (en) * 2018-07-23 2018-12-18 成都新柯力化工科技有限公司 A kind of nitridation catalyst with base of molybdenum being used to prepare fuel cell hydrogen and preparation method

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