CN107675207A - A kind of oxygen with high activity and stability separates out catalyst and preparation method thereof - Google Patents

A kind of oxygen with high activity and stability separates out catalyst and preparation method thereof Download PDF

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CN107675207A
CN107675207A CN201710841149.6A CN201710841149A CN107675207A CN 107675207 A CN107675207 A CN 107675207A CN 201710841149 A CN201710841149 A CN 201710841149A CN 107675207 A CN107675207 A CN 107675207A
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catalyst
oxygen
separates out
high activity
suspension
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邢巍
高红梅
肖瑶
刘长鹏
葛君杰
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9091Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The present invention relates to a kind of oxygen with high activity and stability to separate out catalyst and preparation method thereof, is related to water electrolysis and fuel cell catalyst technical field.Solve the complexity of conventional template method preparation process in the prior art and the not high technical problem of catalyst activity.Oxygen provided by the invention separates out the Co that catalyst is Zn doping3O4Hollow dodecahedron structure or Co3O4Hollow dodecahedron structure.The catalyst is by calcining presoma ZnxCo MOF or Co MOF are made.It is demonstrated experimentally that the Co that the Zn prepared using the inventive method is adulterated3O4Hollow dodecahedron catalyst has bigger serface and abundant oxygen defect, improves Co in oxygen precipitation process3O4Electric conductivity and to OHAbsorption.Meanwhile catalyst prepared by the inventive method is precipitated with good catalytic activity and stability under alkaline environment to oxygen, this hollow dodecahedron structure catalyst is provided effective way for water electrolysis.Method provided by the invention is simple to operate, mild condition, and operating procedure is simple, is easy to large-scale production.

Description

A kind of oxygen with high activity and stability separates out catalyst and preparation method thereof
Technical field
The present invention relates to water electrolysis and fuel cell catalyst technical field, and in particular to one kind is with high activity and stably Property oxygen separate out catalyst and preparation method thereof.
Background technology
With the raising to energy demand, and pollution of the fossil energy increasingly sharpened to environment, evoke researcher To sustainable energy development research interest.Electrochemical reaction is a kind of simple side that electric energy is effectively stored by chemical bond Method.For example, energy can produce hydrogen and oxygen by electrolysis water, this restructuring can provide the energy-electric energy of cleaning, And unique accessory substance is exactly water.However, because oxygen separates out slow dynamic process, the efficiency of water-splitting production hydrogen seriously by Limit.Therefore, it is necessary to which a kind of effective oxygen separates out elctro-catalyst to undertake the high current under low overpotential to put forward energy conversion effect Rate.Separate out material although yttrium oxide and ruthenium-oxide are considered as best so far oxygen, material it is rare and high into Originally their widely use is limited.Therefore, we there is an urgent need to the alternative energy source of developing low-cost as oxygen precipitation process Efficient elctro-catalyst.
In the past few years, a series of high activities are proposed, the metal oxygen of low cost separates out material.These analysis oxygen materials have It is that the oxide of transition metal, especially nickel and cobalt is expected to substitute yttrium oxide and ruthenium-oxide, because their rich reserves, in alkali There is corrosion resistance under property environment, also multiple variable valences.Generally using following methods to Co3O4It is excellent that oxygen separates out performance progress Change.First, it is well known that catalyst performance depends on the structural parameters of itself, including particle size, surface area and shape State.The method for being commonly used to adjustment structure is to sacrifice template, such as silicon, carbon and monodisperse polymer template.However, it is conventionally used to The template auxiliary law for preparing nanostructured is complicated, or needs further to remove template.According to this background, use in recent years Metal organic frame (MOFs) and the complex class material being made up of metal ion and organic molecule do sacrifice template, and pass through letter Single pyrolytic process is successfully prepared big specific surface area and advanced porous material.For example, Huang is used as mould by the use of ZIF-67 Plate, the Co being in perfect proportion is synthesized by heat treatment3O4Hollow dodecahedron structure (R.Wu, X.Qian, X.Rui, H.Liu, B.Yadian,K.Zhou,J.Wei,Q.Yan,X.Q.Feng and Y.Long,Small,2014,10,1932.);Also with ball Shape MOFs as sacrifice template, using its unique reactivity be prepared for double-level-metal organic frame (F.Caruso, R.A.Caruso and H.Mohwald,Science,1998,282,1111-1114.).Secondly, it is higher active in order to obtain Oxygen separates out catalyst, Co3O4In would generally add some dopants.It is by using new point as the good oxygen of performance separates out material The Zn of layerxCo3-xO4For nanostructured come what is realized, it is a kind of small secondary nanotube being grown on rhombus column subarray. Alexander Eychm ü ller develop a kind of hollow nanosponges shape structure of nickel cobalt, with Co3O4Complex is compared, this Structure oxygen is precipitated with higher catalytic activity (C.Zhu, D.Wen, S.Leubner, M.Oschatz, W.Liu, M.Holzschuh,F.Simon,S.Kaskel and A.Eychmüller,Chemical Communications,2015, 51,7851-7854.).However, the Co of doping3O4The performance improvement of catalyst, be typically considered to be due to cobalt valence state transfer draw The increase of the avtive spot risen, and for the influence of doping, do not illustrate comprehensively deeply.Improved and urged based on both the above The inspiration of agent activity methods, the catalyst gesture developed new structure and oxygen precipitation catalytic activity is improved by adding dopant exist It must go.
The content of the invention
The invention solves the not high skill of the complexity of conventional template method preparation process in the prior art and catalyst activity Art problem, there is provided a kind of oxygen with high activity and stability separates out catalyst and preparation method thereof.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows:
A kind of oxygen with high activity and stability separates out catalyst, and it is the Co of Zn doping3O4Hollow dodecahedron knot Structure;
It is as being total to/co-catalyst, with the Zn/Co's of different mol ratio example using Zn that the oxygen, which separates out catalyst,
MOF presomas do template, and presoma is made first, then the Zn that presoma is prepared by heat treatment method mixes Miscellaneous Co3O4The catalyst of hollow dodecahedron structure.
In the above-mentioned technical solutions, the molar ratio of the Zn/Co is 1:1、1:3、1:5.
A kind of oxygen with high activity and stability separates out catalyst, and it is Co3O4Hollow dodecahedron structure;
It is to be prepared Co-MOF presomas using cabaltous nitrate hexahydrate as raw material that the oxygen, which separates out catalyst, then by presoma The Co being prepared by heat treatment method3O4The catalyst of hollow dodecahedron structure.
A kind of oxygen with high activity and stability separates out the preparation method of catalyst, comprises the following steps:
A-1) at room temperature, zinc nitrate hexahydrate and cabaltous nitrate hexahydrate are scattered in methanol, obtain the first suspension;
Or a-2) at room temperature, cabaltous nitrate hexahydrate is scattered in methanol, obtains the first suspension;
B) methylimidazole is scattered in other methanol, obtains the second suspension;
C) the first suspension and the second suspension are mixed and stirred for obtaining the first sediment at room temperature;
D) by the first precipitates washed with EtOH and centrifuge, dry, obtain presoma;
E) presoma is calcined, is heated to 350 DEG C, N2Kept for half an hour under environment, change air after half an hour into, after Continue and kept for half an hour obtain the Co of Zn doping at 350 DEG C3O4The catalyst or Co of hollow dodecahedron structure3O4Hollow 12 The catalyst of face body structure.
In the above-mentioned technical solutions, the Zn/Co of zinc nitrate hexahydrate used in step a) and cabaltous nitrate hexahydrate rubs Your ratio is 1:1、1:3、1:5.
In the above-mentioned technical solutions, it is 24h to the time that the first suspension and the second suspension are stirred in step c).
In the above-mentioned technical solutions, the temperature the first sediment being dried in step d) is 80 DEG C, time 12h.
In the above-mentioned technical solutions, it is with 5 DEG C of min to carry out calcining in step e) to the second sediment-1Speed be heated to 350℃。
The beneficial effects of the invention are as follows:
The Co of Zn doping provided by the invention with high activity and stability3O4Hollow dodecahedron structure oxygen is separated out and urged Agent, relative to traditional catalyst, the present invention with the addition of Zn as altogether/co-catalyst, with the Zn/Co's of different mol ratio example MOF presomas are the Co that template prepares Zn doping by heat treatment method3O4Hollow dodecahedron structure.In hollow dodecahedron In forming process, most zinc evaporates in presoma forms meso-hole structure.Abundant hollow pore structure has larger ratio Surface area, be advantageous to increase the activity of catalyst.In addition, part zinc instead of Co on tetrahedron2+Position.Under normal circumstances Co3+It is the activated centre that oxygen separates out, improves Co3+/Co2+Ratio is advantageous to improve the Co of Zn doping3O4Hollow dodecahedron structure The performance of catalyst.Finally, due to the difference of Co (0.75A °) and Zn (0.74A °) ionic radius, Zn doping is induction of a large amount of Lacking oxygen.During oxygen separates out, the Co of Zn doping3O4Substantial amounts of Lacking oxygen is advantageous to adsorb in hollow dodecahedron structure OH-, electron conduction is improved, reaches the purpose that increase oxygen separates out activity.In order to study different content Zn to catalyst electrochemistry The influence of performance, the present invention is controlled different Zn/Co molar content when preparing catalyst, so as to take into account to obtain most The Co of the Zn doping of high catalytic reaction activity and stability3O4The catalyst of hollow dodecahedron structure.The tool that the present invention also provides There is the Co of high activity and stability3O4Hollow dodecahedron structure oxygen separates out the catalytic performance of catalyst also superior to commercial catalysts Co3O4
The Co of Zn doping provided by the invention with high activity and stability3O4Hollow dodecahedron structure oxygen is separated out and urged Agent is by calcining presoma Znx(x=1 obtained by Co-MOF:5,1:3,1:1), different Zn/Co are rubbed when preparing catalyst You are controlled content, so as to take into account to obtain the Co of the Zn doping of highest catalytic reaction activity and stability3O4Hollow 12 face Body structure oxygen separates out catalyst.Described Co3O4It is by calcining presoma Co- that hollow dodecahedron structure oxygen, which separates out catalyst, Obtained by MOF.It is demonstrated experimentally that the catalyst prepared using the inventive method has good chemical property, its processing method Easy to operate, fabrication cycle is shorter, and chemical property is obviously improved.In addition, method provided by the invention it is simple to operate, Mild condition, operating procedure is simple, is easy to large-scale production.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 is linear sweep voltammetry curve map of the five kinds of catalyst of embodiment and comparative example in 1M KOH solutions;
Fig. 2 is double layer capacity (CDL) figure of five kinds of catalyst of embodiment and comparative example;
Fig. 3 is the x-ray diffraction pattern (XRD) of five kinds of catalyst of embodiment and comparative example;
Fig. 4 be embodiment 1 prepare catalyst under 500nm scales Co3O4The scanning of hollow dodecahedron structure catalyst Electromicroscopic photograph (SEM);
Fig. 5 is the catalyst Co that Zn is adulterated under 500nm scales prepared by embodiment 33O4Hollow dodecahedron structure catalysis The stereoscan photograph (SEM) of agent;
Fig. 6 is ac impedance spectroscopy (AC impedance spectrums) figure of three kinds of catalyst of embodiment 1,3 and comparative example;
Fig. 7 is the timing potential test figure of three kinds of catalyst of embodiment 1,3 and comparative example.
Embodiment
A kind of Co of Zn doping with high activity and stability provided by the invention3O4Hollow dodecahedron structure oxygen analysis Go out catalyst, be using Zn as altogether/co-catalyst, do template with the Zn/Co of different mol ratio example MOF presomas, pass through heat Processing method is prepared.It is preferred that the molar ratio of the Zn/Co is 1:1、1:3、1:5.
A kind of Co with high activity and stability provided by the invention3O4Hollow dodecahedron structure oxygen separates out catalyst It is that Co-MOF presomas are prepared by raw material of cabaltous nitrate hexahydrate, then presoma is prepared by heat treatment method 's.
A kind of oxygen with high activity and stability separates out a kind of concrete scheme of the preparation method of catalyst including following Step:
A-1) at room temperature, zinc nitrate hexahydrate and cabaltous nitrate hexahydrate are scattered in 100mL methanol, it is suspended obtains first Liquid;Zinc nitrate hexahydrate used and the Zn/Co of cabaltous nitrate hexahydrate molar ratio are 1:1、1:3、1:5;
Or a-2) at room temperature, cabaltous nitrate hexahydrate is scattered in 100mL methanol, obtains the first suspension;
B) 3.056g methylimidazole is scattered in other 100mL methanol, obtains the second suspension;
C) the first suspension and the second suspension are mixed and stirred for 24h at room temperature and obtain the first sediment;
D) by the first precipitates washed with EtOH and centrifuge, 12h is dried at 80 DEG C, obtains presoma;
E) presoma is calcined, with 5 DEG C of min-1Speed be heated to 350 DEG C, N2Kept for half an hour under environment, half is small When after change air into, continue at 350 DEG C keep half an hour obtain Zn doping Co3O4The catalyst of hollow dodecahedron structure Or Co3O4The catalyst of hollow dodecahedron structure.
In the step a), by being dispersed with stirring, mixing time is not strict for zinc nitrate hexahydrate and cabaltous nitrate hexahydrate Limitation, is uniformly dispersed.
In the step b), by being dispersed with stirring, mixing time does not limit strictly methylimidazole, is uniformly dispersed i.e. Can.
In the step e), Co3O4The catalyst of hollow dodecahedron structure is synthesized by calcining presoma Co-MOF Gained.The Co of Zn doping3O4Hollow dodecahedron structure catalyst is synthesized by calcining presoma Znx(x obtained by Co-MOF =1:5,1:3,1:1).The Co of Zn doping3O4Hollow dodecahedron structure catalyst source is in ZnCo-MOF, ZnCo3- MOF and ZnCo5- MOF, Zn-Co is designated as respectively3O4- 1, Zn-Co3O4- 2, Zn-Co3O4-3。
The present invention is described in detail below in conjunction with the accompanying drawings.
The present invention provides the Co of the Zn doping of a kind of high activity and high stability3O4Hollow dodecahedron oxygen separates out catalyst. For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but it is to be understood that These descriptions are simply further explanation the features and advantages of the present invention, rather than limiting to the claimed invention.Due to Zn/Co molar ratio is in Zn-Co3O4The performance of catalyst is had a major impact in complex carrier, therefore embodiment is enumerated respectively With investigating Zn/Co molar content in Zn-Co3O4The performance of corresponding catalyst in complex carrier.It is excellent to have selected Zn/Co's Optimum molar ratio, take into account to obtain the Co of the Zn doping of highest catalytic reaction activity and stability3O4Hollow dodecahedron structure is urged Agent.
Raw materials used in following embodiment is to analyze pure, the general chemical bought from the market, and need not be near The processing of one step.
Embodiment 1
(1) at room temperature, added into the beaker containing 100mL methanol quantitative cabaltous nitrate hexahydrate stir to dissolve One suspension;3.056g methylimidazoles are added into the beaker in addition containing 100mL methanol and obtain the second suspension;Second is hanged Turbid adds in the first suspension and stirs 24 hours to obtain sediment;Sediment is washed, is dried 12 hours at 80 DEG C and obtains Co- MOF presomas;Co-MOF presomas are placed in tube furnace and calcined, with 5 DEG C of min-1Speed be heated to 350 DEG C, N2Under environment Kept for half an hour.Change air after half an hour into, continue to be kept for half an hour obtain Co at 350 DEG C3O4Hollow dodecahedron structure is urged Agent, it is designated as Co3O4dodecahedra。
(2) it is 5% that 50 μ L Aldrich are produced, mass fraction is added into the beaker containing 950 μ L ethanol solutions Nafion solution, then the Co prepared in 5mg steps (1) is added thereto3O4Dodecahedra catalyst, ultrasonic disperse 30min, Obtain mixed solution;The above-mentioned mixed solution drop coatings of 5 μ L are taken after room temperature is dried, to obtain membrane electrode on glass-carbon electrode;With Hg/ HgO electrodes, as the three-electrode system to electrode, enter line as reference electrode, Pt pieces in the KOH solution by 1mol/L Property scanning volt-ampere (LSV) test, sweep speed 5mV/s, as a result referring to Fig. 1, Fig. 1 is that LSV of the catalyst in KOH solution is bent Line, wherein, curve Co3O4Nanoparticles is LSV curve of the commercial catalysts of the offer of comparative example 1 in KOH solution, by Knowable to Fig. 1, the Co of the preparation of embodiment 13O4Dodecahedra catalyst is 10mAcm in current density-2Overpotential be 379mV, the Co provided well below comparative example 13O4nanoparticles(η10mAcm-2=430mV) overpotential.
(3) Co prepared in a certain amount of step (1) is weighed3O4Dodecahedra catalyst surveys double layer capacity (CDL), referring to Fig. 2.
(4) Co prepared in a certain amount of step (1) is weighed3O4Dodecahedra catalyst surveys XRD, referring to Fig. 3.
(5) Co prepared in a certain amount of step (1) is weighed3O4Dodecahedra catalyst surveys SEM, referring to Fig. 4.
(6) Co prepared in a certain amount of step (1) is weighed3O4Dodecahedra catalyst test crosses flow impedance (AC impedances), Referring to Fig. 6.Co as can be seen from Figure 63O4Dodecahedra electronics transfer resistance is much smaller than Co3O4Nanopaticle, show Hollow dodecahedron structure adds specific surface area of catalyst, so as to provide superior chemical property for OER.
(7) under the three-electrode system of step (2), current density 10mAcm-2, a length of 4 small survey at present during electrolysis Co3O4Potential during dodecahedra catalyst gauges, is as a result shown in Fig. 7.Co as can be seen from Figure 73O4Dodecahedra rates of decay For 2.25mV h-1, much smaller than Co in comparative example 13O4nanoparticles(6mV h-1) catalyst rate of decay.
Comparative example 1
(1) it is 5% that 50 μ L Aldrich are produced, mass fraction is added into the beaker containing 950 μ L ethanol solutions Nafion solution, then 5mg business Co is added thereto3O4Nanoparticles catalyst, ultrasonic disperse 30min, is mixed Solution;The above-mentioned solution drop coatings of 5 μ L are taken after room temperature is dried, to obtain membrane electrode on glass-carbon electrode;Ginseng is used as using Hg/HgO electrodes Than electrode, Pt pieces as the three-electrode system to electrode, linear sweep voltammetry is carried out in the KOH solution by 1mol/L (LSV) testing, sweep speed 5mV/s, as a result referring to Fig. 1, Fig. 1 is LSV curve of the catalyst in KOH solution, wherein, it is bent Line Co3O4Nanoparticles is LSV curve of the commercial catalysts of the offer of comparative example 1 in KOH solution
(2) a certain amount of business Co is weighed3O4Nanoparticles catalyst surveys double layer capacity (CDL), referring to Fig. 2.
(3) a certain amount of business Co is weighed3O4Nanoparticles catalyst surveys XRD, referring to Fig. 3.
(4) a certain amount of business Co is weighed3O4Nanoparticles catalyst test crosses flow impedance (AC impedances), referring to Fig. 6.From Fig. 6 can be seen that Co3O4Nanoparticle electronics transfer resistance is maximum.
(5) under the three-electrode system of step (1), current density 10mAcm-2, a length of 4 small survey at present during electrolysis Co3O4Potential during nanoparticles catalyst gauges, is as a result shown in Fig. 7.Co as can be seen from Figure 73O4Nanoparticles decays Speed is 6mV h-1
Embodiment 2
(1) at room temperature, Zn/Co mol ratios are added into the beaker containing 100mL methanol and meets 1:1 zinc nitrate hexahydrate Stirred with cabaltous nitrate hexahydrate to dissolving to obtain the first suspension;3.056g bis- is added into the beaker in addition containing 100mL methanol Methylimidazole obtains the second suspension;Second suspension is added in the first suspension and stirs 24 hours to obtain sediment;Will precipitation Thing washs, and is dried 12 hours at 80 DEG C and obtains ZnCo-MOF presomas;ZnCo-MOF presomas are placed in tube furnace and calcined, with 5℃min-1Speed be heated to 350 DEG C, N2Kept for half an hour under environment.Change air after half an hour into, continue to protect at 350 DEG C Holding half an hour obtains Zn-Co3O4The catalyst of -1 hollow dodecahedron structure, is designated as Zn-Doped Co3O4-1。
(2) it is 5% that 50 μ L Aldrich are produced, mass fraction is added into the beaker containing 950 μ L ethanol solutions Nafion solution, then the Zn-Doped Co prepared in 5mg steps (1) are added thereto3O4- 1 catalyst, ultrasonic disperse 30min, Obtain mixed solution;The above-mentioned mixed solution drop coatings of 5 μ L are taken after room temperature is dried, to obtain membrane electrode on glass-carbon electrode;With Hg/ HgO electrodes, as the three-electrode system to electrode, enter line as reference electrode, Pt pieces in the KOH solution by 1mol/L Property scanning volt-ampere (LSV) test, sweep speed 5mV/s, as a result referring to Fig. 1, Fig. 1 is that LSV of the catalyst in KOH solution is bent Line.
(3) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 1 catalyst surveys double layer capacity (CDL), referring to Fig. 2.
(4) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 1 catalyst surveys XRD, referring to Fig. 3.
Embodiment 3
(1) at room temperature, Zn/Co mol ratios are added into the beaker containing 100mL methanol and meets 1:3 zinc nitrate hexahydrate Stirred with cabaltous nitrate hexahydrate to dissolving to obtain the first suspension;3.056g bis- is added into the beaker in addition containing 100mL methanol Methylimidazole obtains the second suspension;Second suspension is added in the first suspension and stirs 24 hours to obtain sediment;Will precipitation Thing washs, and is dried 12 hours at 80 DEG C and obtains ZnCo3- MOF presomas;By ZnCo3- MOF presomas are placed in tube furnace and calcined, With 5 DEG C of min-1Speed be heated to 350 DEG C, N2Kept for half an hour under environment.Change air after half an hour into, continue at 350 DEG C Kept for half an hour obtain Zn-Co3O4The catalyst of -2 hollow dodecahedron structures, is designated as Zn-Doped Co3O4-2。
(2) it is 5% that 50 μ L Aldrich are produced, mass fraction is added into the beaker containing 950 μ L ethanol solutions Nafion solution, then the Zn-Doped Co prepared in 5mg steps (1) are added thereto3O4- 2 catalyst, ultrasonic disperse 30min, Obtain mixed solution;The above-mentioned mixed solution drop coatings of 5 μ L are taken after room temperature is dried, to obtain membrane electrode on glass-carbon electrode;With Hg/ HgO electrodes, as the three-electrode system to electrode, enter line as reference electrode, Pt pieces in the KOH solution by 1mol/L Property scanning volt-ampere (LSV) test, sweep speed 5mV/s, as a result referring to Fig. 1, Fig. 1 is that LSV of the catalyst in KOH solution is bent Line, the Zn-Doped Co that as can be seen from the figure prepared by embodiment 33O4- 2 catalyst are 10mAcm in current density-2It is excessively electric Position is 353mV, and chemical property is better than other catalyst.
(3) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 2 catalyst survey double layer capacity (CDL), referring to Fig. 2.
(4) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 2 catalyst survey XRD, referring to Fig. 3.
(5) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 2 catalyst survey SEM, referring to Fig. 5.
(6) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 2 catalyst test cross flow impedances (AC impedances), Referring to Fig. 6.Zn-Doped Co as can be seen from Figure 63O4- 2 and Co3O4Dodecahedra electronics transfer resistance is much smaller than Co3O4Nanopaticle, show that surface oxygen defect adds electronic conductivity as caused by zinc doping, so as to be provided for OER Superior chemical property.
(7) under the three-electrode system of step (2), current density 10mAcm-2, a length of 4 small survey Zn- at present during electrolysis Doped Co3O4Potential during -2 catalyst gauge, is as a result shown in Fig. 7.Zn-Doped Co as can be seen from Figure 73O4- 2 rates of decay are 2mV h-1, much smaller than Co3O4nanopaticle(6mV h-1) rate of decay.
Embodiment 4
(1) at room temperature, Zn/Co mol ratios are added into the beaker containing 100mL methanol and meets 1:5 zinc nitrate hexahydrate Stirred with cabaltous nitrate hexahydrate to dissolving to obtain the first suspension;3.056g bis- is added into the beaker in addition containing 100mL methanol Methylimidazole obtains the second suspension;Second suspension is added in the first suspension and stirs 24 hours to obtain sediment;Will precipitation Thing washs, and is dried 12 hours at 80 DEG C and obtains ZnCo5- MOF presomas;By ZnCo5- MOF presomas are placed in tube furnace and calcined, With 5 DEG C of min-1Speed be heated to 350 DEG C, N2Kept for half an hour under environment.Change air after half an hour into, continue at 350 DEG C Kept for half an hour obtain Zn-Co3O4The catalyst of -3 hollow dodecahedron structures.It is designated as Zn-Doped Co3O4-3。
(2) it is 5% that 50 μ L Aldrich are produced, mass fraction is added into the beaker containing 950 μ L ethanol solutions Nafion solution, then the Zn-Doped Co prepared in 5mg steps (1) are added thereto3O4- 3 catalyst, ultrasonic disperse 30min, Obtain mixed solution;The above-mentioned mixed solution drop coatings of 5 μ L are taken after room temperature is dried, to obtain membrane electrode on glass-carbon electrode;With Hg/ HgO electrodes, as the three-electrode system to electrode, enter line as reference electrode, Pt pieces in the KOH solution by 1mol/L Property scanning volt-ampere (LSV) test, sweep speed 5mV/s, as a result referring to Fig. 1, Fig. 1 is that LSV of the catalyst in KOH solution is bent Line.
(3) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 3 catalyst survey double layer capacity (CDL), referring to Fig. 2.
(4) the Zn-Doped Co prepared in a certain amount of step (1) are weighed3O4- 3 catalyst survey XRD, referring to Fig. 3.
As seen from Figure 1, Zn doping made from catalyst to oxygen separate out performance there is certain castering action, when mole Than for Zn:Co=1:Corresponding Zn-Doped Co when 33O4- 2 catalyst are in 10mAcm-2When overpotential it is minimum, be 353mV, than undoped Co3O4The low 26mV of hollow dodecahedron catalyst, than business Co3O4Nanoparticles catalyst is low 77mV.As seen from Figure 2, the CDL of catalyst can directly influence catalyst activity (Zn-Doped Co3O4-2>Zn- Doped Co3O4-3>Co3O4dodecahedra>Zn-Doped Co3O4-1>Co3O4nanopaticle).Can be with bright by Fig. 4~5 The pattern of the aobvious catalyst for finding out preparation is the hollow dodecahedron structure of rule, increases the specific surface area of catalyst and carries Its high dispersiveness, and then improve catalyst oxygen and separate out performance.It will be appreciated from fig. 6 that Zn-Doped Co3O4- 2 and Co3O4Dodecahedra electronics transfer resistance is much smaller than Co3O4Nanopaticle, show the Surface Oxygen as caused by zinc doping Defect adds electronic conductivity, so as to provide superior chemical property for OER.Can be with from Fig. 7 timing potential Find out, Co3O4Dodecahedra rates of decay are 2.25mV h-1, Zn-Doped Co3O4- 2 rates of decay are 2mV h-1, it is remote small In Co3O4nanopaticle(6mV h-1) rate of decay.Show hollow dodecahedron structure and Zn doping to the steady of catalyst The qualitative lifting having by a relatively large margin, it is adapted to do oxygen and separates out catalyst and promote the use of.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (8)

1. a kind of oxygen with high activity and stability separates out catalyst, it is characterised in that it is the Co of Zn doping3O4Hollow ten Dihedron structure;
It is using Zn as altogether/co-catalyst that the oxygen, which separates out catalyst, is made of the Zn/Co of different mol ratio example MOF presomas Template, presoma, then the Co that the Zn that presoma is prepared by heat treatment method is adulterated are made first3O4Hollow 12 face The catalyst of body structure.
2. the oxygen according to claim 1 with high activity and stability separates out catalyst, it is characterised in that the Zn/ Co molar ratio is 1:1、1:3、1:5.
3. a kind of oxygen with high activity and stability separates out catalyst, it is characterised in that it is Co3O4Hollow dodecahedron knot Structure;
It is that Co-MOF presomas are prepared by raw material of cabaltous nitrate hexahydrate that the oxygen, which separates out catalyst, then presoma is passed through The Co that heat treatment method is prepared3O4The catalyst of hollow dodecahedron structure.
4. a kind of preparation method of the precipitation catalyst of the oxygen with high activity and stability described in claim 1 or 3, including with Lower step:
A-1) at room temperature, zinc nitrate hexahydrate and cabaltous nitrate hexahydrate are scattered in methanol, obtain the first suspension;
Or a-2) at room temperature, cabaltous nitrate hexahydrate is scattered in methanol, obtains the first suspension;
B) methylimidazole is scattered in other methanol, obtains the second suspension;
C) the first suspension and the second suspension are mixed and stirred for obtaining the first sediment at room temperature;
D) by the first precipitates washed with EtOH and centrifuge, dry, obtain presoma;
E) presoma is calcined, is heated to 350 DEG C, N2Kept for half an hour under environment, change air after half an hour into, continued Kept for half an hour obtain the Co of Zn doping at 350 DEG C3O4The catalyst or Co of hollow dodecahedron structure3O4Hollow dodecahedron The catalyst of structure.
5. the oxygen according to claim 4 with high activity and stability separates out the preparation method of catalyst, its feature exists In the Zn/Co of zinc nitrate hexahydrate used and cabaltous nitrate hexahydrate molar ratio is 1 in step a):1、1:3、1:5.
6. the oxygen according to claim 4 with high activity and stability separates out the preparation method of catalyst, its feature exists In being 24h to the time that the first suspension and the second suspension are stirred in step c).
7. the oxygen according to claim 4 with high activity and stability separates out the preparation method of catalyst, its feature exists In the temperature that the first sediment is dried in step d) is 80 DEG C, time 12h.
8. the oxygen according to claim 4 with high activity and stability separates out the preparation method of catalyst, its feature exists In it is with 5 DEG C of min to carry out calcining in step e) to the second sediment-1Speed be heated to 350 DEG C.
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CN108439549A (en) * 2018-04-03 2018-08-24 北京工业大学 A kind of preparation of array structure transition metal selenides electrode and its application in electrolysis water
CN109921039A (en) * 2019-03-27 2019-06-21 华南师范大学 A kind of VPO catalysts and its preparation method and application having both high carrying capacity and active site
CN111346652A (en) * 2020-04-15 2020-06-30 同济大学 Fluorine-doped spinel structure cobaltosic oxide electrocatalytic material and preparation method thereof
CN112086649A (en) * 2020-09-21 2020-12-15 福州大学 Preparation of spinel type composite cathode material and application thereof in solid oxide fuel cell
CN114142049A (en) * 2021-11-26 2022-03-04 武汉科思特仪器股份有限公司 Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst
CN114855186A (en) * 2022-05-10 2022-08-05 中汽创智科技有限公司 Hydrogen production catalyst and preparation method and application thereof
CN115646488A (en) * 2022-10-13 2023-01-31 华东师范大学 Application of catalyst in decarboxylation of L-lysine to preparation of 1, 5-pentanediamine

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CN108439549A (en) * 2018-04-03 2018-08-24 北京工业大学 A kind of preparation of array structure transition metal selenides electrode and its application in electrolysis water
CN108439549B (en) * 2018-04-03 2021-07-09 北京工业大学 Preparation of array structure transition metal selenide electrode and application thereof in electrolytic water
CN109921039A (en) * 2019-03-27 2019-06-21 华南师范大学 A kind of VPO catalysts and its preparation method and application having both high carrying capacity and active site
CN109921039B (en) * 2019-03-27 2020-06-12 华南师范大学 Oxygen catalyst with high loading capacity and active sites and preparation method and application of thermal of
CN111346652A (en) * 2020-04-15 2020-06-30 同济大学 Fluorine-doped spinel structure cobaltosic oxide electrocatalytic material and preparation method thereof
CN112086649A (en) * 2020-09-21 2020-12-15 福州大学 Preparation of spinel type composite cathode material and application thereof in solid oxide fuel cell
CN114142049A (en) * 2021-11-26 2022-03-04 武汉科思特仪器股份有限公司 Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst
CN114142049B (en) * 2021-11-26 2024-06-07 武汉科思特仪器股份有限公司 Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst
CN114855186A (en) * 2022-05-10 2022-08-05 中汽创智科技有限公司 Hydrogen production catalyst and preparation method and application thereof
CN114855186B (en) * 2022-05-10 2024-03-08 中汽创智科技有限公司 Hydrogen production catalyst and preparation method and application thereof
CN115646488A (en) * 2022-10-13 2023-01-31 华东师范大学 Application of catalyst in decarboxylation of L-lysine to preparation of 1, 5-pentanediamine

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