CN109072458A - The analysis oxygen elctro-catalyst of cobalt (II, III) oxide skin(coating) containing carbon coating - Google Patents
The analysis oxygen elctro-catalyst of cobalt (II, III) oxide skin(coating) containing carbon coating Download PDFInfo
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- CN109072458A CN109072458A CN201780020908.0A CN201780020908A CN109072458A CN 109072458 A CN109072458 A CN 109072458A CN 201780020908 A CN201780020908 A CN 201780020908A CN 109072458 A CN109072458 A CN 109072458A
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- Prior art keywords
- carbon
- catalyst
- cobalt
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- elctro
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 248
- 239000003054 catalyst Substances 0.000 title claims abstract description 210
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001301 oxygen Substances 0.000 title claims abstract description 38
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004458 analytical method Methods 0.000 title description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 104
- 239000010941 cobalt Substances 0.000 claims description 103
- 229910017052 cobalt Inorganic materials 0.000 claims description 100
- 239000002243 precursor Substances 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
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- 239000000126 substance Substances 0.000 claims description 26
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 150000001722 carbon compounds Chemical class 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
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- 239000008103 glucose Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
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- 150000002431 hydrogen Chemical class 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 150000002340 glycosyl compounds Chemical class 0.000 claims description 2
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 39
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
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- 229910052751 metal Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 102000004316 Oxidoreductases Human genes 0.000 description 5
- 108090000854 Oxidoreductases Proteins 0.000 description 5
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- 235000019441 ethanol Nutrition 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PGMOXNFVYWQBSR-UHFFFAOYSA-N [O].[O].[Co] Chemical compound [O].[O].[Co] PGMOXNFVYWQBSR-UHFFFAOYSA-N 0.000 description 2
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- 150000001868 cobalt Chemical class 0.000 description 2
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- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 2
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- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J23/75—Cobalt
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
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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
- C25B11/04—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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
Describe oxygen evolution reaction (OER) catalyst and application thereof.Discrete catalytic cobalt (II, III) oxide (Co that OER catalyst may include carbon carrier, directly contact with the carbon carrier3O4) nanometer layer and amorphous state continuous carbon-coating.Co3O4Nanometer layer is between the carbon carrier and amorphous state continuous carbon-coating.
Description
Cross reference to related applications
This application claims the U.S. Provisional Patent Application submitted the 62/324093rd priority on April 18th, 2016 power
Benefit is incorporated herein by reference.
Background technique
A. technical field
The present invention relates generally to oxygen evolution reaction (OER) elctro-catalysts comprising directly contacts with carbon carrier discrete
Catalytic Co3O4Nanometer layer and amorphous state continuous carbon-coating.Discrete Co3O4Catalytic nanometer layer is located at carbon carrier and amorphous state connects
Between continuous carbon-coating.
B. description of Related Art
As needs minimize the CO from fossil fuel2Discharge amount, hydrogen have increased as the use of the energy.Hydrogen
A kind of source can be water-splitting Cheng Qing and oxygen.Electrochemical apparatus (such as electrolytic cell) can be used and realize water crack on a large scale
Solution.In a cell, by making electric current by the inclusion of the aqueous solution of electrolyte to decompose water, by water-splitting at hydrogen (H2) and oxygen
(O2).Hydrogen manufacturing can be limited by the dynamics of the oxygen evolution reaction (OER) on anode in electrolysis water cracking reaction.It has attempted to
Various solutions improve the generation of oxygen at anode.For example, will contain metal or noble metal such as iridium (Ir), ruthenium (Ru)
And its elctro-catalyst of the oxide form of alloy is coated on anode.However, their scarcity and relevant high cost pole
The earth limits the extensive implementation of commercial plant.In addition, these catalyst can be unstable in caustic acid.Raising oxygen effect
Other trials of rate include oxide/hydroxide that cobalt (Co), iron (Fe), nickel (Ni) and manganese (Mn) are used in alkaline solution
Object, phosphide, disulphide and some nonmetallic compounds are as OER catalyst.However, the development of alkaline water electrolytic by
To the limitation of some problem including the cross-diffusion of low current density and produced gas.In contrast, in acid
Proton exchange membrane (PEM) electrolysis has had shown that the key in terms of current density, voltage efficiency and produced gas purity
Advantage.A variety of anode catalysts such as ruthenium-oxide (RuO suitable for acid is developed2) and yttrium oxide (IrO2) and they
Ternary oxide is used for the application of these types.It will include tin (Sn), antimony for the use for reducing noble metal (such as Ru and Ir)
(Sb), other metallic elements of niobium (Nb), lead (Pb), nickel (Ni), copper (Cu), tantalum (Ta), zirconium (Zr) and molybdenum (Mo) are added to expensive
To form alloy or nucleocapsid structure in metal.However, the anode made of these metals is also subject to corruption in use
Erosion.
The trial for preparing OER elctro-catalyst recently concentrates on cobalt (II, III) oxide (Co3O4) use.Co3O4In alkali
Catalytic property and chemical stability are had shown that in property solution, however, due to Co3O4Higher than 1.47V (relative to RHE)
Corroded under potential, Co3O4OER application in acid medium is not yet successful.It, can be by Co under these potentials3O4It is formed
Cobalt (IV) oxide (CoO2), then cobalt (IV) oxide (CoO2) soluble cobalt (II) oxide CoO can be resolved into, together
When discharge O2.In addition, the Co of cobalt OER electrode3O4It is poor with the adhesion of electrode basement (for example, titanium foil substrate).It has been disclosed and changes
Into the various trials containing cobalt electrode.For example, Leng et al. is in " Carbon-encapsulated
Co3O4Nanoparticles as Anode Materials with Super Lithium Storage Performance ",
Scientific Reports, in November, 2015 disclose the Co of carbon encapsulating in page 1 to 113O4Nano particle (i.e. Co3O4@C
Structure) it is embedded in the application in carbon carrier.The shortcomings that these electrodes, is, since cobalt is separated from solution by two layers of carbon, into
The electric charge stream of cobalt core is inefficient out.The various trials for preparing cobalt OER catalyst include cobalt-carbon complex (referring to Yiming etc.
The Chinese Patent No. of people 104056630) and in the hole of porous carbon skeleton equally distributed metal hydroxides (referring to
The Chinese patent application of Cheng et al. discloses No. 10495582).These OER catalyst higher than 1.47V potential under by
Anodic attack.
As described above, be currently available that many OER catalyst in acidic environment by anodic attack, catalysis material is from load
The manufacture of leaching and/or OER catalyst in body material is not cost-benefit.
Summary of the invention
Made discovery, in OER catalyst the relevant issues of cobalt substance used provide good solution
Scheme.The premise of the solution be provided between carbon carrier and amorphous state continuous carbon-coating discrete catalytic cobalt (II,
III) oxide (Co3O4) nanometer layer.Discrete catalytic Co3O4Nanometer layer is directly contacted with carbon carrier.It is not intended to by theory
Constraint, it is believed that when OER catalyst is used as one group of electrode in cell reaction, cobalt provides cobalt object with directly contacting for carbon carrier
Effective charge transfer between matter and carbon carrier, and carbon-coating inhibits catalytic Co3O4It is peeled off from carbon support.It is worth noting
, solution of the invention do not need using noble metal to provide low overpotential and acceptable in acid or alkaline solution
Current density.In addition, OER elctro-catalyst equal long-time stable (for example, will not decompose) in acid and alkaline solution.
The solution further includes producing the new method of OER elctro-catalyst.This method includes that two steps of carbon carrier are calcined
Journey, the carbon carrier include the discrete cobalt precursors layer of deposition on the carbon carrier.The first step may include under vacuum conditions
(oxygen lean conditions) heat treated carbon carrier.In the first step, the surface integrity of carbon carrier (for example, carbon paper or carbon cloth) obtains
Enhancing, cobalt precursors are converted into CoO.Second calcining step is heat-treated the carbon carrier from the first step in oxygen-enriched environment, will
CoO is converted into Co3O4Without reducing Co3O4The mechanical strength at carbon carrier interface.Discrete Co3O4Layer can be coated with amorphous
State carbon-coating.This carbon-coating can be by Co3O4It is attached on carbon carrier.
In a specific aspect of the invention, oxygen evolution reaction (OER) elctro-catalyst is described.OER elctro-catalyst can wrap
Include carbon carrier；The discrete catalytic Co directly contacted with carbon carrier3O4Nanometer layer；With amorphous state continuous carbon-coating (for example, carbon
Fibrous paper and/or the processed carbon fiber paper of acid).Discrete catalytic Co3O4Nanometer layer can be located at carbon carrier and amorphous state
Between continuous carbon-coating.The thickness of amorphous state carbon-coating can be 0.5nm to 15nm, and preferably 1nm to 10nm, more preferably 3nm are extremely
5nm and/or discrete catalytic Co3O4Nanometer layer with a thickness of 1nm to 1000nm, preferably 500nm.In an example
In, carbon carrier can substantially be coated with discrete catalytic Co3O4Nanometer layer.In some cases, discrete catalytic
Co3O4Nanometer layer can also include the hydroxide (CO (OH) of cobalt (II) oxide (CoO), cobalt2), or both.For example,
OER catalyst may include the CO (OH) of at most 25 weight %2With the Co of 75 weight % or more3O4.In some cases, OER
Unordered (the D)-Raman peak (Disorder (D)-Raman) and graphite (G)-Raman (Graphite (G)-Raman) of elctro-catalyst
Peak (ID/IG) ratio can be 0.2 to 0.9, preferably 0.6, which may indicate that the minimum defect on carbon support.This
The OER elctro-catalyst of invention may include in the electrodes.This electrode may include for by water electrolysis resolve into hydrogen and/or
In the equipment (for example, electrolytic cell) of oxygen.The equipment can also include for accommodating the container of electrolyte aqueous solution, to electrode and match
It is set to and applies alive power supply on the electrode.
In another aspect of this invention, the method for preparing OER elctro-catalyst is described.This method may include: that (a) is obtained
Carbon carrier, it includes the discontinuous cobalt precursors nanometer layer of deposition on the carbon carrier；(b) heat treatment comes from step under vacuum conditions
(a) cobalt substance is converted CoO by carbon carrier；(c) carbon carrier of the heat treatment from step (b) in oxygen-enriched environment, with
Cobalt (II, III) oxide (CO is converted by COO3O4).In some cases, the carbon carrier from step (a) may include heavy
Product is carbon containing (for example, hydrocarbon, glycosyl compound, sulfonation carbon compound, nitrogen base carbon compound, carbon-based on discontinuous cobalt precursors layer
Monomer, aromatic compound, or any combination thereof, preferred glucose) layer, heat treatment step (b) and/or (c) by carbon-containing bed conversion
For amorphous state carbon-coating.(i) acid processing carbon carrier can be passed through；(ii) is being enough discontinuous cobalt species precursor nanolayer deposition
Make to contact through the carbon carrier of acid processing with cobalt precursors under the conditions of on carbon support, to obtain the carbon carrier of step (a)
Material (such as carbon fiber paper or carbon cloth).For example, electrochemical deposition (ECD), atomic layer deposition (ALD) can be used or change
Vapor deposition (CVD) is learned to deposit cobalt precursors.
In some examples of the invention, the method that water electrolysis is resolved into hydrogen and/or oxygen is described.This method can wrap
Include: aqueous solution of the electrolysis comprising any one of electrolyte and OER or HER catalyst of the invention simultaneously generates hydrogen, oxygen
Or both.Hydrogen, oxygen or both can be collected.
The definition of various terms and phrase used in this specification included below.
Any variant of phrase " water-splitting " or the phrase describes the chemical reaction that water is separated into oxygen and hydrogen.
Term " about " or " approximation " be defined be understood by ordinary skill in the art close to.It is unrestricted at one
Property embodiment in, which is defined as within 10%, within preferably 5%, within more preferably 1%, and be most preferably
Within 0.5%.
Term " weight % ", volume % " or " mole % " are respectively referred to based on the material total weight including component, material
Weight percent, percent by volume or the molar percentage of the component of total volume or total moles.In a non-limiting implementation
In example, 10 grams of groups in 100 grams of materials are divided into the component of 10 weight %.
Term " substantially " and its variant are defined as including the model within 10%, within 5%, within 1% or within 0.5%
It encloses.
When in claim and/or specification in use, term " inhibition " or " reduction " or " preventing " or " avoiding " or
Any variant of these terms includes any measurable reduction or complete inhibition in order to reach expected result.
The term used in specification and/or claim " effective " mean to be enough to realize it is required, expected or
Desired result.
When not no numeral-classifier compound element in claims or specification with term "comprising", " comprising ", " containing " or
When " having " is used together, can indicate " one ", but its also with " one or more ", "at least one" and " one or be more than
One " meaning it is consistent.
Word "comprising", " having ", " comprising " or " containing " are inclusive or open and are not excluded for additional
Unlisted element or method and step.
Elctro-catalyst of the invention can with "comprising" disclosed special component, component, composition etc. in the specification,
Or " consisting essentially of ", or " being made from it ".It is unrestricted at one about transitional phrases " substantially by ... form "
Property aspect, the essential characteristic and novel feature of OER and/or HER elctro-catalyst of the invention are their catalytic water cracking reactions
Ability.
According to the following drawings, detailed description and embodiment, other objects of the present invention, feature and advantage will be aobvious and easy
See.It should be understood, however, that although attached drawing, detailed description and embodiment show specific embodiments of the present invention,
But it only provides and is not intended to limit in an exemplary manner.Furthermore it is possible to be contemplated by the detailed description, spirit of the invention and
Change and modification in range will be apparent those skilled in the art.In other embodiments, from specific
The feature of embodiment can be combined with the feature from other embodiments.For example, the feature from an embodiment
It can be combined with the feature from any other embodiment.In other embodiments, supplementary features can be added to
In specific embodiment described herein.
Detailed description of the invention
By having benefited from following specific embodiments and with reference to attached drawing, advantages of the present invention for those skilled in the art and
Speech will be apparent.
Figure 1A to Fig. 1 C is the cross-sectional view of catalyst of the present invention.Figure 1A depicts the discontinuous Co on carbon carrier two sides3O4
Nanometer layer.Figure 1B depicts the discontinuous Co on carbon carrier side3O4Nanometer layer.Fig. 1 C is discontinuous on description carbon carrier
Co3O4The top view of the catalyst of nanometer layer.
Fig. 2 is the schematic diagram that the method for OER elctro-catalyst is prepared using two-step thermal processing method of the invention.
Fig. 3 is the signal of the method for the OER elctro-catalyst for having carbon-coating using two-step thermal processing method preparation of the invention
Figure.
Fig. 4 is the schematic diagram reacted using the water-splitting of OER catalyst of the invention.
Fig. 5 shows X-ray diffraction (XRD) map of catalyst and comparative catalyst of the present invention.
Fig. 6 is shown in the catalyst of the present invention before and after acid-OER test and the X-ray diffraction of comparative catalyst
(XRD) map.
Fig. 7 A is scanning electron microscope (SEM) image of the cobalt substance of the electro-deposition on CP.
Fig. 7 B is the SEM image of catalyst of the present invention.
Fig. 8 A is transmission electron microscope (TEM) image of the thin slice peeled off from the electrode including catalyst of the present invention.
Fig. 8 B is the high-resolution TEM image for the Slice Image peeled off from the electrode including catalyst of the present invention.Fig. 8 B
In illustration be diffraction image.
Fig. 8 C is high angle annular diffractive field scan transmission electron microscope (HAADF-STEM) figure of catalyst of the present invention
Picture.
Fig. 9 shows the Raman spectrum of catalyst and comparative catalyst of the present invention.
Figure 10 shows the Raman spectrum of carbon paper under a variety of heat treatments.
Figure 11 A to Figure 11 D shows the not carbon-containing bed catalyst of the present invention of (A) catalyst of the present invention, (B), (C) comparison
Co3O4The x-ray photoelectron spectroscopy (XPS) of the Co 2p of/CP catalyst and (D) comparison CoO/CP catalyst.
Figure 12 A to figure 12 C describes the electrochemical measurement figure of catalyst and comparative catalyst of the present invention.Figure 12 A is with 5mV/s
Sweep speed, in 0.5M H2SO4The catalyst of the present invention of middle measurement and the polarization curve of comparative catalyst, wherein electric current is by carbon
The geometric area of fibrous paper normalizes and potential is corrected by internal resistance；Figure 12 B is catalyst of the present invention and comparative catalyst
Double layer capacity (Cdl) curve graph；Figure 12 (C) is the Tafel slope (Tafel extracted from the polarization curve in Figure 12 A
slopes)。
Figure 13 is shown in the Co (OH) of the invention prepared under various temperature2Precursor material, cobalt/cobalt oxide and cobalt phosphide
The SEM image of catalyst.
Figure 14 shows comparative catalyst and cobalt phosphide catalyst of the invention for the electro catalytic activity of the OER in water.
Figure 15 shows comparative catalyst and cobalt phosphide catalyst of the invention for the electro catalytic activity of the HER in water.
Although the present invention is easy to carry out various modifications and alternative forms, specific embodiment is in the accompanying drawings with example
Mode show and can be described in detail herein.Attached drawing may be not drawn to scale.
Specific embodiment
Have been found that solution to the problem relevant to routine OER catalyst.The solution be in carbon carrier and
There is discrete catalytic Co between amorphous state carbon-coating3O4The OER catalyst of nanometer layer, wherein discrete catalytic Co3O4
Nanometer layer is directly contacted with carbon carrier.In addition, the method that the present invention prepares OER catalyst is provided Co3O4It is attached to carbon carrier
On without reduce Co3O4The means of the mechanical strength at carbon carrier interface.In Co3O4Top is formed in situ amorphous state carbon-coating and can incite somebody to action
Catalytic Co3O4Discontinuous nanometer layer is attached on carbon carrier, and which suppress cobalt substances from the separation or dissolution on carbon carrier, from
And provide stable catalyst in acid or alkaline medium.It is worth noting that, the Co as shown in embodiment part3O4OER
Catalyst is with high activity and has than conventional catalyst (for example, by RuO2Nano particle is in the phase covered by ionomer
With the OER catalyst prepared on carbon carrier, and/or the Co by casting on the carbon paper that ionomer covers3O4Nano particle system
Standby OER catalyst (for example,DuPont, the U.S.)) longer service life.Coated carbon-coating restrained effectively
The direct degradation on the surface CP, and mechanical support layer is provided to further suppress the discontinuous Co of catalytic3O4Nanometer layer is from substrate
On peeling.
The non-limiting aspect of these and other of the invention is discussed in more detail in following part.
A.OER elctro-catalyst
OER elctro-catalyst of the invention includes carbon carrier (for example, carbon fiber paper), which there is deposition (coating) to exist
Discontinuous catalytic Co on carbon support3O4Nanometer layer.Catalytic Layer can be at one, two, three, four of carbon carrier
Or on all surface, preferably on all surface.It can be in carbon carrier/discontinuous catalytic Co3O4Amorphous is formed around nanometer layer
State continuous carbon-coating, to provide stability for catalyst.
The structure of 1.OER elctro-catalyst
Figure 1A and 1B is the cross-sectional view of unrestricted OER catalyst 100 and 100' of the invention.Catalyst 100 is retouched
The discontinuous Co on all surface of carbon carrier is drawn3O4Nanometer layer, catalyst 100' depict discontinuous on a surface
Co3O4Nanometer layer.Fig. 1 C is the top view of the OER catalyst 100 of no amorphous carbon coating.Every kind of catalyst includes carbon carrier
102, with the discontinuous Co in region 1063O4Nanometer layer 104 and amorphous state continuous carbon-coating 108.Co as shown in the figure3O4Nanometer layer
104 have space between region 106.In some embodiments, amorphous state continuous carbon-coating 108 and nonessential.
OER elctro-catalyst can have a large amount of sp in the skeleton of carbon carrier2Carbon.Raman spectroscopy measurement can be used
Sp in carbon carrier2Carbon, and determine sp2The carbon material (D) and graphene (sp of hydridization2Carbon) in ratio between disordered structure
(ID/IG).With the increase of ratio, there is less orderly sp in structure2Carbon atom.In the present invention, the I of OER catalystD/IG
Can be 0.2 to 0.9 or 0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.70,0.75,0.8,
0.85,0.9 or any range or value therebetween.In some cases, the I of carbon carrierD/IGIt is 0.6.It is not wishing to be bound by theory,
Think that the method that OER elctro-catalyst is prepared as follows and described in the whole instruction provides stable carbon support structure.
A. carbon carrier
Carbon carrier can have big surface area, good electric conductivity and have in various liquid electrolytes excellent
Chemical stability.Carbon carrier can be has a large amount of sp in carbon carrier skeleton2Any conductive carbon material of carbon.The I of carbon carrierD/
IGCan be 0.1 to 0.8 or 0.1,0.15,0.20,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,
0.7,0.75,0.8 or any range or value therebetween.In some cases, the I of carbon carrierD/IGIt is 0.17.Carbon carrier it is non-
Restricted embodiment includes carbon cloth, carbon fiber paper, Reticulated vitreous carbon and graphene, Toray paper or Bucky paper.Preferably implementing
In scheme, carbon carrier is carbon fiber paper.Carbon carrier can be obtained from various commercial suppliers, such as Shenglongpan
Electric Co., Ltd. (China) or Hobby Carbon CNC Ltd. (China).
B. discontinuous catalytic nanometer layer
Discontinuous catalytic cobalt nanometer layer (nanometer layer) can be made as described in embodiment part and the whole instruction
It is standby.Nanometer layer may include Co3O4And hydroxide (the CO (OH) of optional Co (II) oxide (CoO) and/or cobalt2).It urges
The property changed cobalt substance can promote to be formed oxygen by water (for example, 2H2O+4e-→O2+4H+)。
Discontinuous Co3O4The thickness of nanometer layer can be 1nm to 1000nm, preferably 500nm or 1nm, 25nm, 50nm,
75nm、100nm、125nm、150nm、175nm、200nm、225nm、250nm、300nm、325nm、350nm、375nm、400nm、
425nm、450nm、475nm、500nm、525nm、550nm、575nm、600nm、625nm、650nm、675nm、700nm、
725nm, 750nm, 775nm, 800nm, 825nm, 850nm, 825nm, 900nm, 925nm, 950nm, 975nm, 1000nm or its
Between any value or range.In some embodiments, discontinuous Co3O4Nanometer layer can be Co3O4Particle, Co3O4Particle
Combination or the most Co to be arranged with multilayer3O4Particle (for example, particle stacking).The diameter of these particles and/or the height of stacking
It can determine the thickness of nanometer layer.For example, the diameter of each particle and/or stack height can be 1 to 1000nm, preferably
500nm or 1nm, 25nm, 50nm, 75nm, 100nm, 125nm, 150nm, 175nm, 200nm, 225nm, 250nm, 300nm,
325nm、350nm、375nm、400nm、425nm、450nm、475nm、500nm、525nm、550nm、575nm、600nm、
625nm、650nm、675nm、700nm、725nm、750nm、775nm、800nm、825nm、850nm、825nm、900nm、
Range between 925nm, 950nm, 975nm, 1000nm or any value or both.Catalytic nanometer layer can attach to carbon carrier
Surface on.For example, Co3O4It can attach in substrate.It is not wishing to be bound by theory, it is believed that the chemical stability of catalyst is returned
Because in Co3O4Stability and/or Co3O4Adhesion between carbon substrate.
Catalytic cobalt nanometer layer may include 75 weight % or more or 75 weight %, 76 weight %, 77 weight %, 78
Weight %, 79 weight %, 80 weight %, 81 weight %, 82 weight %, 83 weight %, 84 weight %, 85 weight %, 86 weights
Measure %, 87 weight %, 88 weight %, 89 weight %, 90 weight %, 91 weight %, 92 weight %, 93 weight %, 94 weight %,
95 weight %, 96 weight %, 97 weight %, 98 weight %, 99 weight %, 100 weight % or any range therebetween or value
Co (II, III) oxide (Co3O4)。CO(OH)2It can be at most 25 weight %, or with 25 weight %, 24 weight %, 23 weights
Measure %, 22 weight %, 20 weight %, 19 weight %, 18 weight %, 17 weight %, 16 weight %, 15 weight %, 14 weight %,
13 weight %, 12 weight %, 11 weight %, 10 weight %, 9 weight %, 8 weight %, 7 weight %, 6 weight %, 5 weight %, 4
The amount of weight %, 3 weight %, 2 weight %, 1 weight %, 0 weight % or any range therebetween or value exists.CoO can be with
At most 1 weight %, 0.5 weight %, 0.25 weight %, 0.1 weight %, 0 weight % or any value or range therebetween amount deposit
?.CoO can be at most 1 weight %, 0.5 weight %, 0.25 weight %, 0.1 weight %, 0 weight % or any value therebetween
Or the amount of range exists.Catalytic nanometer layer can have the Co of 95 weight %3O4With the CO (OH) of 5 weight %2, 90.2 weights
Measure the Co of %3O4With the CO (OH) of 9.8 weight %2Or 79.0 weight % Co3O4With the Co (OH) of 21.0 weight %2Group
At.
C. amorphous state continuous carbon-coating
Amorphous state continuous carbon-coating can be prepared as described in embodiment and the whole instruction.Amorphous state continuous carbon-coating can
And have it is few even without crystal structure and/or be it is significant porous, the reactants and products that are (such as water, molecular oxygen and
Hydrogen ion) discontinuous catalytic nanometer layer can be passed in and out.Amorphous state continuous carbon-coating can have the thickness of 1 carbon-coating,
For 0.5nm to 15nm, or preferably 1nm to 10nm, more preferable 3nm to 5nm or 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm,
10nm, 11nm, 12nm, 13nm, 14nm, 15nm or any value or range therebetween.In some embodiments, amorphous state carbon-coating can
To be conductive.
B.The preparation of OER elctro-catalyst
OER elctro-catalyst can be prepared as described in embodiment and the whole instruction.It is worth noting that, this method
Including two-step thermal processing, which mainly reduces the degradation of carbon support structure, while converting cobalt precursors material to
Co3O4.First heat treatment can carry out under anoxic conditions (for example, under vacuum), and convert CoO for cobalt precursors, to be formed
CoO/ carbon support material.CoO/ carbon support material can be under excess oxygen (for example, existing in air, oxygen or oxygen-enriched air
Under) heating, Co is converted by CoO3O4.Chemically stable OER elctro-catalyst is provided using gradually heat treatment and/or by Co3O4
It is attached on carbon carrier.For example, OER elctro-catalyst is stable in corrosivity acidic environment and will not be by Co3O4Acid point
Solution forms solubility CoO and O2。
1. two-step thermal processing
Fig. 2 is the schematic diagram for preparing the method 200 of OER elctro-catalyst.In the first step of this method, before cobalt being obtained
Body/carbon support material 202.Cobalt precursors/carbon support material 202 includes with the cobalt precursors 204 being deposited on carbon support
Carrier 102.As shown, cobalt precursors 204 are coated in the two sides of carrier material 202, it should be understood, however, that all sides are all
It may include cobalt precursors 204.
In step 2, cobalt precursors/carbon support material 202 can be heated, under vacuum (anaerobic environment) to generate CoO/ carbon
Carrier material 206.During the heat treatment of cobalt precursors/carbon support material 202, cobalt precursors 204 can be converted into the oxide region Co
Domain 208, to generate CoO/ carbon support material 206.The region CoO 208 constitutes CoO layers discrete.It is not wishing to be bound by theory,
For task in the presence of the oxygen of minimum, heat treatment cobalt precursors/carbon support material 202 maintains the surface integrity of carbon carrier,
Co (II) O is converted by cobalt precursors simultaneously.First heat treatment condition may include 300 DEG C to 550 DEG C, 350 DEG C to 500 DEG C, or
300 DEG C, 325 DEG C, 350 DEG C, 375 DEG C, 400 DEG C, 425 DEG C, 450 DEG C, 475 DEG C, 500 DEG C, 525 DEG C, 550 DEG C or times therebetween
The temperature and 1mTorr to 10mTorr (0.14 Pascal to 1.3 Pascals) of what range or value, 3mTorr to 8mTorr,
4mTorr to 7mTorr or 1mTorr, 2mTorr, 3mTorr, 4mTorr, 5mTorr, 6mTorr, 7mTorr, 8mTorr,
9mTorr, 10mTorr, or it is less than 500mTorr, or the reduced pressure (vacuum) of any value or range therebetween, until cobalt precursors
It has been essentially converted to CoO (for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 10 hours).Under these conditions,
It does not generate Co metal substantially, or does not generate Co metal.
In step 3, CoO/ carbon support material 206 can be heat-treated under oxygen-enriched environment, convert CoO to
Co3O4And generate Co3O4/ carbon carrier 210.Co3O4/ carbon carrier 210 includes discontinuous layer 204, which includes Co3O4
Region 106.Co3O4/ carbon carrier 210 may be used as OER elctro-catalyst.Second heat treatment condition may include 20 DEG C to 300 DEG C,
25 DEG C to 200 DEG C, 30 DEG C to 100 DEG C or 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 100 DEG C, 150 DEG C, 200
DEG C or any range therebetween or value temperature and 500mTorr to 1500mTorr (66 Pascals to 200 Pascals),
600mTorr to 1000mTorr, 800mTorr to 700mTorr or 500mTorr, 600mTorr, 700mTorr, 800mTorr,
900mTorr, 1000mTorr, 1200mTorr, 1300mTorr, 1400mTorr, 1500mTorr or any value or model therebetween
The reduced pressure (vacuum) enclosed, until CoO has been essentially converted to Co3O4(for example, 1 hour, 2 hours, 3 hours, 4 hours, it is 5 small
When or 10 hours).Under these conditions, micro Co metal and Co are only generated3O4The mechanical strength at carbon carrier interface will not
It reduces.
2. the two-step thermal processing of carbon compound
In some embodiments, OER elctro-catalyst may include amorphous state continuous carbon-coating.Fig. 3 is to be used to prepare OER electricity
The schematic diagram of the method 300 of catalyst 100, with amorphous state pantostrat 108.The heat treatment of 2 steps described in Fig. 2 can be used
Method prepares OER elctro-catalyst 100 or 100', and adds following substance.Cobalt precursors/carbon support material 202 may include carbon containing
Layer, this is carbon-containing bed can be converted into amorphous state carbon-coating 108 during the first and/or second heat treatment step.Referring to Fig. 3, in step
In rapid 1, cobalt precursors/carbon support material 202 can be contacted with carbon compound to form coated cobalt precursors/carbon support material
302.Coated cobalt precursors/carbon support material 302 may include containing carbon coating 304, carrier 102 and cobalt precursors 206.Containing carbonization
Closing object can be any carbon compound that can be carbonized when heated.The non-limiting example of carbon compound includes hydrocarbon, sugar
Based compound, sulfonation carbon compound, nitrogen base carbon compound, carbon-based monomer, aromatic compound, or any combination thereof.In specific feelings
Under condition, glucose is used.Contacted with carbon compound with formed coated cobalt precursors/carbon support material 302 may include by
Cobalt precursors/carbon support material 202, which immerses, to be contained in carbon solution (for example, alcoholic solution containing carbon solution), in cobalt precursors/carbon support material
Other known methods of upper spraying or atomization carbon compound or coated substrate.In some embodiments, carbon compound is only
Part applied to the elctro-catalyst containing cobalt precursors.The amount of carbon compound be can change to adjust the thickness of amorphous state carbon-coating
Degree.For example, cobalt precursors/carbon support material 202 can be immersed in 1mg/L to 10mg/L or 1mg/mL, 2mg/L, 3mg/L,
4mg/L, 5mg/lL, 6mg/L, 7mg/L, 8mg/L, 9mg/L, 10mg/L, preferably in the glucose solution of 5mg/L.In step 2 and
In 3, coated cobalt precursors/carbon support material 302 can undergo two steps described in embodiment, Fig. 2 and the whole instruction
Heat treatment, to form OER elctro-catalyst 100.During two-step thermal processing, carbon compound is converted into amorphous state carbon-coating, and cobalt
Nanometer layer keeps its form.It is not wishing to be bound by theory, it is believed that conversion of the carbon compound to amorphous carbon helps to increase cobalt
The combination of substance and carbon carrier.OER elctro-catalyst 100' can be prepared in a similar way, the difference is that cobalt precursors 206
It is only applied to the side of carbon carrier.
3. the preparation of cobalt precursors/carbon support material
Cobalt precursors/carbon carrier material can be prepared by providing cobalt precursors to one or more than one surface of carbon carrier
Material.In non-limiting embodiment, electrochemical deposition (ECD), atomic layer deposition (ALD) or chemical vapor deposition can be passed through
(CVD) method deposits cobalt precursors on the carbon carrier.Cobalt precursors can be any suitable cobalt salt, such as cobalt nitrate (II) six
Hydrate.Cobalt salt can be bought from various commercial sources, such as Sigma-(U.S.).The amount of cobalt precursors can be based on
It is supplied to the total amount of the element cobalt of the carbon carrier of given weight.
In some embodiments, carbon carrier is handled through acid.The acid processing of carbon carrier can promote carbon surface and cobalt substance
Combination.Acid processing may include under oxidative conditions with acid processing carbon carrier.The non-limiting embodiment of acid includes sulfuric acid
(H2SO4), hydrochloric acid (HCl), hydrophily organic acid, or combinations thereof, with formed through acid processing carbon carrier (for example, through acid processing
Carbon carrier 102).It is not wishing to be bound by theory, it is believed that a part of acid oxidase carbon support, then it can be with cobalt substance knot
It closes.For example, carbon carrier can be impregnated with alcohol (for example, methanol or ethyl alcohol), which is added to containing electrolyte
In acid solution (for example, aqueous sulfuric acid containing potassium chloride), then carried out in 1.5V between 2.3V with cyclic voltammetry
Oxidation.
4. the preparation of cobalt phosphorus/carbon support material
CoP and/or CoP can be prepared by obtaining cobalt precursors/carbon support material2Electrode.Cobalt precursors/carbon support material
It may include the carrier with the cobalt precursors being deposited on carbon support.In some embodiments, cobalt precursors/carrier material
It is the CO (OH) being electrodeposited on carbon cloth2。
Cobalt precursors/carbon support material can contact under vacuum (anaerobic environment) with phosphorus source (such as red phosphorus), to generate
CoP/ carbon support material and COP2/ carrier material.During the heat treatment of cobalt precursors/carbon support material, phosphorus precursor can be with cobalt
Precursors reaction forms CoP and/or COP2Region, to generate CoP and/or COP2/ carbon support material.It is not wishing to be bound by theory, recognizes
For in the presence of phosphorus source and minimal amount of oxygen, processing cobalt precursors/carbon support material maintains the surface integrity of carbon carrier, together
When by cobalt precursors convert Co (III) P or Co (IV) P2.Heat treatment condition may include 300 DEG C to 850 DEG C, 350 DEG C to 550
DEG C or 300 DEG C, 325 DEG C, 350 DEG C, 375 DEG C, 400 DEG C, 425 DEG C, 450 DEG C, 475 DEG C, 500 DEG C, 525 DEG C, 550 DEG C, 600 DEG C,
The temperature and 1mTorr to 10mTorr of 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or any range therebetween or value
(0.14 Pascal to 1.3 Pascals), 3mTorr to 8mTorr, 4mTorr to 7mTorr or 1mTorr, 2mTorr, 3mTorr,
4mTorr, 5mTorr, 6mTorr, 7mTorr, 8mTorr, 9mTorr, 10mTorr or less than 500mTorr or therebetween any
The reduced pressure (vacuum) of value or range, until cobalt precursors have been essentially converted to (for example, 1 hour, 2 hours, 3 hours, it is 4 small
When, 5 hours or 10 hours) cobalt phosphide is (for example, CoP, COP2、Co2P3Or mixtures thereof).Under these conditions, substantially
Co metal is not generated, or does not generate Co metal.Cobalt phosphide may be used as HER elctro-catalyst and/or OER elctro-catalyst.
The purposes of C.OER elctro-catalyst
OER elctro-catalyst of the invention can be used for by water hydrogen manufacturing and oxygen.For example, catalyst of the present invention can be based on
The hydrolyzer of PEM is integrated, for expeditiously by water hydrogen manufacturing and oxygen.Referring to Fig. 4, water-splitting system 30 of the invention is provided
Non-limiting representative.System 400 may include container 402, OER elctro-catalyst 100, to electrode 404 (for example, HER of the invention
Elctro-catalyst), for ion transmission Porous barriers 406, power supply 408 and aqueous, alcohol or organic conducting solution
410.In some embodiments, conductive aqueous solution 410 may include electrolyte.The non-limiting embodiment of electrolyte
Including Li+、Rb+、K+、Cs+、Ba2+、Sr2+、Ca2+、Na+And Mg2+Hydroxide, sulfuric acid, methanesulfonic acid, nitric acid, the mixing of HCl
Object, organic acid such as acetic acid etc..Electrolyte is also possible to gel and/or solid.OER elctro-catalyst 100 may be used as anode, to electricity
Pole 404 can be cathode.Any suitable cathode, such as platinum or platinum/graphen cathode can be used.Power supply 408 can be just
Negative electrode both ends apply voltage, so that enough electric currents are by conducting solution water-splitting is generated hydrogen and anode at cathode
Place generates oxygen.Oxygen is generated at anode with the contact of OER elctro-catalyst 100 by water.Due to sinking on carbon support
Discontinuous Co is accumulated3O4Nanometer layer and it is enclosed in discontinuous Co3O4Amorphous state carbon-coating in nanometer layer, the water of catalytic cobalt substance
Lytic activity is extended.When using cobalt phosphide nanometer layer, cobalt phosphide substance can produce cobalt/cobalt oxide (for example,
Co3O4), this causes on carrier surface (such as carbon cloth or carbon paper), and there are the mixtures of cobalt phosphide and cobalt/cobalt oxide.
Embodiment
It will the present invention will be described in more detail by specific embodiment.It provides following embodiment to be for illustration purposes only, not
It is intended to limit the invention in any way.Those skilled in the art will readily recognize that can change or modify and is various non-key
Parameter is to generate substantially the same result.
Embodiment 1
(preparation of OER elctro-catalyst of the invention)
Material: all chemical reagent are purchased from Sigma(U.S.) comprising cobalt nitrate (II) hexahydrate, Portugal
Grape sugar, potassium hydroxide (KOH), sulfuric acid (H2SO4) and ethyl alcohol.Ultrapure water is obtained from Millipore filtration system.
The electrochemical deposition of Co substance on carbon fiber paper: carbon paper (1cm × 2.5cm) is impregnated with ethyl alcohol first, is then existed
0.5M H2SO4It is followed between 1.5V to 2.3V (relative to Ag/AgCl, in saturation KCl solution) in solution with cyclic voltammetry
Ring 10 times is aoxidized.Then the carbon paper of oxidation (1cm × 1cm) is immersed into 0.1M Co (NO3)2To electro-deposition in solution
Co- precursor.Pt foil and Ag/AgCl (in saturation KCl solution) electrode are used separately as to electrode and reference electrode.In PGSTAT
With 10 minutes to 60 minutes constant-current mode (- 10mA/cm in 302N Autolab work station2) carry out electro-deposition.Then
By the sample exposure of deposited in air to form the superficial layer of oxide and hydroxide, for further processing (before Co-
Body/carbon paper).
Preparation is coated with the Co of carbon compound on carbon paper3O4: Co precursor/carbon paper of preparation is soaked under slow stirring
Enter in 5mg/mL glucose solution 4 hours, takes out from solution, be then dried at room temperature for.
Two-step thermal processing: the Co- precursor/carbon paper for being coated with glucose is put into tube furnace, then vacuumize (<
5mTorr).Then heating furnace is heated in 2 hours 350 DEG C and kept again at such a temperature 1 hour.Later, air is led to
Enter heating furnace chamber and vacuum pressure is adjusted to 1000mTorr and is kept for 4 hours, wherein glucose is thermal decomposited into amorphous carbon
And it is equably covered on and is formed by Co3O4/ carbon paper [is coated with Co3O4C/ carbon paper (vacuum 1h+ air 4h)] on.Use height
The Co that precision is weighed on balance measurement carbon paper3O4Catalyst loading quantity is 12.6mg.
Embodiment 2
(Co3O4The preparation of/carbon paper OER elctro-catalyst)
Co is prepared using experiment condition in the same manner as in Example 13O4/ carbon paper, the difference is that being omitted carbon-containing bed.
Use the Co on high-precision weighing balance measurement carbon paper3O4Catalyst loading quantity (50 minutes) are 12.6mg.
Embodiment 3
(preparation of OER elctro-catalyst contrast sample)
CoO/ carbon paper (embodiment 3A).Cobalt precursors are deposited on carbon paper using the step in embodiment 1, then in vacuum
Processing lower heating 1 hour to obtain CoO/ carbon paper.
Co3O4/ carbon paper (embodiment 3B).Cobalt precursors are deposited on carbon paper using the step in embodiment 1, then in sky
5 hours are heated to obtain Co in gas with 350 DEG C3O4/ carbon paper.Use the carbon paper of high-precision weighing balance measurement embodiment 3A and 3B
On Co3O4Catalyst loading quantity is 12.6mg ± 2mg.
Co coated with Nafion3O4/ carbon paper (embodiment 3C) and RuO2The preparation of/carbon paper (embodiment 3D): by porcelain
Directly anneal Co (NO in boat3)2·6H2O and RuCl3Precursor prepares Co3O4And RuO2Powder is placed in Muffle furnace, then with
2.5 DEG C/min of slope is heated to 350 DEG C and is kept for 5 hours in air.Later, it is cooled to room temperature heating furnace.Nafion
(DuPont, the U.S.) is normally used as the polymer of coating, for guard catalyst from peeling off during OER.
Co coated with Nafion3O4/ carbon paper catalyst.First by Co3O4Powder (62.5mg) is dispersed in by equal volume amounts
2- propyl alcohol (0.5mL) and water (0.5mL) composition in the mixed solvent, and mixture is ultrasonically treated using ultrasonic oscillator
30 minutes.Then, by the mixture drop coating of 200 μ L fine dispersions on the carbon paper through acid oxidase, 70 μ L, 1.0 weight % is added
The 2- propanol solution of Nafion catalyst to be fixed on carbon paper surface, further at 40 DEG C in air drying to carry out
Electrochemical measurement.In addition, preparing the carbon paper (RuO through acid oxidase using step similar as described above2@nafion/ carbon paper) on
RuO2。
Embodiment 4
(performance characterization)
Method
Before and after electrochemical measurement, using X-ray diffraction (XRD), field emission scanning electron microscope (ESEM),
Transmission electron microscope (TEM), Raman spectrum and x-ray photoelectron spectroscopy (XPS) characterize catalyst sample.
XRD analysis: by X-ray diffraction (XRD, Bruker D8 Discover diffractometer, are radiated using CuK α,) analysis sample crystal structure.FESEM:FESEM (FEI Quanta 600) is for observing catalyst
Configuration of surface and electron energy loss spectroscopy (EELS) mapping.TEM: by transmission electron microscope (FEI Titan ST,
Operated under 300KV) display nano crystals structure.
Raman spectrum: using Raman spectrometer LabRAMAramis (HoribaJobinYvon) and 100cm is studied-1Extremely
3500cm-1Range.Use diode-pumped solid (DPSS) laser that wavelength is 473nm as excitaton source.Use difference
Filter adjust sample surfaces on laser power, to avoid the heating effect to sample.Fourier transform infrared spectroscopy
The functionalizing group and urge that (Nicolet iS10 FT-IR spectrometer, Thermo Scientific) is used to characterize on carbon fiber
Agent.
XPS:XPS research is in Kratos Axis Ultra DLD spectrometer in 1 × 10-9It is carried out under the vacuum of mbar, it should
Spectrometer is detected equipped with monochromatic Al K α x-ray source (h ν=1486.6eV), multi-channel plate and the delay line operated at 150W
Device.Logical in fixed analyzer can be respectively to collect measurement result and high-resolution spectroscopy under 160eV and 20eV.In conjunction with can refer to
Sp from sample2The peak C 1s (being set in 284.4eV) of hydridization (C=C) carbon.
Performance characterization
XRD analysis: the sample using XRD analysis from embodiment 1,2,3A and 3B.Fig. 5 is shown from embodiment 1,2,3A
With the XRD spectrum of the cobalt electrode of 3B.Data line 500 is the XRD spectrum of embodiment 3B (CoO/ carbon paper).Data line 502 is to implement
Example 3B (Co3O4/ carbon paper) XRD spectrum.Data line 504 is the XRD spectrum of 1 catalyst of the embodiment of the present invention.2 θ=26.2 °
It is related to (002) of the graphite-like structure of carbon paper and (004) face to the broad peak at 53.9 °.The peak of embodiment 3A comparative catalyst
The cubic structure (JCPDS the 65-2902nd) of CoO, and embodiment 3B comparative catalyst and reality of the invention can be attributed to
Apply the peak XRD of 1 catalyst of example be it is similar, this is attributed to Co3O4Cubic structure (JCPDS the 42-1467th).
Fig. 6 shows the XRD spectrum in acid before and after OER test.Data line 600 is that the cobalt being electroplated on carbon paper (is not added
Heat) XRD spectrum, data line 602 is 2 catalyst (Co of the embodiment of the present invention3O4/ carbon paper) XRD spectrum, data line 604 is
Embodiment 3B comparative catalyst (Co3O4/ carbon paper) XRD spectrum.Data line 606 is 1 catalyst of the embodiment of the present invention after OER
XRD, data line 608 is the XRD of the embodiment 3A comparative catalyst (CoO/ carbon paper) after OER.According to XRD spectrum 600, determine
The Co- substance being electrodeposited on carbon paper (Co- substance/CP) is CO (OH)2, CoO and unordered Co3O4Mixture.
SEM: the Co/ carbon paper catalyst of electro-deposition is further analyzed by scanning electron microscope (SEM).Fig. 7 A is heating
The SEM image of cobalt precursors on preceding carbon paper.According to the image, determine that carbon paper surface is covered by discontinuous cobalt precursors nanometer layer completely.
Fig. 7 B is the SEM image of 1 catalyst of the embodiment of the present invention.It is determined according to the image, high surface area nanometer layer is soaked in glucose
Its form is still maintained after bubble, is then heated to convert carbon compound/Co precursor/CP to the Co of carbon coating3O4/ carbon paper.No
Wish bound by theory, it is believed that under anoxic conditions with the raising of heating temperature, adsorbed glucose molecule starts to be dehydrated
And crosslinking, and with the continuation of reaction, by further occurrence aromatisation and carbonization, results in the shell that is carbonized and be covered on Co3O4Piece
On the surface of shape structure (i.e. nanometer layer).
TEM: TEM, high-resolution TEM and high angle annular diffractive field scan transmission electron microscope (HAADF- are used
STEM 1 catalyst of the embodiment of the present invention) is analyzed.From flake on the electrode containing 1 catalyst of embodiment and carry out structure
Analysis.Fig. 8 A to Fig. 8 C is that the TEM of the OER catalyst from 1 catalyst of the embodiment of the present invention schemes (Fig. 8 A), HRTEM figure (figure
8B) and HAADF-STEM schemes (Fig. 8 C).From the tem analysis in Fig. 8, the amorphous state carbon-coating that thickness is about 3.6nm ± 0.5nm is found
It is uniformly coated on Co3O4On crystal.(FFT- fast Flourier becomes for the HRTEM image of selected areas and corresponding electronic diffraction
Changing) map is shown in Fig. 8 B.The image, which is shown, corresponds respectively to Co3O4Crystal face (220) and the 0.28nm of (222) and
Two spacings of lattice of 0.23nm.According to the analysis (Fig. 8 C) of HAADF-STEM image, element mapping display Co and O is uniformly distributed
In selected areas, and amorphous carbon is coated on Co3O4On plane of crystal.
Raman spectrum: Raman spectrum is for characterizing the Co catalysts from embodiment 1,2,3A and 3B.Fig. 9 shows catalyst
Raman spectrum.It is determined according to Raman Measurement, under a variety of heat treatment conditions, structure transformation and XRD the and TEM institute of Co- precursor
It is consistent to obtain result.Data line 900 is Co- precursor/carbon paper Raman spectrum (no heating), and data line 902 is embodiment 3A comparison
The Raman spectrum of catalyst, data line 904 are the Raman spectrums of embodiment 3B comparative catalyst, and data line 906 is of the invention real
The Raman spectrum of 2 catalyst of example is applied, data line 908 is the Raman spectrum of 1 catalyst of the embodiment of the present invention.
Raman spectrum is also used to detect the interfacial area between the integrality of CP, especially carbon paper and cobalt substance.About
1585cm-1The G band and sp at place2Carbon atom vibration is related；And in about 2725cm-1The 2D band at place is derived from double resonance process: photon-
Electronic band structure.In about 1370cm-1The D band peak of the original CP at place is derived from sp2Disordered structure in hydridization carbon material.Figure 10 is aobvious
The Raman spectrum of carbon paper catalyst is shown.Data line 1000 is the Raman spectrum of original carbon paper, and data line 1002 is through acid oxidase
Carbon paper Raman spectrum, data line 1004 be heated in air at 350 DEG C 5 hours carbon paper Raman spectrum, data
Line 1006 be heated in vacuum at 350 DEG C 1 hour carbon paper Raman spectrum, data line 1008 is that 1 is heated in vacuum
Hour, then heated in air 4 hours (heat treatment of 2 steps) carbon paper Raman spectrum.As shown in Figure 10, at 350 DEG C in
After annealing 5 hours in air, the I of carbon paperD/IGRatio is 0.91, this is higher than 0.62 of annealing (350 DEG C, 1 hour) in vacuum.No
Wish bound by theory, it is believed that the surface texture of carbon paper is significantly degenerated after calcining in air.However, according to embodiment 3A's
XRD analysis, 1 hour vacuum heat treatment only generates CoO/CP without generating Co at 350 DEG C3O4Catalyst.It is surprising
It is the I that two-step thermal processing process (4 hours in 1 hour+air in vacuum) providesD/IGRatio is 0.60.It is not intended to by theoretical beam
It ties up, it is believed that the first step processing in vacuum is vital to carbon paper surface texture is stablized, to provide such as electrochemical measurement
OER stability shown in part.
XPS measuring: XPS measuring is used to determine the atom composition and chemical state of embodiment 1,2,3A and 3B.According to XPS light
Spectrum, it is determined that the sample of all preparations contains carbon, oxygen and cobalt element without other impurities.Figure 11 A to Figure 11 D shows embodiment
1, the high-resolution Co 2p spectrum of 2,3A and 3B.Figure 11 A shows the high-resolution obtained by 1 catalyst of the embodiment of the present invention
Rate Co 2p spectrum, by corresponding respectively to 2p3/2、2p1/2The 779.6eV of spin(-)orbit line and two main width at 794.7eV
Peak composition.The spectrum is also included in 2p3/2And 2p1/2The high weak satellite structure for combining energy side of main peak, this shows that there are oxides
The cobalt of form.For the oxidation state of clear Co, Co 2p is carried out3/2Peak fitting.Method for peak fitting is similar to
It is combined used in Biesinger et al. (Appl.Surf.Sci., page 2011,257,2717 to 2730) with satellite structure
To the method for wide main peak fitting.To the Co 2p of spectrum3/2Peak application Shirley background.Using from Co3O4With Co (OH)2Standard
The combination of the parameter of sample has been fitted the Co 2p from 1 catalyst of embodiment well3/2.The result shows that sample contains 90.2%
Co3O4With 9.8% Co (OH)2.Similar fitting parameter is applied to Figure 11 B (2 catalyst of embodiment) and Figure 11 C (is implemented
Example 3B catalyst).2 catalyst of the embodiment (Co prepared by two-step thermal processing3O4/ carbon paper) group become 79.0% Co3O4
With 21.0% Co (OH)2.Embodiment 3B catalyst (Co3O4/ CP, air 5h) group become 84.0% Co3O4With 16.0%
Co (OH)2.Using from Co metal, CoO and Co (OH)2The combination of the parameter of standard sample has been fitted embodiment 3A well
(CoO/CP) the Co 2p in Figure 11 D3/2.According to these analyses, determine that CoO/ carbon paper contains 8.8% Co, 4.3% Co
(OH)2With 86.9% CoO.From result it was determined that most of Co- substance/carbon paper converts under vacuum heating conditions first
For CoO/ carbon paper, it is then further oxidized to Co in the air stream3O4/ CP and Co (OH)2/ CP, this and dinectly bruning in air
Co- substance/carbon paper surface composition it is similar.However, them and 1 catalyst of the embodiment of the present invention (Co coated with carbon3O4/
Carbon paper) it is very different.Carbon coating reduces Co (OH)2The content of/CP substance, this is attributed to the catalysis of the embodiment of the present invention 1
Stability of agent under the conditions of OER.
Embodiment 5
(electrochemical measurement)
Measuring condition
Reference electrode calibration: in PGSTAT 302N Autolab Potentiostat/Galvanostat (Metrohm)
Middle carry out electrochemical measurement.Graphite rod and Ag/AgCl (in saturation KCl solution) electrode are used separately as to electrode and reference electricity
Pole.Solution for reference electrode calibration is to use H before measuring230 minutes 0.5M H of purging2SO4With 1.0M KOH solution.
It uses Pt as working electrode respectively in the hydrogen saturation electrolyte solution of high-purity and reference electrode calibration is carried out to electrode.With
The average value of two potentials when sweep speed sweep current-voltage curve of 5mV/s, obtaining current get over zero passage is anti-as hydrogen electrode
The thermodynamic electric potential answered.In 0.5M H2SO4Middle E (Ag/AgCl) is 0.215V lower than E (RHE), the low 1.022V in 1M KOH.
Electrochemical measurement: by 0.5M H2SO4With in 1.0M KOH solution with the sweep speed linear scan of 5mV/s
Voltammetry (LSV) measures polarization curve to assess the OER activity of catalyst.Embodiment is carried out with time dependent potential measurement
Stability test, wherein providing constant current density (100mA/cm2).Small resistive voltage is carried out to all data based on impedance method
The correction of drop.
Electrochemical measurements: determine embodiment 1,2,3A and 3B catalyst electrochemical measurement (for example, in acid
Overpotential, electro catalytic activity and stability).
Overpotential measurement: Figure 12 A shows the polarization curve that sweep speed is 5mV/s in 0.5M sulfuric acid.Pass through carbon fiber
Electric current is normalized in the geometric area of paper, records potential after the internal resistance correction of sample.Data line 1200 is embodiment
3C comparative catalyst, data line 1202 are the curve graphs of embodiment 3B comparative catalyst, and data line 1204 is the embodiment of the present invention 1
Catalyst, data line 1206 are 2 catalyst of the embodiment of the present invention, and data line 1208 is embodiment 3A comparative catalyst, data line
1210 be embodiment 3D comparative catalyst.The onset potential of the plating catalyst of 1,2 and 3A of embodiment be all it is similar (about
1.54V), wherein they respectively reach 10mA/cm under the overpotential of 370mV, 390mV and 460mV2、20mA/cm2And 100mA/
cm2Current density.Current density is 10mA/cm2Overpotential commonly used in assessment OER catalyst electro-chemical activity.Although
1 catalyst (10mA/cm of the embodiment of the present invention2) 370mV overpotential be higher than the prior art embodiment 3C compare catalysis
Agent (220mV).
Electro catalytic activity: the electro catalytic activity of given material is proportional to its active surface area, therefore can pass through circulation
Voltammetry is associated with the double layer capacity at solid-liquid interface.
Double layer capacity analysis: in order to obtain double layer capacity, in non-faraday potential window (non-Faradaic
Potential window) in potential scanned from 1.10V to 1.24V with different sweep speeds, and by obtained electric current
Density is mapped at 1.17V relative to sweep speed, is shown in Figure 12 B.Data line 1212 is that the embodiment of the present invention 1 is catalyzed
Agent, data line 1214 are embodiment 3D comparative catalysts, and data line 1216 is the carbon paper through acid oxidase.The embodiment of the present invention 1
The capacitor of catalyst is 113.3mF/cm2, under same catalyst load capacity, which is in carbon paper (38.4mF/cm2) on
Co coated with Nafion3O4About 3 times of the capacitor of the embodiment 3D comparative catalyst of nano particle.It shows in Figure 12 B through acid
Capacitor (the 25.0mF/cm of the carbon paper of processing2) as reference.According to these as a result, determining the Co through electrochemistry3O4Nanometer layer ratio
Co on carbon paper3O4Nano particle has higher active surface area.Figure 12 C shows a variety of OER comparative catalyst (embodiments
3A, 3B and 3D) and catalyst of the present invention (Examples 1 and 2) Ta Feiertu.Data line 1218 is embodiment 3D, data line
1220 be 1 catalyst of the embodiment of the present invention, and data line 1222 is 2 catalyst of the embodiment of the present invention, and data line 1224 is real
A 3A comparative catalyst is applied, data line 1226 is embodiment 3D comparative catalyst.Co coated with carbon of the invention3O4/ carbon paper is urged
The Tafel slope of agent (embodiment 1) is about 82mV/dec, this and be coated with Nafion RuO2/ carbon paper (embodiment 3C, not
Display) value it is similar, and less than comparison the Co coated with Nafion3O4/ carbon paper (about 112mV/dec) or the CoO/ of comparison
Carbon paper (106mV/dec).According to these as a result, determining that 1 catalyst of the embodiment of the present invention is the effective catalyst for OER.
Electrochemical stability: determined 1,2 and 3A of embodiment to 3D catalyst in constant current density 100mA/cm2Under
Electrochemical stability.For all elctro-catalysts, virtual electrode potential gradually increases at any time.Determined potential steeply rise to
The time of 2.0V.Table 1 lists catalyst and reaches the hourage of 2.0V.
Table 1
According to as a result, determine embodiment 3A comparative catalyst be it is most unstable, this is attributed to it at acidic not
Stability.Compared with embodiment 3A to 3C, the catalyst of the embodiment of the present invention 1 and 2 shows longer catalyst life, simultaneously
1 catalyst of the embodiment of the present invention shows longest catalyst life.In addition to the chemical stability of catalyst, there are also it is several because
Element is considered as the reason of OER electrode failure.These factors include weak between the low electric conductivity of catalyst and catalyst and substrate
Stick.The minimum OER stability of embodiment 3B comparative catalyst found is attributed to the weak interface between catalyst and substrate
Interaction, wherein oxygen-enriched environment (during heating treatment) can degrade the surface of carbon paper substrate.According to data, determine in air
Vacuum heat treatment is added before middle oxidation and significantly improves Co3O4OER stability.According to these data, it is determined that OER stablizes
Property depends not only on the chemical stability of catalyst, additionally depends on Co3O4Adhesive force between substrate.Therefore, because discontinuous
Co3O4The protection of amorphous state carbon-coating in nanometer layer, 1 catalyst of the embodiment of the present invention show optimal stability.
The stability of media base:The electricity from embodiment 3A and embodiment 1 is assessed in alkaline medium (1.0M KOH)
The stability of catalyst.Service life is (in 100mA/cm2Constant current density under reach the potential of 2.0V) for 292.7h (embodiment
3A comparative catalyst) and 413.8h (1 catalyst of the embodiment of the present invention).1 catalyst of the embodiment of the present invention is in alkaline solution
In show excellent activity.Figure 12 A shows the polarization curve and Tafel slope number of 1 catalyst of the embodiment of the present invention
According to.For 1 catalyst of the embodiment of the present invention, Tafel slope is determined as 68.8mV/dec.It observes and generates 10mA/cm2's
Overpotential is only 310mV in 1.0M KOH, this is lower than most of reported base metal alkalinity OER elctro-catalysts.According to
The data, the stability of determining 1 catalyst of the embodiment of the present invention in media base highest in comparison OER catalyst.
In short, in acid and alkaline medium, urged with amorphous state continuous carbon-coating and deposition on the carbon carrier discontinuous
The property changed Co3O4The catalyst of the present invention of nanometer layer has at higher current densities than commercially available RuO2/ carbon paper is preferably electrochemically stable
Property.In addition, two-step thermal processing method of the invention inhibits the degradation of carbon paper surface, therefore enhance Co3O4Between substrate
Boundary strength, this is attributed to high OER stability.It is not wishing to be bound by theory, it is believed that the thin layer of carbon coating inhibits catalyst
It is peeled off from substrate.Therefore, catalyst of the invention and the method for preparing elctro-catalyst provide related to routine OER elctro-catalyst
The problem of and cost solution.
Embodiment 6
(CoP/CC and CoP of the invention2The preparation of elctro-catalyst)
Pass through the Co (OH) for making red phosphorus (0.1) Yu being electrodeposited on carbon cloth2Reaction is to prepare on CoP and carbon cloth on carbon cloth
CoP2, which continues 30 minutes in 450 DEG C, 500 DEG C, 550 DEG C, 650 DEG C, 750 DEG C, 850 DEG C under vacuum.Also 450
The reference material of red phosphorus and carbon cloth is prepared at DEG C.Temperature and loading capacity are listed in Table 2 below.Table 3 lists electrocatalyst materials, crystal knot
The granular size of structure and crystal.Figure 13 depicts the elctro-catalyst prepared at the temperature disclosed above, the Co (OH) on carbon cloth2And
The SEM image of the CoO prepared at 350 DEG C.The scale of SEM image above is 40 microns, and the scale of image below is 10 micro-
Rice.According to image, cobalt phosphide is attached to amorphous state carbon-coating in discontinuous manner.
Table 2
Table 3
Embodiment 7
(electrochemical measurement of the elctro-catalyst of embodiment 6)
By measuring polarization in 1.0M KOH solution, with the sweep speed of 5mV/s, with linear sweep voltammetry (LSV)
Curve is active come the OER and HER for evaluating the cobalt phosphide catalyst prepared in embodiment 6 and comparing CoO catalyst.With the time according to
Bad potential measurement carries out the stability test of embodiment, and which provide constant current density (100mA/cm2).Based on impedance
Spectrum carries out the correction of small ohmic drop to all data.Figure 14 shows comparison cobalt/cobalt oxide (CoO) and cobalt phosphorus of the invention
Compound sample is in the polarization curve that sweep speed is in 5mV/s, 1M KOH.It (is made under 269mV to 234mV) at 450 DEG C to 650 DEG C
The overpotential of standby sample is higher than the sample prepared at 750 DEG C and 850 DEG C.Figure 15 show comparison cobalt/cobalt oxide (CoO) and
The hydrogen of cobalt phosphide sample of the invention generates polarization curve.The cobalt phosphide sample prepared at 450 DEG C to 650 DEG C has most
Low overpotential, thus it is most active as HER elctro-catalyst.
Claims (20)
1. a kind of oxygen evolution reaction (OER) elctro-catalyst comprising:
Carbon carrier；
Discrete catalytic cobalt (the II, III) oxide (Co directly contacted with carbon carrier3O4) nanometer layer；With
Amorphous state continuous carbon-coating,
Wherein discrete catalytic Co3O4Nanometer layer is between the carbon carrier and the amorphous state continuous carbon-coating.
2. OER elctro-catalyst according to claim 1, wherein amorphous state carbon-coating with a thickness of 0.5nm to 15nm, preferably
1nm to 10nm, more preferable 3nm to 5nm.
3. OER elctro-catalyst according to claim 2, wherein discrete catalytic Co3O4Nanometer layer with a thickness of
1nm to 1000nm, preferably 500nm.
4. OER elctro-catalyst according to claim 1, wherein the carbon carrier is carbon fiber paper.
5. OER elctro-catalyst according to any one of claim 1 to 4, wherein discrete catalytic Co3O4It receives
Rice layer also includes the hydroxide (Co (OH) of Co (II) oxide (CoO), cobalt2) or both.
6. OER elctro-catalyst according to claim 5, it includes at most 25 weights of the total weight based on EOR elctro-catalyst
Measure the Co (OH) of %2With the Co of 75 weight % or more3O4。
7. OER elctro-catalyst according to any one of claim 1 to 6, wherein carbon carrier is through peracid treatment.
8. OER elctro-catalyst according to any one of claim 1 to 7, wherein D- Raman peaks and G- Raman peaks (ID/IG)
Ratio be 0.2 to 0.9, preferably 0.6.
9. OER elctro-catalyst according to any one of claim 1 to 8, wherein the OER elctro-catalyst is included in electrode
In.
10. OER elctro-catalyst according to claim 9, wherein the electrode is included in for water electrolysis to be resolved into hydrogen
And/or in the equipment of oxygen, the equipment also includes for accommodating the container of electrolyte aqueous solution, to electrode and is configured in electrode
Apply alive power supply in both ends.
11. a kind of method for preparing oxygen evolution reaction (OER) elctro-catalyst, which comprises
(a) carbon carrier is obtained, it includes the discontinuous cobalt precursors nanometer layers being deposited on the carbon carrier；
(b) heat treatment comes from the carbon carrier of step (a) to convert CoO for cobalt substance under vacuum；With
(c) heat treatment comes from the carbon carrier of step (b) to convert cobalt (II, III) oxide for CoO in oxygen-enriched environment
(Co3O4)。
12. method according to claim 11, wherein the carbon carrier of step (a) also includes before being deposited on the discontinuous cobalt
It is carbon-containing bed on body layer, and wherein heat treatment step (b) and/or carbon-containing bed amorphous state carbon-coating (c) is converted into for described.
13. method described in any one of 1 to 12 according to claim 1, wherein the carbon support material includes carbon paper.
14. method described in any one of 1 to 13 according to claim 1, wherein obtaining the carbon support material packet of step (a)
It includes:
(i) acid handles the carbon carrier；With
(ii) being enough the discontinuous cobalt precursors nanolayer deposition under conditions of on the carbon support, make through at acid
The carbon carrier of reason is contacted with cobalt precursors.
15. according to the method for claim 14, wherein the deposition in step (ii) is electrochemical deposition (ECD), atomic layer
Deposit (ALD) or chemical vapor deposition (CVD).
16. method described in any one of 2 to 15 according to claim 1, wherein it is described it is carbon-containing bed comprising hydrocarbon, glycosyl compound,
Sulfonation carbon compound, nitrogen base carbon compound, carbon-based monomer, aromatic compound, or any combination thereof, preferred glucose.
17. method described in any one of 1 to 16 according to claim 1, wherein the amorphous carbon layer with a thickness of 0.5nm extremely
15nm。
18. method described in any one of 1 to 17 according to claim 1, wherein discrete catalytic Co3O4The thickness of nanometer layer
Degree is 1nm to 1000nm, preferably 500nm.
19. a kind of method that water electrolysis is resolved into hydrogen and/or oxygen, which comprises
Any aqueous solution of the electrolysis comprising OER catalyst described in electrolyte and claims 1 to 10；With
Generate hydrogen, oxygen, or both.
20. according to the method for claim 19, further include collect hydrogen, oxygen, or both.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662324093P | 2016-04-18 | 2016-04-18 | |
| US62/324,093 | 2016-04-18 | ||
| PCT/IB2017/052154 WO2017182923A1 (en) | 2016-04-18 | 2017-04-13 | Oxygen evolution electrocatalysts with carbon coated cobalt (ii, iii) oxide layers |
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| CN109072458A true CN109072458A (en) | 2018-12-21 |
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|---|---|
| US (1) | US20190055657A1 (en) |
| EP (1) | EP3445894A1 (en) |
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| CN114300676A (en) * | 2021-11-01 | 2022-04-08 | 北京航空航天大学 | Flexible sodium-ion battery negative electrode material, preparation method thereof and battery negative electrode |
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| KR102077263B1 (en) * | 2017-12-29 | 2020-02-13 | 연세대학교 산학협력단 | Catalyst composite for conversion of mathane gas and method for converting mathane gas using the same |
| US11447882B2 (en) | 2018-04-12 | 2022-09-20 | University Of Houston System | Methods for making bifunctional porous non-noble metal phosphide catalyst for overall water splitting, electrodes for overall water splitting, and methods for electrocatalytic water splitting |
| US20210198792A1 (en) * | 2018-08-22 | 2021-07-01 | The University Of North Carolina At Greensboro | Compositions and methods for enhancing electrocatalytic efficiencies |
| US11702756B2 (en) | 2019-02-26 | 2023-07-18 | King Fahd University Of Petroleum And Minerals | Cobalt oxide film upon electron sink |
| US11408084B2 (en) | 2020-01-09 | 2022-08-09 | King Fahd University Of Petroleum And Minerals | Thin film electrode containing nanostructured cobalt oxide for water splitting |
| CN111420692B (en) * | 2020-03-23 | 2023-11-03 | 云南电网有限责任公司电力科学研究院 | Composite catalyst and preparation method thereof |
| CN114561664B (en) * | 2022-02-17 | 2023-09-26 | 广东省科学院资源利用与稀土开发研究所 | Alkaline electrocatalytic water oxygen evolution material and preparation method and application thereof |
| CN114590844A (en) * | 2022-05-04 | 2022-06-07 | 台州学院 | Mesoporous Co3O4CoO/CoP and preparation method thereof |
| CN115744849B (en) * | 2022-11-28 | 2024-06-21 | 无锡科技职业学院 | Cobalt phosphide preparation method based on tetrabutylphosphonium chloride |
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| EP3445894A1 (en) | 2019-02-27 |
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