CN107029792A - A kind of metal organic frame and graphene electro-catalysis composite and preparation method thereof - Google Patents
A kind of metal organic frame and graphene electro-catalysis composite and preparation method thereof Download PDFInfo
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- CN107029792A CN107029792A CN201710225097.XA CN201710225097A CN107029792A CN 107029792 A CN107029792 A CN 107029792A CN 201710225097 A CN201710225097 A CN 201710225097A CN 107029792 A CN107029792 A CN 107029792A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000006555 catalytic reaction Methods 0.000 title description 7
- 239000002131 composite material Substances 0.000 title description 5
- 239000002184 metal Substances 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000001273 butane Substances 0.000 claims abstract 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000010583 slow cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 1,4- Oxazolyl Chemical group 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/33—
-
- 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
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of cobalt metal-organic framework materials with electrocatalytic hydrogen evolution performance and preparation method thereof, belong to environmentally friendly electrocatalysis material preparation field.Material therefor synthetic method of the present invention is hydro-thermal method.Comprise the following steps that：First by cobaltous perchlorate, 1,4 naphthalene diacid (H2Ndc), double (base of imidazole radicals 1) butane of Isosorbide-5-Nitrae) and sodium hydroxide evenly spread in polyethylene glycol (PEG 400), then the turbid liquid of above-mentioned mixing is transferred in ptfe autoclave and carries out hydro-thermal reaction.Products therefrom is washed, dry after obtain purple bulk crystals, the grinding of the graphene of purple crystals and certain mass is obtained into the electrocatalysis material Co (ndc) (bidp)2.Preparation process of the present invention is simple, and gained elctro-catalyst possesses the ability of preferable electrolysis water liberation of hydrogen, and Tafel slope can reach 100 mV/decade.The field such as producing in eco-friendly power source has applications well prospect.
Description
Technical field
The present invention relates to a kind of cobalt metal-organic framework materials with electrocatalysis characteristic and preparation method thereof, belong to environment
Friendly electrocatalytic hydrogen evolution field of material preparation.
Background technology
Metal-organic framework materials (Metal-organic frameworks, MOFs) are one kind by metal ion and had
The inorganic-organic hybridization functional material that machine part is assembled by coordinate bond.Due to its flexible porous, big specific surface area,
The characteristics such as unsaturated coordinate bond so that in recent years in molecular recognition, magnetics, luminescence generated by light, drug delivery, gas storage, catalysis
In terms of be widely used.MOFs materials are formed by metal ion or metal ion cluster by the connection of organic ligand
The structure of three dimensions infinite expanding, thus have the advantage of inorganic and organic materials concurrently.By materials such as base metal phosphorus sulfide
The inspiration of electrocatalysis characteristic research, the trial by MOFs materials applications in electro-catalysis field is more and more in recent years.Due to MOFs
Not only there is highly regular pore structure, porous, and be also equipped with the activity of the opening of lewis acid and redox active
Metallic site, therefore possess as the application in terms of catalyst tempting prospect, but MOFs electric conductivity limits MOFs in electricity
Solving the application of elutriation hydrogen, therefore the combination of MOFs and some conductive materials can be obtained into some has the new of electrocatalysis characteristic
Type electrocatalysis material.At present, it is also relatively fewer for the report of the elctro-catalyst based on MOFs composites.
The content of the invention
The research of novel electro-catalytic agent based on MOFs materials not yet obtains in-depth study, the kind of such elctro-catalyst
It is worth further investigation in terms of class, preparation method and performance.It is an object of the invention to provide the cobalt of higher water electrolysis hydrogen production performance
Metal organic frame elctro-catalyst and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions, and a kind of sulfuric acid in 0.5M has certain stability
Prepared by the hydro-thermal method of the cobalt metal organic frame elctro-catalyst of energy, comprise the following steps：
1）Cobaltous perchlorate, 1,4- naphthalene diacid (H are weighed by certain mol proportion2Ndc), 1,4- double (imidazole radicals base) and 0.1M hydrogen-oxygens
Change sodium solution in container；
2）To step 1）PEG-400 is added in container used, and ultrasonic disperse is uniform；
3）By step 2）Gained mixed solution is transferred in ptfe autoclave；
4）Reactor is put into 140-180oReacted in C baking ovens 72 hours, then with the time slow cooling of 5 hours to 30oC
Obtain purple bulk crystals；
5）Gained bulk crystals are washed with deionized and product are obtained after being dried at 60 DEG C.
6）By step 5）The graphene of products therefrom and certain mass is combined at random, and mechanical lapping obtains final product,
As MOFs composites elctro-catalyst.
Electricity can be carried out in 0.5 M sulfuric acid as elctro-catalyst using the Co-MOFs materials prepared by above step
Solve the test of elutriation hydrogen.
Beneficial effects of the present invention：
（1）Product prepared by the present invention is Co (ndc) (bidp)2, simply, controllability is strong for its preparation method.
（2）New MOFs materials class elctro-catalyst prepared by the present invention be bulk crystals material, its good crystallinity, easily
Separation.
（3）Co (ndc) (bidp) prepared by the present invention2Elctro-catalyst has excellent electrolysis water liberation of hydrogen ability.
（4）The preparation of the present invention only needs the conventional conventional equipment in laboratory, is not required to special equipment, technical process is simply easily grasped
Make.
（5）The raw materials used naphthalene diacid of the present invention etc. is cheap and easy to get, can effectively reduce the preparation cost of catalyst, be conducive to
Prepared by large-scale production, be adapted to future industrialization in terms of pollutant photocatalytic degradation, environmental improvement and protection and on a large scale should
With.
Brief description of the drawings
The coordination context diagram of the elctro-catalysts of Co (ndc) (bidp) 2 prepared by the method for Fig. 1 embodiments 1.
The X-ray diffraction of elctro-catalyst prepared by the method for Fig. 2 embodiments 1（XRD）Figure.
Linear scan cyclic voltammogram of the elctro-catalyst in 0.5M sulfuric acid prepared by Fig. 3 embodiments 1.
Tafel curve figure of the electro-catalysis in 0.5M sulfuric acid prepared by the method for Fig. 4 embodiments 1.
Embodiment
Embodiment 1
Double (the imidazoles of 1,4- of 0.1mmol cobaltous perchlorate, 0.1mmol 1,4- naphthalenes diacid (H2ndc), 0.1mmol are weighed first
Base) and 2ml sodium hydroxide solutions (0.1M) in beaker, thereto plus 6 ml PEG-400, stirring 30 minutes is with scattered equal
It is even.Above-mentioned mixed solution is transferred in ptfe autoclave and is put into 140 DEG C of baking ovens and is reacted 72 hours, then with 5
Hour slow cooling obtains purple bulk crystals product to 30 DEG C.Dried after being cleaned by ultrasonic with deionized water at 60 DEG C, system
Obtain Co (ndc) (bidp)2Take 40mg Co-MOFs and 10mg graphene to grind 30 min and elctro-catalyst is made.It is made in Fig. 2
The X-ray diffraction of standby elctro-catalyst（XRD）Figure, as can be seen from the figure tests diffraction peak in gained spectrogram and analogue spectrums
Put and coincide substantially.Illustrate that Co (ndc) (bidp) 2 purity produced are higher.Prepared elctro-catalyst is in 0.5M sulfuric acid in Fig. 3
Linear scan cyclic voltammogram.Illustrate that the composite possesses preferable redox active.Fig. 4 is the method institute of embodiment 1
Tafel curve figure of the electro-catalysis of preparation in 0.5M sulfuric acid, when adding the Co-MOFs of 4 wt% graphenes as can be seen from Fig.
Tafel slopes be 100mV/decade.
Embodiment 2
0.1mmol cobaltous perchlorate, 0.2mmol 1,4- naphthalene diacid (H is weighed first2Ndc), double (miaows of 0.1mmol 1,4-
Oxazolyl base) and 2 ml sodium hydroxide solutions (0.1M) in beaker, thereto plus 6 ml PEG-400, stirring 30 minutes with
It is uniformly dispersed.Above-mentioned mixed solution is transferred in ptfe autoclave and 160 are put intooReacted 72 hours in C baking ovens,
Then with the time slow cooling of 5 hours to 30oC is to obtain purple bulk crystals product.After being cleaned by ultrasonic with deionized water
60oDried under C, Co (ndc) (bidp) is made2, take 40 mg Co-MOFs and 10mg graphene to grind 30 min and electricity be made
Catalyst.
Embodiment 3
The 1,4- for weighing 0.1 mmol cobaltous perchlorate, 0.2 mmol 1,4- naphthalenes diacid (H2ndc), 0.2 mmol first is double
(imidazole radicals) and 2 ml sodium hydroxide solutions (0.1M) in beaker, thereto plus 6 ml PEG-400, stirring 30 minutes with
It is uniformly dispersed.Above-mentioned mixed solution is transferred in ptfe autoclave and reaction 72 hours in 180 DEG C of baking ovens are put into, so
Afterwards purple bulk crystals product is obtained with the time slow cooling of 5 hours to 30 DEG C.60 after being cleaned by ultrasonic with deionized water
Dried at DEG C, Co (ndc) (bidp) is made2Take 40 mg Co-MOFs and 10 mg graphene to grind 30 min and electro-catalysis is made
Agent.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the limitation for the present invention, this Shen
Please in embodiment and feature in embodiment in the case where not conflicting, can mutually be combined.The protection model of the present invention
Enclose the equivalent substitution side of technical characteristic in the technical scheme that should be recorded with claim, including the technical scheme of claim record
Case is protection domain.Equivalent substitution i.e. within this range is improved, also within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of the elctro-catalyst based on cobalt metal-organic framework material, the chemical formula of electrocatalysis material is Co
(ndc)(bidp)2, it is characterised in that it is as follows the step of preparation method：
（1）By cobaltous perchlorate, 1,4- naphthalene diacid (H2Ndc), double (imidazole radicals -1- bases) butane of 1,4-) and 0.1M sodium hydroxides it is molten
Simultaneously ultrasound is uniform in container, plus in 2 ml deionized waters and 4 ml absolute ethyl alcohols for liquid；
（2）By above-mentioned steps（1）Gained mixed solution, which is transferred in ptfe autoclave, carries out hydro-thermal reaction, by reactor
It is put into slow cooling after being reacted in baking oven and obtains purple bulk crystals to 30 DEG C；
（3）It is cleaned by ultrasonic the purple bulk crystals of acquisition and 80 with deionized wateroDried under C, you can obtain electrocatalysis material Co
(ndc)(bidp)2。
2. the preparation method of cobalt metal-organic framework material elctro-catalyst according to claim 1, it is characterised in that step
（2）The hydrothermal temperature interval is 140-180oC, the reaction time is 72 hours, and temperature fall time is 5 hours.
3. the preparation method of cobalt metal-organic framework material elctro-catalyst according to claim 1, it is characterised in that high chlorine
Sour cobalt, 1,4- naphthalene diacid (H2Ndc), the mol ratio of double (imidazole radicals -1- bases) butane of 1,4- and 0.1M sodium hydroxides is 2：1：
1：2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955182A (en) * | 2017-11-30 | 2018-04-24 | 三峡大学 | A kind of micro incorporation composite metal organic framework material, preparation method and applications |
| CN111905827A (en) * | 2020-08-21 | 2020-11-10 | 三峡大学 | Preparation method of nickel-based heterogeneous composite material and application of nickel-based heterogeneous composite material in catalyzing methanol oxidation |
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| CN104131309A (en) * | 2014-08-01 | 2014-11-05 | 太原理工大学 | Method for hydrogen production and storage through catalysis of water splitting by MOF composite electrode |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105289733A (en) * | 2015-10-28 | 2016-02-03 | 西南大学 | Preparation method of hydrogen evolution electric catalyst based on metal-organic framework compound |
| CN105977467A (en) * | 2016-07-01 | 2016-09-28 | 北京工业大学 | Preparation method for preparing Co3O4@CoP composite electrode based on MOF template |
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- 2017-04-07 CN CN201710225097.XA patent/CN107029792B/en active Active
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| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN104131309A (en) * | 2014-08-01 | 2014-11-05 | 太原理工大学 | Method for hydrogen production and storage through catalysis of water splitting by MOF composite electrode |
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| CN105289733A (en) * | 2015-10-28 | 2016-02-03 | 西南大学 | Preparation method of hydrogen evolution electric catalyst based on metal-organic framework compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107955182A (en) * | 2017-11-30 | 2018-04-24 | 三峡大学 | A kind of micro incorporation composite metal organic framework material, preparation method and applications |
| CN107955182B (en) * | 2017-11-30 | 2020-08-04 | 三峡大学 | Micro-doped composite metal organic framework material, preparation method and application thereof |
| CN111905827A (en) * | 2020-08-21 | 2020-11-10 | 三峡大学 | Preparation method of nickel-based heterogeneous composite material and application of nickel-based heterogeneous composite material in catalyzing methanol oxidation |
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