CN111974397A - Thermo-electric coupled phase water oxidation catalyst for recycling low-grade waste heat - Google Patents
Thermo-electric coupled phase water oxidation catalyst for recycling low-grade waste heat Download PDFInfo
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- CN111974397A CN111974397A CN202010765676.5A CN202010765676A CN111974397A CN 111974397 A CN111974397 A CN 111974397A CN 202010765676 A CN202010765676 A CN 202010765676A CN 111974397 A CN111974397 A CN 111974397A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 229910001868 water Inorganic materials 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 239000002918 waste heat Substances 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 230000008878 coupling Effects 0.000 claims abstract description 15
- 238000010168 coupling process Methods 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 17
- 150000003624 transition metals Chemical class 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 13
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000013384 organic framework Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000012360 testing method Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000002440 industrial waste Substances 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C18/02—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 thermal decomposition
- C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The thermo-electric coupling bulk water oxidation catalyst with variable-valence transition metal ions is applied to a conductive substrate layer to prepare an electrode, wherein the conductive substrate layer is three-dimensional foamed nickel, copper, titanium, iron and carbon paper and can provide a larger contact area between the catalyst and electrolyte; the thermo-electric coupled bulk phase hydro-oxidation catalyst is a bulk phase catalytic material containing transition metal ions which can be used as catalytic active centers to participate in catalytic reaction, and contains Ni2+、Fe2+、Co2+、Mn2+The catalytic material with high specific surface area, low crystallinity or flexible structure of variable valence transition metal ions is prepared by an electrodeposition method or a hydrothermal method; the bulk electro-catalyst utilizes power waste heat or industrial low-grade waste heat in a coupling manner in the electro-catalysis process, so that the energy utilization rate is improved.
Description
Technical Field
The invention relates to a thermo-electric coupling water oxidation catalyst which utilizes power waste heat and industrial waste heat as heat sources; the invention also relates to a structure, a material, a preparation method and application of the high-efficiency oxygen evolution electrocatalyst.
Background
The increasing exhaustion of fossil fuels accompanied by serious environmental pollution makes it imperative to develop various clean renewable energy sources, among which hydrogen is widely regarded as a sustainable and abundant energy carrier with great potential to solve the current energy crisis[1]. In the process of hydrogen production by water electrolysis, the oxygen evolution reaction involves the transportation of four electrons, the kinetic process is very slow, and a higher potential is needed to overcome a reaction barrier, so that the water decomposition reaction is driven[2]. In actual working conditions, on one hand, the power waste heat is generated due to entropy increase, so that the whole reaction system operates in the environment of 30-80 ℃; on the other hand in industrySurplus Heat generationThe waste heat is recycled in enterprises with much waste heat, but most of the waste heat is only high-grade waste heat which is used for heating, heating water, process heat compensation and the like, and the rest of the waste heat is completely discharged in a cooling mode or directly, so that a great part of low-grade heat energy is completely wasted[3]. Generally, an increase in temperature can significantly increase the kinetics of the water oxidation reaction, but the kinetics of the ionic oxidation step are not significantly promoted. Therefore, the development of the water oxidation electrocatalyst which can simultaneously promote the kinetics of the ionic oxidation and oxygen evolution reaction and has low cost, high efficiency and environmental protection by combining the utilization of the power waste heat and the industrial waste heat has very important significance.
Reference documents:
[1]Steele B C H,Heinzel A.Materials for fuel-cell technologies[J].Nature,2001,414：345-352.
[2]Yue L,Kai Y,Longlu W,et al.Engineering MoS2nanomesh with holes and lattice defects for highly active hydrogen evolution reaction[J].Applied Catalysis B:Environmental,2018,239:537-544.
[3] wangguangzi, Wangguang. Engineering practice of waste heat recovery and hot water production of a certain power plant [ J ], energy conservation, 2011, 30(7): 79-81.
Disclosure of Invention
The invention provides a thermo-electric coupling water oxidation catalyst which utilizes power waste heat or industrial waste heat as a heat source; the invention also relates to a structure, a material, a preparation method and application of the high-efficiency oxygen evolution electrocatalyst. The invention aims to design and develop a thermo-electric coupled bulk water oxidation catalyst which utilizes power waste heat or industrial waste heat as a heat source; the invention also aims to provide a preparation method and application of the thermoelectric coupling oxygen evolution electrocatalyst material.
The invention utilizes a hydrothermal method or an electrodeposition method to prepare the electrocatalytic material with low crystallinity and a flexible structure, such as the low-crystallization transition metal hydroxide ultrathin nanosheet or the organic structural material containing the transition metal hydroxide, which has weaker lattice atom binding capacity. The prepared material has bulk catalytic material characteristics, i.e. has highThe specific surface area and the porosity are favorable for the electrolyte to permeate into a bulk phase, and the weak lattice constraint force is favorable for realizing that most of transition metal ions can be valence-changed to be used as a catalytic active center to participate in an oxygen precipitation reaction. The bulk electrode material preferably has variable valence transition metal ions such as Ni2+、Fe2+、Co2+、Mn2+Etc. as precursors. The prepared bulk catalytic material can be loaded on a three-dimensional conductive substrate with high specific surface area and high porosity to prepare an electrode device. The three-dimensional conductive substrate is preferably made of three-dimensional structural materials such as foam metal (nickel, copper, titanium and iron), carbon paper and the like so as to improve the contact area between the electrolyte and the electrode and promote the effective exertion of the catalytic performance of the bulk-phase electro-catalytic material. The prepared three-dimensional electrode can couple power waste heat and industrial low-grade waste heat in the electrocatalysis water oxidation process, and the energy utilization efficiency is improved.
In order to achieve the above purpose of the present invention, the following two similar technical solutions are adopted:
technical scheme one, transition metal hydroxide M (OH) with variable valence ions2The thermo-electric coupled bulk catalyst is prepared by an electrodeposition method and consists of a three-dimensional conductive substrate and an active component. The active component is hydroxide nanosheets containing variable valence transition metal ions; the substrate is any conductive substrate.
(1) Ultrasonically cleaning a conductive substrate by using acid, deionized water and ethanol respectively to serve as a working electrode to be deposited;
(2) weighing metal nitrate, and dissolving the metal nitrate in deionized water to obtain electroplating solution for electrodeposition; preparing electroplating solution, and placing the prepared electroplating solution in an electrolytic cell for preparing electrodeposition;
(3) placing the working electrode to be deposited obtained in the step (1) into the electroplating solution obtained in the step (2) under continuous magnetic stirring, and carrying out electrodeposition treatment at a constant potential of-1.4 to-1.0V (relative to a reversible hydrogen electrode), wherein the electrodeposition temperature range is 20-50 ℃, and the pH range is 5.0-6.5;
(4) all electrodes were rinsed with ethanol and water, respectively, after deposition and dried to obtain a low-crystallized thermo-electrically coupled transition metal hydroxide catalyst.
Preferably, the acid for treating the substrate in step (1) is nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and is selected according to the characteristics of the substrate.
Preferably, in the step (2), the metal nitrate is nickel nitrate, cobalt nitrate, ferric nitrate, manganese nitrate and the like, the dosage of the metal nitrate solution is 0.5-6 mmol, and the dosage of the deionized water is 50-300 mL.
Preferably, the electrodeposition potential in the step (3) is-1.4 to-1.0V, the electrodeposition charge amount is 0.5 to 5C, the treatment environment is a drying environment at 50 to 80 ℃, and the treatment time is 1 to 5 hours.
Preferably, the metal hydroxide is an ultrathin nanosheet with a thickness of 2-15 nm.
Second technical scheme, transition metal hydroxide M (OH)2The preparation method of the organic framework catalytic material is characterized in that the organic framework catalytic material is a transition metal hydroxide M (OH) containing variable valence ions2The organometallic framework catalyst for the thermo-electric coupled bulk phase is prepared by a hydrothermal method and consists of a three-dimensional conductive substrate and an active component. The active component is hydroxide nanosheets containing variable-valence transition metal ions and having limited domain of organic framework structure; the substrate is any conductive substrate.
(1) Ultrasonically cleaning a conductive substrate (foamed nickel and carbon paper) by using acid, deionized water and ethanol respectively, and placing the conductive substrate into a polytetrafluoroethylene reaction kettle for later use;
(2) weighing transition metal nitrate and terephthalic acid, and respectively dissolving in deionized water and N, N-dimethylformamide;
(3) and (3) pouring the transition metal nitrate solution and the terephthalic acid solution in the step (2) into a reaction kettle, reacting at the temperature of 150-200 ℃ to obtain the metal organic framework loaded foam nickel or carbon paper electrode, cleaning with deionized water and ethanol, and drying for later use.
(4) Applying a voltage of 1.5-1.9V to the electrode obtained by the treatment in the step (3), oxidizing for 5-10h, and carrying out electrooxidation until the current is stable to obtain a transition metal hydroxide organic framework structure electrode;
preferably, the acid for treating the substrate in step (1) is nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and may be selected according to the characteristics of the substrate.
Preferably, the dosage of the metal nitrate solution in the step (2) is 0.5-6 mmol, and the dosage of the deionized water is 50-300 mL.
Preferably, the dosage of the metal nitrate in the step (2) is 0.5-6 mmol, the dosage of the terephthalic acid is 2-10 mmol, the dosage of the deionized water is 20-60 mL, and the dosage of the N, N-dimethylformamide is 10-70 mL.
Preferably, the reaction time in the step (3) is 10-36 h.
Preferably, the organic framework confinement metal hydroxide ultrathin nanosheet porous structure has a specific surface area of 50-400 m2g-1The pore size distribution is 1-10 nm.
In the first and second technical solutions, the arbitrary conductive substrate is preferably a material with high specific surface area and porosity, such as a foam metal (nickel, copper, titanium, iron), carbon paper, carbon cloth, and the like. The foam metal is preferably foam nickel, the thickness of the foam metal is 1.0-2.0 mm, and the porosity of the foam metal is 20-99%; the carbon paper has a thickness of 0.1-0.3 mm and a porosity of 20-99%.
The working mechanism of the thermo-electric coupling transition metal water oxidation catalyst is as follows: the first step, thermally coupled with an electrically driven ion oxidation step, promotes the oxidation of transition metal ions from II valence to III valence on a catalytic electrode; and the second step, which is a thermal coupling electrocatalytic ion reduction step, accelerates the reduction rate of the transition metal ions from III valence to II valence, and improves the oxygen precipitation kinetics. As shown in fig. 2, 6, 7 and 8, at high temperature, the metal ions are not completely oxidized, and the oxygen evolution reaction is started, so that the action mechanism of the thermal-electrochemical reaction coupling is verified.
M-OH+OH-→M-OOH+H2O+e- (i)
M-OOH+H2O→M-OH+O2↑ (ii)
The invention relates to a transition metal ion (Ni) with variable valence2+、Fe2+、Co2+、Mn2+Etc.) bulk phase water oxidation electrocatalyst, which adopts power waste heat and industrial waste heat as heat sources and can promote the oxidation of transition metal ions simultaneouslyAnd oxygen evolution kinetics, thereby achieving thermoelectric coupling. The thermocouple phase water oxidation catalyst designed by the invention has universality and wide practical application prospect, requires variable-valence transition metal ions, has simple preparation process, convenient operation and low cost, and shows excellent electrocatalysis performance and electrode stability; the method can be applied to new energy systems based on oxygen evolution reaction, such as electrolytic water, electrocatalytic carbon dioxide reduction, electrocatalytic nitrogen reduction, metal-air batteries and the like; is especially suitable for alkaline electrolyte with the temperature ranging from 20 ℃ to 95 DEG C
Has the advantages that: compared with the prior art, the invention has the following advantages: (1) the novel oxygen precipitation electrode designed by the invention complementarily uses electric energy and heat energy, provides an efficient utilization way for power waste heat, industrial low-grade waste heat and off-peak electricity in actual working conditions, realizes cascade utilization of various energy sources, and has universality and wide industrialized application prospect; (2) according to the invention, by coupling thermochemistry and electrochemical reactions, the voltage required by the oxygen precipitation reaction is greatly reduced, and the oxygen precipitation rate is increased. (3) The preparation method of the electrocatalyst with variable-valence transition metal oxygen precipitation, which is designed by the invention, is simple, low in cost, mild in reaction conditions, green and safe, and the existing industrial equipment can meet the operation requirements of all operation steps.
Drawings
FIG. 1 shows Ni prepared in example 1x(OH)yHRTEM image of/NF catalyst.
FIG. 2 shows Ni prepared in example 1x(OH)yThe electro-oxidation treatment process diagram of the/NF catalyst.
FIG. 3 shows Ni prepared in example 1x(OH)yComparative LSV tests of/NF catalysts under different temperature conditions.
FIG. 4 shows Ni prepared in example 2xCo0.003x(OH)yHRTEM image of/NF catalyst.
FIG. 5 shows Ni prepared in example 2xCo0.003x(OH)yThe electro-oxidation treatment process diagram of the/NF catalyst.
FIG. 6 shows Ni prepared in example 2xCo0.003x(OH)yComparative LSV tests of/NF catalysts under different temperature conditions.
FIG. 7 shows Ni prepared in comparative example 2-1xCo0.003x(OH)yComparative LSV tests of/NF catalysts under different temperature conditions.
FIG. 8 is a comparison of LSV tests at different temperatures for the NiFe/NF catalysts prepared in example 3.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention are described in further detail, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
The oxygen evolution activity test conditions used in the present invention were: 1.0mol L in different temperature ranges (20 ℃ -95 ℃)-1KOH is used as electrolyte for oxygen precipitation, a test is carried out by adopting a three-electrode system, a platinum sheet is used as a counter electrode, the purity is higher than 99.99 percent, saturated Ag/AgCl is used as a reference electrode, and a test instrument is a Shanghai Chenghua CHI 730e electrochemical workstation. All test voltage values are converted into voltage values for the standard hydrogen electrode, and the influence of temperature on the reference electrode voltage is considered.
Example 1
(1) Cleaning foam Nickel (NF) with dilute hydrochloric acid, deionized water and ethanol respectively, and placing the cleaned foam Nickel (NF) in a polytetrafluoroethylene reaction kettle for later use;
(2) weighing 5mmol of nickel nitrate and 5mmol of terephthalic acid, and respectively dissolving in deionized water and N, N-dimethylformamide;
(3) successively pouring the nickel nitrate solution and the terephthalic acid solution in the step (2) into a reaction kettle, and reacting for 24 hours at 180 ℃ to obtain Ni BDC/NF, namely a Ni BDC metal organic framework loaded on the foamed nickel;
(4) cleaning the Ni BDC/NF obtained in the step (3) with deionized water and ethanol respectively, and drying for later use;
(5) applying 1.7V voltage to the Ni BDC/NF processed in the step (4), and electrifying the Ni BDC/NFOxidizing for 12h until the current is stable to obtain Nix(OH)y/NF Metal hydroxide catalyst. HRTEM image is shown in FIG. 1, the process of electro-oxidation treatment is shown in FIG. 2, and the test image of oxygen evolution performance at different temperatures is shown in FIG. 3.
Example 2
(1) Cleaning foam Nickel (NF) with dilute hydrochloric acid, deionized water and ethanol respectively, and placing the cleaned foam Nickel (NF) in a polytetrafluoroethylene reaction kettle for later use;
(2) weighing 5mmol of nickel nitrate, cobalt nitrate (wherein the mass of the cobalt nitrate is 3 percent of that of the nickel nitrate) and 5mmol of terephthalic acid, and respectively dissolving in deionized water and N, N-dimethylformamide;
(3) pouring the nickel nitrate and cobalt nitrate solution and the terephthalic acid solution in the step (2) into a reaction kettle, and reacting at 180 ℃ for 24 hours to obtain NiCo (3%) BDC/NF;
(4) washing the Co BDC/NF obtained in the step (3) with deionized water and ethanol respectively, and drying for later use;
(5) applying 1.7V voltage to the Co BDC/NF obtained by the treatment of the step (4), and carrying out electrooxidation for 12h until the current is stable to obtain NixCo0.003x(OH)za/NF catalyst. HRTEM image is shown in FIG. 4, the process of electro-oxidation treatment is shown in FIG. 5, and the test image of oxygen evolution performance at different temperatures is shown in FIG. 6.
Comparative example 2-1
In the step (2) of the example 2, the weighing amount of the cobalt nitrate is changed to 0.45mmol, namely 3 percent of the mass of the nickel nitrate, and the rest steps are unchanged. The oxygen evolution performance test chart is shown in FIG. 7.
Example 3
(1) Ultrasonically cleaning foamed Nickel (NF) by using acid, deionized water and ethanol respectively to serve as a working electrode to be deposited;
(2) weighing 1mmol of nickel nitrate and 1mmol of ferric nitrate, adding into 100mL of deionized water, and performing ultrasonic dispersion to obtain electroplating solution for electrodeposition;
(3) placing the working electrode to be deposited obtained in the step (1) in the electroplating solution obtained in the step (2) under continuous magnetic stirring, and carrying out electrodeposition treatment at a constant potential of-1.4V (relative to a reversible hydrogen electrode), wherein the deposition electric quantity is 1C;
(4) all electrodes were rinsed with ethanol and water, respectively, after deposition and dried at 60 ℃ for 2h to give a thermo-electrically coupled nickel iron hydroxide hydro-oxidation catalyst. The oxygen evolution performance test chart at different temperatures is shown in FIG. 8.
With reference to fig. 1-8, the following conclusions can be drawn: in the invention, the temperature is increased, so that the oxidation of transition metal ions can be promoted, and the oxygen precipitation reaction kinetics can be accelerated, namely, the ion oxidation step and the oxygen precipitation ion reduction step are integrally realized by utilizing the thermo-electric coupling.
The oxygen evolution electrode prepared by the electrocatalyst in the embodiment can be applied to water electrolysis, electrocatalytic carbon dioxide reduction, electrocatalytic nitrogen reduction and metal-air battery systems.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A thermo-electric coupled phase hydro-oxidation catalyst with variable-valence transition metal ions is characterized in that the catalyst can be applied to a conductive substrate layer to prepare an electrode, wherein the conductive substrate layer is made of three-dimensional foam metal (nickel, copper, titanium, iron), carbon paper and the like and can provide a larger contact area between the catalyst and electrolyte; the thermo-electric coupled bulk phase hydro-oxidation catalyst is a bulk phase catalytic material containing transition metal ions which can be used as catalytic active centers to participate in catalytic reaction, and contains Ni2+、Fe2+、Co2+、Mn2+The catalytic material with high specific surface area, low crystallinity or flexible structure of variable valence transition metal ions is prepared by an electrodeposition method or a hydrothermal method; the bulk electro-catalyst utilizes power waste heat or industrial low-grade waste heat in a coupling manner in the electro-catalysis process, so that the energy utilization rate is improved.
2. The thermo-electric coupled bulk water oxidation catalyst with variable valence transition metal ions according to claim 1, wherein the catalyst is low-crystallization transition metal hydroxide ultrathin nanosheet or transition metal hydroxide organic framework structure material with weak lattice atom binding force, has high specific surface area and porosity, and is preferably variable valence transition metal hydroxide M (OH)2And comprising M (OH)2Wherein M is Ni2+、Fe2+、Co2+、Mn2+Plasma single ion or mixture of multiple ions.
3. The thermo-electric coupling bulk water oxidation catalyst with variable-valence transition metal ions, which is claimed in claim 1, is characterized in that the bulk water oxidation catalyst can be used as an electro-catalytic layer to be supported on any conductive substrate to prepare an electrode device, preferably foamed metal (nickel, copper, titanium, iron), carbon paper, carbon cloth and other materials with high specific surface area and porosity, wherein the thickness of the foamed metal substrate is 1.0-2.0 mm, and the porosity is 20-99%; the thickness of the carbon paper or the carbon cloth is 0.1-0.3 mm, and the porosity is 20-99%.
4. The transition metal hydroxide M (OH) according to any one of claims 1 to 32The preparation method of the catalyst is characterized by comprising the following steps:
(1) ultrasonically cleaning a conductive substrate by using acid, deionized water and ethanol respectively to serve as a working electrode to be deposited;
(2) weighing metal nitrate, and dissolving the metal nitrate in deionized water to obtain electroplating solution for electrodeposition; preparing electroplating solution, and placing the prepared electroplating solution in an electrolytic cell for preparing electrodeposition;
(3) placing the working electrode to be deposited obtained in the step (1) in the electroplating solution obtained in the step (2) under continuous magnetic stirring, and carrying out electrochemical reduction deposition treatment at a constant potential of-1.4 to-1.0V (relative to a reversible hydrogen electrode), wherein the electrodeposition temperature range is 20-50 ℃, and the pH range is 5.0-6.5;
(4) all electrodes were rinsed with ethanol and water, respectively, after deposition and dried to obtain a low-crystallized thermo-electrically coupled transition metal hydroxide catalyst.
Wherein the acid for treating the substrate in the step (1) is nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, and is selected according to the characteristics of the substrate;
in the step (2), the metal nitrate is nickel nitrate, cobalt nitrate, ferric nitrate, manganese nitrate and the like, the dosage of the metal nitrate solution is 0.5-6 mmol, and the dosage of the deionized water is 50-300 mL.
In the step (3), the electro-deposition potential is-1.4 to-1.0V, the electro-deposition charge amount is 0.5 to 5C, the treatment environment is a drying environment at 50 to 80 ℃, and the treatment time is 1 to 5 hours.
5. The composition according to claim 1 to 3, comprising a transition metal hydroxide M (OH)2The preparation method of the organic framework catalytic material is characterized in that,
(1) ultrasonically cleaning a conductive substrate (foamed nickel and carbon paper) by using acid, deionized water and ethanol respectively, and placing the conductive substrate into a polytetrafluoroethylene reaction kettle for later use;
(2) weighing transition metal nitrate and terephthalic acid, and respectively dissolving in deionized water and N, N-dimethylformamide;
(3) and (3) pouring the transition metal nitrate solution and the terephthalic acid solution in the step (2) into a reaction kettle, reacting at the temperature of 150-200 ℃ to obtain the metal organic framework loaded foam nickel or carbon paper electrode, cleaning with deionized water and ethanol, and drying for later use.
(4) Applying a voltage of 1.5-1.9V to the electrode obtained by the treatment in the step (3), oxidizing for 5-10h, and carrying out electrooxidation until the current is stable to obtain a transition metal hydroxide organic framework structure electrode;
wherein the acid for treating the substrate in the step (1) is nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, and can be selected according to the characteristics of the substrate.
Wherein the dosage of the metal nitrate solution in the step (2) is 0.5-6 mmol, and the dosage of the deionized water is 50-300 mL.
Wherein the dosage of the metal nitrate in the step (2) is 0.5-6 mmol, the dosage of the terephthalic acid is 2-10 mmol, the dosage of the deionized water is 20-60 mL, and the dosage of the N, N-dimethylformamide is 10-70 mL.
Wherein the reaction time in the step (3) is 10-36 h.
6. The variable valence thermo-electric coupled bulk water oxidation catalyst for transition metal ions according to claim 1, wherein the bulk electro-catalyst can utilize power waste heat or industrial low grade waste heat in a coupling manner during the electro-catalysis process, and the coupled heat energy can promote the oxidation kinetics of the transition metal ions and the oxygen evolution reaction kinetics at the same time.
7. The application of the thermo-electric coupling transition metal water oxidation catalyst is characterized in that the catalyst is applied to new energy systems comprising oxygen evolution reaction, such as electrolytic water, electrocatalytic carbon dioxide reduction, electrocatalytic nitrogen reduction, metal-air batteries and the like; the electrolyte is particularly suitable for alkaline electrolyte, and the temperature range of the electrolyte is 20-95 ℃.
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