CN108686710A - Two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material and preparation method thereof - Google Patents
Two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material and preparation method thereof Download PDFInfo
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- CN108686710A CN108686710A CN201810461343.6A CN201810461343A CN108686710A CN 108686710 A CN108686710 A CN 108686710A CN 201810461343 A CN201810461343 A CN 201810461343A CN 108686710 A CN108686710 A CN 108686710A
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- molybdenum disulfide
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 19
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NPHULPIAPWNOOH-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(2,3-dihydroindol-1-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCC2=CC=CC=C12 NPHULPIAPWNOOH-UHFFFAOYSA-N 0.000 description 2
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- -1 Dimethyl methyl Amide Chemical compound 0.000 description 1
- 150000008538 L-cysteines Chemical class 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, and the material includes two-dimensional metallic the organic frame nanometer sheet M-TCPP and molybdenum disulfide nano sheet MoS disperseed mutually2, wherein the M is selected from Co2+,Ni2+At least one of, the TCPP is 5,10,15,20- tetra- (4- carboxyl-phenyls)-porphyrins, and the molar ratio of the M and Mo ions is 1:0.4~8, the present invention also provides a kind of preparation methods of the material;The preparation method can be such that the evolving hydrogen reaction active site of material surface increases, MoS2Electric conductivity enhancing, significantly improve the electrocatalytic hydrogen evolution performance of the two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, a kind of new method provided for exploitation low price, efficient electrocatalytic hydrogen evolution catalyst.
Description
Technical field
The present invention relates to electrocatalytic hydrogen evolution technical field, specifically a kind of two-dimensional metallic organic frame/molybdenum disulfide nano
Composite electro catalytic liberation of hydrogen material and preparation method thereof.
Background technology
As energy crisis and problem of environmental pollution are increasingly sharpened, people, which normally live and produce, has been subjected to serious prestige
The side of body.But fossil energy (coal, oil and natural gas), always as the main body of world energy sources, they are non-renewable energy resources storages
Limited and combustion product is measured to would seriously pollute the environment.Increase and fossil fuel reserves now with fossil fuel demand
It reduces, people more urgent need exploitation green, efficient regenerative resource.It is most clean that Hydrogen Energy is referred to as 21st century
The energy, because of its series of advantages, for example abundance, combustion heat value are high, only generate water etc. after combustion of hydrogen and have extensive
Application prospect.Current most common hydrogen production process is water electrolysis hydrogen production and fossil fuel hydrogen manufacturing.But fossil fuel be can not be again
The raw energy, although this method can a large amount of hydrogen manufacturing, application prospect is troubling.Water is very abundant in the resource of the earth,
It can be described as come hydrogen manufacturing by electrolysis water inexhaustible.Currently, electric energy can in several ways directly
It produces, cost is relatively low.So water electrolysis hydrogen production can have with large-scale production and application, this method, hydrogen production efficiency is high,
The advantages that technique and operating process are simple, and there are no pollution to the environment.Electrolysis water can be divided into two half-cell reactions, i.e. liberation of hydrogen is anti-
Answer (hydrogen evolution reaction, HER) and oxygen evolution reaction (oxygen evolution reaction, OER).
Oxygen evolution reaction and evolving hydrogen reaction are required to reduce the overpotential of electrochemical reaction using elctro-catalyst.Overpotential refers in electrification
During, the difference between the voltage and thermodynamical reaction electromotive force of application.Overpotential is bigger, needs the applied voltage applied
Bigger, the electric energy of consumption is more.So it is very must to develop the efficient liberation of hydrogen catalyst that some can significantly reduce overpotential of hydrogen evolution
It wants.Currently, platinum-group noble metals are the highest elctro-catalysts of liberation of hydrogen efficiency, it can be in very close thermodynamical reaction electromotive force
Evolving hydrogen reaction is realized under voltage.It is expensive but since Precious Metals Resources are rare, it can not large-scale industrial production hydrogen.Section
Scholars have been devoted to develop a kind of abundance, the catalyst with efficient catalytic hydrogen evolution performance to replace the expensive gold of platinum family
Belong to.In these materials, two-dimentional two chalcogenide (TMD) nanometer sheet of (2D) transition metal has become a kind of fascinating
HER elctro-catalyst types have good electrocatalytic hydrogen evolution performance.Molybdenum disulfide as typical stratiform TMD materials
(MoS2) nanometer sheet has been widely used as HER catalyst recently, several thin S- are shown by weak Van der Waals interaction
Mo-S layers.Theoretical and experimental study shows MoS2Δ GH*Really close to neutral so that MoS2It is likely to become a kind of effective
HER catalyst, be concerned because its is resourceful, cheap.But its own poorly conductive, and the liberation of hydrogen of exposure
Reactivity site is relatively fewer, its electrocatalytic hydrogen evolution performance is caused to need big improvement.
Invention content
It is an object of the invention to solve above-mentioned problems of the prior art, providing a kind of two-dimensional metallic has machine frame
Frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material and preparation method thereof, the material have high electrocatalytic hydrogen evolution performance.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, the material include mutual
Two-dimensional metallic the organic frame nanometer sheet M-TCPP and molybdenum disulfide nano sheet MoS of dispersion2, wherein the M is selected from Co2+,Ni2+
At least one of, the TCPP is 5,10,15,20- tetra- (4- carboxyl-phenyls)-porphyrins, the molar ratio of the M and Mo ions
It is 1:0.4~8.
A kind of preparation method of the two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, packet
Include following steps:
(1) synthesis two-dimensional metallic organic frame nanometer sheet M-TCPP, wherein M are selected from Co2+,Ni2+At least one of,
TCPP is 5,10,15,20- tetra- (4- carboxyl-phenyls)-porphyrin;The two-dimensional metallic organic frame nanometer sheet is dispersed in dispersion
Dispersion liquid A is prepared in agent;
(2) synthesis of carbon/molybdenum disulfide nanometer sheet MoS2, the molybdenum disulfide nano sheet is dispersed in prepare in dispersant and is disperseed
Liquid B;
(3) the dispersion liquid A is added drop-wise in the dispersion liquid B, is stirred after supersound process, through detaching, drying
To the two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material.
Preferably, the two-dimensional metallic organic frame nanometer sheet passes through solvent structure;The molybdenum disulfide nano sheet
It is synthesized by hydro-thermal method.
Preferably, the solvent-thermal method is that organic ligand solution is added drop-wise in metal ion solution, molten in 80 DEG C of progress
Agent thermal response obtains the two-dimensional metallic organic frame nanometer sheet through isolating and purifying.
Preferably, the hydro-thermal method is using soluble molybdenum hydrochlorate as molybdenum source, and L-cysteine is sulphur source, at 180 DEG C into
Row hydro-thermal reaction obtains molybdenum disulfide nano sheet through isolating and purifying.
Preferably, the dispersant is ethyl alcohol.
Preferably, sonication treatment time described in step (3) is 25 minutes, and the mixing time is 12 hours.
The beneficial effects of the invention are as follows:Preparation method provided by the invention is by two-dimensional metallic organic frame (MOF) nanometer
Piece is introduced into MoS2In nanometer sheet, two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material is prepared
Two-dimentional MOF/MoS2, using thickness ultra-thin two-dimentional MOF, big specific surface area and fast electronic transmission performance, make material surface
Evolving hydrogen reaction active site increase, specific surface area increase, and then improve material electrocatalytic hydrogen evolution performance, meanwhile, transition gold
Belong to ion Co2+Or Ni2+Introducing, MoS can be enhanced2Electric conductivity, regulate and control MoS2Structure and improve its electrocatalytic hydrogen evolution
Can, pass through two-dimentional MOF nanometer sheets and MoS2Cooperative interaction between nanometer sheet, can significantly improve the two-dimensional metallic has
The electrocatalytic hydrogen evolution performance of machine frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, for exploitation low price, efficient electricity
Catalytic hydrogen evolution catalyst provides a kind of new method.
Description of the drawings
Dimensional Co-MOF/MoS described in Fig. 12- 3 with dimensional Co-MOF nanometer sheets, MoS2The electrocatalytic hydrogen evolution performance of nanometer sheet
Comparison diagram.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In following embodiment, BPY 4,4'Bipyridyl, PVP are polyvinylpyrrolidone, DMF N, N'Dimethyl methyl
Amide, TCPP 5,10,15,20- tetra- (4- carboxyl-phenyls)-porphyrin.
Embodiment 1
The preparation method of the two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, including with
Lower step:
(1) by 4.4mg Co (NO3)2·6H2O, the DMF and 1.5ml of 1.6mg BPY, 10mg PVP addition 4.5ml are anhydrous
In alcohol mixeding liquid, magnetic agitation weighs 4mg TCPP and is added to 1.5ml DMF and 0.5ml to being completely dissolved to obtain solution (1)
In absolute ethyl alcohol mixed liquor, ultrasound 15 minutes to being completely dissolved to obtain solution (2), after solution (2) is added dropwise to solution (1)
In, solution is transferred in the reactor of 18ml Teflon- linings, it is Celsius that the temperature of baking oven is adjusted to 80 by ultrasound after 25 minutes
Degree, and put it into baking oven and react 24 hours.After naturally cooling to room temperature, it is centrifugally separating to obtain red precipitate, ethyl alcohol cleaning
Dimensional Co-MOF nanometer sheets are prepared afterwards twice, then distributes it to and forms dispersion liquid A in 0.5ml ethyl alcohol;
(2) by 0.4g Na2MoO4, stir half an hour in 0.65g L-cysteines and 60ml deionized waters, then seal
In the reactor of 100mL Teflon- linings, and heated 18 hours at 180 DEG C, after reacting cooled to room temperature, centrifugation
Black precipitate is collected, is washed 2 times with deionized water and ethyl alcohol, 80 DEG C of vacuum drying 12h obtain MoS2Nanometer sheet, by 10mg institutes
State MoS2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B;
(3) dispersion liquid A is added drop-wise in dispersion liquid B, is ultrasonically treated 20 minutes, is finally stirred at room temperature 12 hours, from
The precipitation that the heart separates and collects is washed for several times with ethyl alcohol, is then dried in vacuo 10 hours at 80 DEG C, is obtained nanocomposite
Co-MOF/MoS2-3。
Embodiment 2
Nanocomposite Co-MOF/MoS is prepared using step same as Example 12- 1, only step (2)
In be by MoS described in 1mg2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 3
Nanocomposite Co-MOF/MoS is prepared using step same as Example 12- 2, only step (2)
In be by MoS described in 5mg2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 4
Nanocomposite Co-MOF/MoS is prepared using step same as Example 12- 4, only step (2)
In be by MoS described in 20mg2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 5
Nanocomposite Ni-MOF/MoS is prepared using step same as Example 12- 1, only step (1)
In be by 4.4mg Ni (NO3)2·6H2O, DMF the and 1.5ml absolute ethyl alcohols mixing of 4.5ml is added in 1.6mg BPY, 10mg PVP
It is by MoS described in 1mg in liquid, in step (2)2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 6
Nanocomposite Ni-MOF/MoS is prepared using step same as Example 12- 2, only step (1)
In be by 4.4mg Ni (NO3)2·6H2O, DMF the and 1.5ml absolute ethyl alcohols mixing of 4.5ml is added in 1.6mg BPY, 10mg PVP
It is by MoS described in 5mg in liquid, in step (2)2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 7
Nanocomposite Ni-MOF/MoS is prepared using step same as Example 12- 3, only step (1)
In be by 4.4mg Ni (NO3)2·6H2O, DMF the and 1.5ml absolute ethyl alcohols mixing of 4.5ml is added in 1.6mg BPY, 10mg PVP
In liquid.
Embodiment 8
Nanocomposite Ni-MOF/MoS is prepared using step same as Example 12- 4, only step (1)
In be by 4.4mg Ni (NO3)2·6H2O, DMF the and 1.5ml absolute ethyl alcohols mixing of 4.5ml is added in 1.6mg BPY, 10mg PVP
It is by MoS described in 20mg in liquid, in step (2)2Nanometer sheet, which is distributed in 20ml ethyl alcohol, obtains dispersion liquid B.
Embodiment 9
Nanocomposite Co is prepared using step same as Example 10.25Ni0.75-MOF/MoS2- 1, only step
(1) it is by 1.1mg Co (NO in3)2·6H2O,3.3mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 1mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 10
Nanocomposite Co is prepared using step same as Example 10.25Ni0.75-MOF/MoS2- 2, only step
(1) it is by 1.1mg Co (NO in3)2·6H2O,3.3mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 5mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 11
Nanocomposite Co is prepared using step same as Example 10.25Ni0.75-MOF/MoS2- 3, only step
(1) it is by 1.1mg Co (NO in3)2·6H2O,3.3mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in.
Embodiment 12
Nanocomposite Co is prepared using step same as Example 10.25Ni0.75-MOF/MoS2- 4, only step
(1) it is by 1.1mg Co (NO in3)2·6H2O,3.3mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 20mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol
Obtain dispersion liquid B.
Embodiment 13
Nanocomposite Co is prepared using step same as Example 10.5Ni0.5-MOF/MoS2- 1, only step
(1) it is by 2.2mg Co (NO in3)2·6H2O,2.2mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 1mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 14
Nanocomposite Co is prepared using step same as Example 10.5Ni0.5-MOF/MoS2- 2, only step
(1) it is by 2.2mg Co (NO in3)2·6H2O,2.2mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 5mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 15
Nanocomposite Co is prepared using step same as Example 10.5Ni0.5-MOF/MoS2- 3, only step
(1) it is by 2.2mg Co (NO in3)2·6H2O,2.2mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in.
Embodiment 16
Nanocomposite Co is prepared using step same as Example 10.5Ni0.5-MOF/MoS2- 4, only step
(1) it is by 2.2mg Co (NO in3)2·6H2O,2.2mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 20mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol
Obtain dispersion liquid B.
Embodiment 17
Nanocomposite Co is prepared using step same as Example 10.75Ni0.25-MOF/MoS2- 1, only step
(1) it is by 3.3mg Co (NO in3)2·6H2O,1.1mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 1mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 18
Nanocomposite Co is prepared using step same as Example 10.75Ni0.25-MOF/MoS2- 2, only step
(1) it is by 3.3mg Co (NO in3)2·6H2O,1.1mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 5mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol and obtains
To dispersion liquid B.
Embodiment 19
Nanocomposite Co is prepared using step same as Example 10.75Ni0.25-MOF/MoS2- 3, only step
(1) it is by 3.3mg Co (NO in3)2·6H2O,1.1mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in.
Embodiment 20
Nanocomposite Co is prepared using step same as Example 10.75Ni0.25-MOF/MoS2- 4, only step
(1) it is by 3.3mg Co (NO in3)2·6H2O,1.1mg Ni(NO3)2·6H2O, 4.5ml is added in 1.6mg BPY, 10mg PVP
DMF and 1.5ml absolute ethyl alcohol mixed liquors in, be by MoS described in 20mg in step (2)2Nanometer sheet is distributed in 20ml ethyl alcohol
Obtain dispersion liquid B.
Test case
Using Shanghai Chen Hua CHI660E electrochemical workstations come the electrocatalytic hydrogen evolution of 1 material prepared of testing example
Can, all potential values are all converted to relatively reversible hydrogen electrode (RHE) voltage plus (0.2415+0.059pH) V.Utilize three
Electrode system is tested, and (diameter is 3mm to glass-carbon electrode, and area is 0.070785cm2) it is working electrode, it is platinum to electrode
Silk, reference electrode are silver-silver chloride (3M KCl), and electrolyte used is the sulfuric acid solution of 0.5mol/L.Linear scan is surveyed
The related setting for trying parameter is as follows:Scanning range is from 0.1~0.6V (vs.RHE), linear scanning velocity 5mV/s, sampling interval
It is 1mV.
Working electrode prepares as follows:First, on chamois leather by glass-carbon electrode with 0.05 μm of Al2O3Polishing powder is polished,
Time control is in 15min, then, after cleaning 2min in ultrasonic machine with absolute ethyl alcohol, places into and is cleaned by ultrasonic two in distilled water
Secondary, each 2min obtains drying after bright minute surface spare.Weigh the dried Co-MOF/MoS of 4mg216 μ are added in -3 samples
Nafion the and 1mL dispersion liquids of L5wt%, draw that 5 μ L catalyst dispersions are cautious drops in polished glass with liquid-transfering gun
The surface of carbon electrode, naturally dry is spare at room temperature.
Fig. 1 gives Co-MOF/MoS under the same terms2-3,MoS2The electro-catalysis of nanometer sheet and dimensional Co-MOF nanometer sheets
Hydrogen Evolution Performance, the results show that Co-MOF/MoS2- 3 nanocomposites, which show, compares MoS2- MOF nanometers of nanometer sheet and dimensional Co
The better electrocatalytic hydrogen evolution activity of piece.By MoS2After being combined with dimensional Co-MOF nanometer sheets, composite nano materials have height to HER
Activity.It is about 170mV that it, which starts the minimum take-off potential of liberation of hydrogen, on after the current potential, cathode current is rapid in 262mV
It rises and reaches 10mA+cm-2。
Finally it should be noted that:The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations;Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that:It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features;
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (7)
1. a kind of two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material, which is characterized in that the material
Including two-dimensional metallic the organic frame nanometer sheet M-TCPP and molybdenum disulfide nano sheet MoS disperseed mutually2, wherein the M is selected from
Co2+,Ni2+At least one of, the TCPP is 5,10,15,20- tetra- (4- carboxyl-phenyls)-porphyrins, the M and Mo ions
Molar ratio be 1:0.4~8.
2. a kind of system of two-dimensional metallic organic frame described in claim 1/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation Method, which is characterized in that include the following steps:
(1) synthesis two-dimensional metallic organic frame nanometer sheet M-TCPP, wherein M are selected from Co2+,Ni2+At least one of, TCPP 5,
10,15,20- tetra- (4- carboxyl-phenyls)-porphyrin;The two-dimensional metallic organic frame nanometer sheet is dispersed in dispersant and is prepared
Dispersion liquid A;
(2) synthesis of carbon/molybdenum disulfide nanometer sheet MoS2, the molybdenum disulfide nano sheet is dispersed in dispersant and prepares dispersion liquid B;
(3) the dispersion liquid A is added drop-wise in the dispersion liquid B, is stirred after supersound process, through detaching, being dried to obtain institute
State two-dimensional metallic organic frame/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material.
3. a kind of two-dimensional metallic organic frame according to claim 2/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation method, which is characterized in that the two-dimensional metallic organic frame nanometer sheet passes through solvent structure;The molybdenum disulfide
Nanometer sheet is synthesized by hydro-thermal method.
4. a kind of two-dimensional metallic organic frame according to claim 3/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation method, which is characterized in that the solvent-thermal method is that organic ligand solution is added drop-wise in metal ion solution, at 80 DEG C
Solvent thermal reaction is carried out, the two-dimensional metallic organic frame nanometer sheet is obtained through isolating and purifying.
5. a kind of two-dimensional metallic organic frame according to claim 3/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation method, which is characterized in that the hydro-thermal method is using soluble molybdenum hydrochlorate as molybdenum source, and L-cysteine is sulphur source, 180
Hydro-thermal reaction is carried out at DEG C, and molybdenum disulfide nano sheet is obtained through isolating and purifying.
6. a kind of two-dimensional metallic organic frame according to claim 2/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation method, which is characterized in that the dispersant be ethyl alcohol.
7. a kind of two-dimensional metallic organic frame according to claim 2/molybdenum disulfide nano composite electro catalytic liberation of hydrogen material
Preparation method, which is characterized in that sonication treatment time described in step (3) be 25 minutes, the mixing time be 12 hours.
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