CN109174187A - A kind of preparation of the composite electrocatalyst of nickel based metal organic backbone - Google Patents
A kind of preparation of the composite electrocatalyst of nickel based metal organic backbone Download PDFInfo
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- CN109174187A CN109174187A CN201811043612.3A CN201811043612A CN109174187A CN 109174187 A CN109174187 A CN 109174187A CN 201811043612 A CN201811043612 A CN 201811043612A CN 109174187 A CN109174187 A CN 109174187A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 5
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000017 hydrogel Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- IVUGCRGCKRHFLS-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.N1=CC=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.N1=CC=CC=C1 IVUGCRGCKRHFLS-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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
- C25B11/073—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
- C25B11/095—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 at least one of the compounds being organic
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to new energy source technology field, especially a kind of preparation for the composite electrocatalyst based on nickel based metal organic backbone that water oxidation susceptibility significantly improves.The present invention causes its catalytic activity significantly limited as electrocatalysis material emerging in recent years primarily directed to metal organic frame (MOFs) while having the shortcomings that many merits such as systematicness nano pore, superelevation specific surface, superelevation porosity because of poorly conductive.Therefore three-dimensional porous graphene (3D Gr) is prepared and as the carrier loaded Ni-MOF using the preparation of ultrasonic wave added method to prepare a kind of three-dimensional grapheme incrustation nickel based metal organic backbone (3D Gr/Ni-MOF) composite material by Freeze Drying Technique, the composite material had not only had the advantages that the excellent electric conductivity of three-dimensional grapheme but also had had nickel based metal organic frame, so that its electro-catalysis water oxidation activity be made to be significantly improved.
Description
Technical field
The invention belongs to new energy source technology field, relate to that a kind of water oxidation susceptibility significantly improves based on nickel based metal
The preparation of the composite electrocatalyst of organic backbone.
Background technique
The fast development of current economic society is strongly depend on the consumption to fossil fuel, and the excessive use of fossil fuel
Exacerbate environmental pollution and greenhouse effects.Therefore, develop a kind of cleaning, renewable, environmental-friendly, free of contamination alternative energy source
It is extremely urgent.In numerous fungible energy sources, Hydrogen Energy is putative most one of clean energy resource as the zero carbon emission energy, such as
Effectively sustainable real estate hydrogen is that the following mankind step into hydrogen economy and first have to solve the problems, such as what.Electrolysis water technology is based on electrochemistry
The principle for decomposing water is hydrogen and oxygen using Reproduceable electricity or Driven by Solar Energy water decomposition, be considered as it is most promising and
The production hydrogen approach of sustainability.However either photocatalytic water or electrolysis water, your non-gold of high activity, high stability be required to
Belong to water reduction and water oxidation catalyst promotes water electrolysis reaction economical and energy saving.Water electrolysis reaction includes two important half-reactions,
That is evolving hydrogen reaction and oxygen evolution reaction, wherein oxygen evolution reaction is one and is related to the complex reaction of the more proton translocations of polyelectron-, needs more
Therefore high overpotential improves the key that electrolysis water oxygen evolution activity is only hydrogen manufacturing.
Compared to miscellaneous base metal elctro-catalyst instantly, metal organic framework compound (MOFs) is by metal
The porous crystalline material for the dimensional network structure that center and multiple tooth organic ligand are formed by coordinate bond, has the advantages that uniqueness,
Such as porosity, large specific surface area, compound with regular structure and Modulatory character, easy functionalization, show unique physics in terms of catalysis
Chemical property and potential application value.However MOFs material makes its catalysis live when as elctro-catalyst because of poorly conductive
Property is restricted significantly.The advantages of based on the above MOFs material and disadvantage, this patent attempt the carbon by introducing excellent electric conductivity
Material graphene is as carrier loaded MOFs material so as to improve its electric conductivity；Meanwhile using Freeze Drying Technique by graphene
It is prepared into three-dimensional structure graphene, substantially increases the specific surface area of carrier, MOF base is compound to urge to improve to the maximum extent
The water oxidation susceptibility of agent.Also, there is employed herein with the ultrasonic wave added that yield is high, the reaction time is short, product recovery rate is high
Method prepares MOF based composites.By test, under equal conditions prepared 3D Gr/Ni-MOF composite catalyst
OER activity ratio Ni-MOF is greatly improved.As non-precious metal catalyst, MOF based composites produced herein have it is at low cost,
Easily preparation, activity significantly improve, the feature that stability is good, can be used as excellent electrolysis water oxidation catalyst candidate.
Summary of the invention
The purpose of the present invention is introducing carrier to improve the electric conductivity of MOF material, a kind of water oxidation susceptibility is provided and is significantly improved
The composite electrocatalyst based on nickel based metal organic backbone preparation.
Thinking of the invention: increased using Freeze Drying Technique preparation specific surface, the three-dimensional structure graphite of excellent electric conductivity
Alkene simultaneously prepares the MOF based composites that three-dimensional grapheme loads as carrier, then by ultrasonic wave added method, obtains 3D Gr/Ni-
MOF catalyst.
Specifically sequentially include the following steps:
(1) graphite oxide is prepared according to Hummers method, weighs 60mg graphite oxide and is dissolved in 20mL water, ultrasonic disperse 1h
Ammonium hydroxide (30%) is added afterwards and adjusts PH to 10, is sealed in 180 DEG C of reaction 20h in polytetrafluoroethyllining lining hydrothermal reaction kettle, obtains
Black cylinder redox graphene (rGO) hydrogel deionized water filtering and washing several times, is put into refrigerator freezing until sample
Complete cryocoagulation, three-dimensional porous shape graphene, sample mark can be prepared by being then placed in freeze-drying 48h in freeze drier
It is denoted as 3D Gr；
(2) 0.75mmol organic ligand 2,5- pyrrole is first added after taking 32mL DMF, 2mL ethyl alcohol, 2mL water ultrasonic mixing uniform
Then pyridine dioctyl phthalate adds 0.75mmol nickel acetate tetrahydrate, tri- second of 0.8mL is added immediately after dissolution completely under ultrasound condition
Amine (TEA) stirs 5min, adds the 3D Gr of certain mass, seals continual ultrasonic (40KHz) certain time, ethyl alcohol, water centrifugation
Several times, 60 DEG C of drying, grinding uniformly, are labeled as 3D Gr/Ni-MOF for washing.
Positive effect obtained by the present invention is: (1) introducing the three-dimensional grapheme of excellent electric conductivity as carrier
The shortcomings that sufficiently compensating for MOF poorly conductive.(2) had using the three-dimensional structure graphene specific surface area of Freeze Drying Technique preparation
Increased, is conducive to the mass transport and electronics transfer when catalytic electrolysis.(3) preparing material by ultrasonic wave added facilitates MOF
Crystal little particle is uniformly distributed on carrier to expose the catalytically active surface with unsatuated metal ligand site sufficiently,
It is beneficial to the promotion of material catalytic activity.(4) by test, the overpotential of 3D Gr/Ni-MOF composite catalyst up to 370mV,
Much smaller than Ni-MOF material under equal conditions, show that prepared composite catalyst OER activity is obviously improved.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of Ni-MOF.
Fig. 2 is the scanning electron microscope (SEM) photograph of 3D Gr/Ni-MOF.
Specific embodiment
Specific embodiment 1: a kind of water oxidation susceptibility of present embodiment significantly improve based on the organic bone of nickel based metal
The preparation of the composite electrocatalyst of frame is to sequentially include the following steps:
(1) graphite oxide is prepared according to Hummers method, weighs 60mg graphite oxide and is dissolved in 20mL water, ultrasonic disperse 1h
Ammonium hydroxide (30%) is added afterwards and adjusts pH to 10, is sealed in 180 DEG C of reaction 20h in polytetrafluoroethyllining lining hydrothermal reaction kettle, obtains
Black cylinder redox graphene (rGO) hydrogel deionized water filtering and washing several times, is put into refrigerator freezing until sample
Complete cryocoagulation, three-dimensional porous shape graphene, sample mark can be prepared by being then placed in freeze-drying 48h in freeze drier
It is denoted as 3D Gr；
(2) 0.75mmol organic ligand 2,5- pyrrole is first added after taking 32mL DMF, 2mL ethyl alcohol, 2mL water ultrasonic mixing uniform
Then pyridine dioctyl phthalate adds 0.75mmol nickel acetate tetrahydrate, tri- second of 0.8mL is added immediately after dissolution completely under ultrasound condition
Amine (TEA) stirs 5min, adds the 3D Gr of certain mass, seals continual ultrasonic (40KHz) certain time, ethyl alcohol, water centrifugation
Several times, 60 DEG C of drying, grinding uniformly, are labeled as 3D Gr/Ni-MOF for washing.
Specific embodiment 2: the present embodiment is different from the first embodiment in that being added 3D Gr's in step (2)
Amount is respectively 3,5,10,15mg.Other are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that being sealed in step (2) super
The sound time is respectively 6,8,10h.Other are the same as one or two specific embodiments.
Had by what following embodiment and comparative example illustrated that a kind of water oxidation susceptibility significantly improves based on nickel based metal
The preparation of the composite electrocatalyst of machine skeleton:
Embodiment one:
(1) graphite oxide is prepared according to Hummers method, weighs 60mg graphite oxide and is dissolved in 20mL water, ultrasonic disperse 1h
Ammonium hydroxide (30%) is added afterwards and adjusts pH to 10, is sealed in 180 DEG C of reaction 20h in polytetrafluoroethyllining lining hydrothermal reaction kettle, obtains
Black cylinder redox graphene (rGO) hydrogel deionized water filtering and washing several times, is put into refrigerator freezing until sample
Complete cryocoagulation, three-dimensional porous shape graphene, sample mark can be prepared by being then placed in freeze-drying 48h in freeze drier
It is denoted as 3D Gr；
(2) 0.75mmol organic ligand 2,5- pyrrole is first added after taking 32mL DMF, 2mL ethyl alcohol, 2mL water ultrasonic mixing uniform
Then pyridine dioctyl phthalate adds 0.75mmol nickel acetate tetrahydrate, tri- second of 0.8mL is added immediately after dissolution completely under ultrasound condition
Amine (TEA) stirs 5min, adds the 3D Gr of 10mg, seals continual ultrasonic (40KHz) 8h, ethyl alcohol, water centrifuge washing several times,
60 DEG C of drying, grinding uniformly, are labeled as 3D Gr/Ni-MOF.
Fig. 1 is nickel acetate and 2, and the Ni-MOF material that 5- pyridinedicarboxylic acid is prepared according to 1:1 molar ratio ultrasound, which is in
Intensive graininess pattern, and Ni-MOF (1:1) granular size is uniform, has regular pore structure, this is that metal is organic
The feature of framework material.
Fig. 2 is the SEM of 3D Gr/Ni-MOF, and carrier of the 3D Gr as composite material has unique space multistory porous
Structure.And Ni-MOF little particle can both be supported on the three-dimensional structure graphene film that single lamella or multiple lamellas are stacked
Layer surface can be supported on again in the pore structure of lamella formation, to increase contact surface of the composite material with electrolyte itself
Product, improves its electrolysis water oxidation susceptibility.
Comparative example one:
0.75mmol organic ligand 2,5- pyridine is first added after taking 32mL DMF, 2mL ethyl alcohol, 2mL water ultrasonic mixing uniform
Then dioctyl phthalate adds 0.75mmol nickel acetate tetrahydrate, 0.8mL triethylamine is added immediately after dissolution completely under ultrasound condition
(TEA) 5min is stirred, then seals continual ultrasonic (40KHz) 8h, several times, 60 DEG C of drying, grinding are equal for ethyl alcohol, water centrifuge washing
It is even, it is labeled as Ni-MOF.
Claims (4)
1. a kind of preparation for the composite electrocatalyst based on nickel based metal organic backbone that water oxidation susceptibility significantly improves, feature
It is that the catalyst is to sequentially include the following steps:
(1) graphite oxide is prepared according to Hummers method, weighs 60mg graphite oxide and is dissolved in 20mL water, added after ultrasonic disperse 1h
Enter ammonium hydroxide (30%) and adjust pH to 10, is sealed in 180 DEG C of reaction 20h in polytetrafluoroethyllining lining hydrothermal reaction kettle, obtains black
Cylindrical redox graphene (rGO) hydrogel deionized water filtering and washing several times, is put into refrigerator freezing until sample is complete
Cryocoagulation, three-dimensional porous shape graphene can be prepared by being then placed in freeze-drying 48h in freeze drier, and sample is labeled as
3D Gr；
(2) 0.75mmol organic ligand 2,5- pyridine two is first added after taking 32mL DMF, 2mL ethyl alcohol, 2mL water ultrasonic mixing uniform
Then formic acid adds 0.75mmol nickel acetate tetrahydrate, 0.8mL triethylamine is added immediately after dissolution completely under ultrasound condition
(TEA) 5min is stirred, the 3D Gr of certain mass is added, seals continual ultrasonic (40KHz) certain time, ethyl alcohol, water centrifugation are washed
It washs several times, 60 DEG C of drying, grinding uniformly, are labeled as 3D Gr/Ni-MOF.
2. the compound electric based on nickel based metal organic backbone that a kind of water oxidation susceptibility according to claim 1 significantly improves
The preparation of catalyst, it is characterised in that the amount that 3D Gr is added in step (2) is respectively 3,5,10,15mg.
3. the compound electric based on nickel based metal organic backbone that a kind of water oxidation susceptibility according to claim 1 significantly improves
The preparation of catalyst, it is characterised in that sealing ultrasonic time is respectively 6,8,10h in step (2).
4. the compound electric based on nickel based metal organic backbone that a kind of water oxidation susceptibility according to claim 1 significantly improves
The preparation of catalyst, it is characterised in that under the conditions of same test, 3D Gr/Ni-MOF composite material is than pure Ni-MOF material in electricity
There is lower overpotential, i.e. prepared 3D Gr/Ni-MOF composite material has the water oxygen significantly increased when solving water oxygen
Activity.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109916973A (en) * | 2019-02-28 | 2019-06-21 | 华中科技大学 | A kind of Graphite alkene-MOFs composite material, its preparation and application |
| CN110038643A (en) * | 2019-04-26 | 2019-07-23 | 常州大学 | A kind of oxygen-separating catalyst of the Ni/N-C NW material derived by MOF |
| CN110104640A (en) * | 2019-05-16 | 2019-08-09 | 宁波石墨烯创新中心有限公司 | Composite air-sensitive material, gas sensor and preparation method thereof |
| CN112430828A (en) * | 2020-09-23 | 2021-03-02 | 浙江大学衢州研究院 | Preparation method of transition metal doped nickel-based metal organic framework three-dimensional electrode material, product and application thereof |
| CN112593247A (en) * | 2020-12-07 | 2021-04-02 | 武汉工程大学 | MOF @ graphene/foamed nickel composite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN105761942A (en) * | 2016-02-29 | 2016-07-13 | 上海应用技术学院 | Super-capacitor electrode material of sandwiched structure and preparation method |
| CN107376837A (en) * | 2017-07-27 | 2017-11-24 | 武汉工程大学 | A kind of preparation method of graphene/metal organic frame aeroge absorption/catalysis material |
| CN107824188A (en) * | 2017-10-27 | 2018-03-23 | 广西师范大学 | The preparation method of nickel cobalt layered double hydroxide/graphene elctro-catalyst |
| CN107871617A (en) * | 2016-09-28 | 2018-04-03 | 中国人民解放军国防科学技术大学 | Graphene metal organic frame composite and its preparation method and application |
-
2018
- 2018-09-07 CN CN201811043612.3A patent/CN109174187A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN105761942A (en) * | 2016-02-29 | 2016-07-13 | 上海应用技术学院 | Super-capacitor electrode material of sandwiched structure and preparation method |
| CN107871617A (en) * | 2016-09-28 | 2018-04-03 | 中国人民解放军国防科学技术大学 | Graphene metal organic frame composite and its preparation method and application |
| CN107376837A (en) * | 2017-07-27 | 2017-11-24 | 武汉工程大学 | A kind of preparation method of graphene/metal organic frame aeroge absorption/catalysis material |
| CN107824188A (en) * | 2017-10-27 | 2018-03-23 | 广西师范大学 | The preparation method of nickel cobalt layered double hydroxide/graphene elctro-catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 何春兰，: ""石墨烯制备及其电催化应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109916973A (en) * | 2019-02-28 | 2019-06-21 | 华中科技大学 | A kind of Graphite alkene-MOFs composite material, its preparation and application |
| CN110038643A (en) * | 2019-04-26 | 2019-07-23 | 常州大学 | A kind of oxygen-separating catalyst of the Ni/N-C NW material derived by MOF |
| CN110104640A (en) * | 2019-05-16 | 2019-08-09 | 宁波石墨烯创新中心有限公司 | Composite air-sensitive material, gas sensor and preparation method thereof |
| CN112430828A (en) * | 2020-09-23 | 2021-03-02 | 浙江大学衢州研究院 | Preparation method of transition metal doped nickel-based metal organic framework three-dimensional electrode material, product and application thereof |
| CN112430828B (en) * | 2020-09-23 | 2021-11-09 | 浙江大学衢州研究院 | Preparation method of transition metal doped nickel-based metal organic framework three-dimensional electrode material, product and application thereof |
| CN112593247A (en) * | 2020-12-07 | 2021-04-02 | 武汉工程大学 | MOF @ graphene/foamed nickel composite material and preparation method and application thereof |
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