CN108295870A - The preparation method of sulfide-graphene composite material photoelectric - Google Patents
The preparation method of sulfide-graphene composite material photoelectric Download PDFInfo
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- CN108295870A CN108295870A CN201810086455.8A CN201810086455A CN108295870A CN 108295870 A CN108295870 A CN 108295870A CN 201810086455 A CN201810086455 A CN 201810086455A CN 108295870 A CN108295870 A CN 108295870A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- -1 sulphur molybdate salt Chemical class 0.000 claims description 6
- 239000011833 salt mixture Substances 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001661 cadmium Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YKHQSWIVNHQJSW-UHFFFAOYSA-N iron;oxalonitrile Chemical compound [Fe].N#CC#N YKHQSWIVNHQJSW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 241000446313 Lamella Species 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910052961 molybdenite Inorganic materials 0.000 description 14
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011684 sodium molybdate Substances 0.000 description 5
- 235000015393 sodium molybdate Nutrition 0.000 description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 240000001492 Carallia brachiata Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
-
- 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
-
- 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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of sulfide graphene composite material photoelectric, first disperse graphene oxide powder in water, obtain graphene oxide dispersion；It is added soluble metallic salt into dispersion liquid again, after standing, washing precipitate, drying, grinding obtain the graphene oxide powder of metal ion mixing；It is dispersed again in deionized water again, after stirring, sulfide precursor salt solution is added, thiocarbamide is added and simultaneously stirs, then reaction product is obtained by one step hydro thermal method, after cooled to room temperature, by reaction product centrifuge washing, is dried to obtain solid powder.Synthesizing sulfide of the present invention/graphene complex preparation method is simple, the seed layer that metal ion is grown as the interface bridging agent and sulfide of sulfide and graphene surface, it is evenly dispersed to promote sulfide lamella, inhibit the stacking of graphene sheet layer, big specific surface area can provide more active site, then effectively improve the catalytic performance of composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of photoelectric, are urged more particularly to a kind of graphene composite material photoelectricity
The preparation method of agent is applied to photo-electrocatalytic technology field.
Background technology
As energy crisis, environmental disruption, atmosphere pollution and global warming issue are on the rise, renewable cleaning
The energy receives more and more attention.Hydrogen be considered as a rich reserves, cleaning, it is environmental-friendly and high fuel value can be again
The raw energy, so far, research is dedicated to water electrolysis liberation of hydrogen, photocatalysis liberation of hydrogen, electrocatalytic hydrogen evolution (HER) etc. mostly, wherein electricity
Catalytic hydrogen evolution is efficient and low energy consumption hydrogen energy source preparation means.However, most effective electrocatalytic hydrogen evolution reaction is to be based at present
The catalytic action of noble metal-platinum, this method rare, expensive limitation by noble metal reserves hinder it real on a large scale
Border is applied, and therefore, the new catalyst that exploitation catalytic performance is high, cost of material is cheap is increasingly urgent.The purpose of the invention be for
Push reproducible clean energy resource production and use and efficient new catalyst is provided.
Graphene (RGO) has excellent physical structural characteristic, such as big specific surface area, the conduction of high electronics and heat transfer
Rate.Graphene has been widely used in the energy, the various fields such as environment due to its unique physical and chemical performance.
[V.Chabot,D.Higgins,A.P.Yu,X.C.Xiao,Z.W.Chen,J.J.Zhang,Energy Environ.Sci.,
2014,7,1564-1596.]
Transition metal stratiform sulfide has also obtained extensive research because it is with performances such as excellent light, electricity, catalysis.
[Y.Y.Liu,J.J.Wu,K.P.Hackenberg,J.Zhang,Y.M.Wang,Y.C.Yang,K.Keyshar,J.Gu,
T.Ogitsu,R.Vajtai,J.Lou,P.M.Ajayan,B.C.Wood,B,I.Yakobson,Nat.Energy,2017,2,
17127.] the features such as laminate sulfide has large specific surface area, and adsorption capacity is strong, reactivity is high, but still suffer from and lead
It is electrically poor, the defects of easy self aggregation.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The preparation method of sulfide-graphene composite material photoelectric provides electronics using metal ion as interface bridging agent
Person's metal sulfide and electron acceptor receptor graphene organically combine, and using graphene there is big specific surface area can provide
The characteristic of a large amount of activity points, prepares efficient, rugged catalyst.The inventive method is simple, of low cost, gained catalyst
Active high, applicable elements are loose, are widely used.The method of the present invention improves the catalytic activity of compound, inhibits graphene and vulcanization
The stacking certainly of object in the reaction, the present invention change the connection mode between graphene and sulfide by addition metal ion, into
And improve the hydrogen evolution activity of electron transfer efficiency and catalyst between graphene and sulfide.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of sulfide-graphene composite material photoelectric, includes the following steps：
(1) graphene oxide is dissolved in deionized water, and carries out ultrasonic disperse, obtain graphene oxide dispersion；It will
Soluble metallic salt is dissolved in above-mentioned dispersion liquid, and graphene oxide-soluble metallic salt mixed liquor is stood after being sufficiently stirred, is removed
At least once, dry, grinding obtains the graphene oxide powder of metal ion mixing for layer washing of precipitate；Soluble metallic salt is excellent
Choosing is using in soluble molysite, cobalt salt, nickel salt, mantoquita, zinc salt, manganese salt, silver salt, titanium salt, platinum salt, gold salt, cadmium salt and chromic salts
Any one salt or arbitrary several salt-mixture；It is preferred that the mass ratio of graphene oxide and soluble metallic salt is 1:1~10:
1；In graphene oxide-soluble metallic salt mixed liquor or metal ion a concentration of 4 × 10-4~7 × 10-3mol/
L；In graphene oxide dispersion, or preferably graphene oxide a concentration of 0.5~1.5mgmL-1；In graphite oxide
In alkene-soluble metallic salt mixed liquor, or preferably the total concentration of metal salt and graphene oxide is 1~5mgmL-1；
(2) the graphene oxide powder ultrasonic disperse of metal ion mixing will be prepared in the step (1) in deionization
In water, sulfide precursor salt solution is added, and be stirred to mixed liquor, add thiocarbamide after thorough mix-ing, be made
Reactant mixed solution, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed, and carried out at 100-250 DEG C
Hydro-thermal reaction at least 16 hours, obtains black precipitate product；It is preferred that the matter of graphene oxide and dissolvable sulfide precursor salt
Amount is than being 1:1~1:10；The sulfide precursor salt preferably uses molybdate salt, iron cyanogen root salt, cobalt acid group salt, hexacyanocobaltate acid
Root salt, sulphur molybdate salt, tungstate radicle salt, titanate radical salt and any one soluble-salt or arbitrary several solvable in mangaic acid root salt
Property salt-mixture；Or the S in the metal M preferably in thiocarbamide and sulfide precursor salt：The molar concentration rate of M is 6:1~2:1；
In reactant mixed solution, or the molar concentration of preferably dissolvable sulfide precursor salt is 0.015~0.15mol/L；
(3) black will be dried to obtain after the middle preparation black precipitate water of the step (2) and ethyl alcohol wash at least once
Solid powder, as sulfide-graphene composite material photoelectric.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the method for the present invention improves the catalytic activity of compound, inhibit the stacking certainly of graphene and sulfide in the reaction,
The present invention improves graphene and sulfide by the way that the connection mode between metal ion change graphene and sulfide is added
Between the hydrogen evolution activity of electron transfer efficiency and catalyst；
2. the method for the present invention prepares the novel sulfide/graphene of various structures using metal ion as interface bridging agent
Compound；
3. the method for the present invention is easy to operate, of low cost；It promotes metal ion as interface bridging agent and seed layer
Lamella sulfide is grown on graphene sheet layer, to improve the catalytic performance of catalyst.
Description of the drawings
Fig. 1 is the scanning electron microscope of sulfide-graphene composite material photoelectric prepared by the embodiment of the present invention one
(SEM) figure.
Fig. 2 is the scanning electron microscope of sulfide-graphene composite material photoelectric prepared by the embodiment of the present invention two
(SEM) figure.
Fig. 3 is the scanning electron microscope of sulfide-graphene composite material photoelectric prepared by the embodiment of the present invention three
(SEM) figure.
Specific implementation mode
Said program is described further below in conjunction with specific examples of the implementation, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one：
In the present embodiment, referring to Fig. 1, a kind of preparation method of sulfide-graphene composite material photoelectric, packet
Include following steps：
(1) 1g graphene oxides are dissolved in 1000mL deionized waters, and carry out ultrasonic disperse, obtain graphene oxide point
Dispersion liquid；1g Copper dichloride dihydrate soluble metallic salts are dissolved in above-mentioned dispersion liquid, graphene oxide-is stood after being sufficiently stirred 1h
Copper chloride mixed liquor, it is primary to remove layer washing of precipitate, is put into vacuum drying oven and is dried at 45 DEG C, is then ground to powder
Shape obtains the graphene oxide powder of metal copper ion doping；
(2) will prepare in the step (1) copper ion doped graphene oxide powder ultrasonic disperse 100mL go from
In sub- water, sodium molybdate solutions of the 2g containing molybdenum element is added, and 1h is stirred to mixed liquor, add 4g after thorough mix-ing
Thiocarbamide ((NH2)2CS), reactant mixed solution is made, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed,
And hydro-thermal reaction 16h is carried out at 200 DEG C, obtain black precipitate product；
(3) black solid will be dried to obtain after the middle preparation black precipitate water of the step (2) and ethyl alcohol washed once
Powder, as molybdenum sulfide/graphene (RGO-Cu-MoS2) composite material photoelectric.
The present embodiment experimental test and analysis：
To molybdenum sulfide manufactured in the present embodiment/graphene (RGO-Cu-MoS2) composite material photoelectric is detected,
The pattern that material surface is observed using scanning electron microscope, referring to Fig. 1.Fig. 1 is sulfide-graphene manufactured in the present embodiment
Scanning electron microscope (SEM) figure of composite material photoelectric, it is observed that apparent layer structure.The structure of the present embodiment synthesis
Sulfide/graphene complex preparation method is simple, using metal ion as the interface bridging agent of sulfide and graphene surface
And the seed layer of sulfide growth, on the one hand promote sulfide lamella evenly dispersed, inhibits the stacking of graphene sheet layer, another party
The big specific surface area in face can provide more active site, then effectively improve the catalytic performance of composite material.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, referring to Fig. 2, a kind of preparation method of sulfide-graphene composite material photoelectric, packet
Include following steps：
(1) 1g graphene oxides are dissolved in 1000mL deionized waters, and carry out ultrasonic disperse, obtain graphene oxide point
Dispersion liquid；Bis- chloride hydrate zinc soluble metallic salts of 1g are dissolved in above-mentioned dispersion liquid, graphene oxide-is stood after being sufficiently stirred 1h
Zinc chloride mixed liquor, it is primary to remove layer washing of precipitate, is put into vacuum drying oven and is dried at 45 DEG C, is then ground to powder
Shape obtains the graphene oxide powder of metallic zinc ion doping；
(2) by prepared in the step (1) zinc ion doping graphene oxide powder ultrasonic disperse 100mL go from
In sub- water, sodium molybdate solutions of the 2g containing molybdenum element is added, and 1h is stirred to mixed liquor, add 4g after thorough mix-ing
Thiocarbamide is made reactant mixed solution, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed, and at 200 DEG C
Lower progress hydro-thermal reaction 16h, obtains black precipitate product；
(3) black solid will be dried to obtain after the middle preparation black precipitate water of the step (2) and ethyl alcohol washed once
Powder, as molybdenum sulfide/graphene (RGO-Zn-MoS2) composite material photoelectric.
The present embodiment experimental test and analysis：
To molybdenum sulfide manufactured in the present embodiment/graphene (RGO-Zn-MoS2) composite material photoelectric is detected,
The pattern that material surface is observed using scanning electron microscope, referring to Fig. 2.Fig. 2 is sulfide-graphene manufactured in the present embodiment
Scanning electron microscope (SEM) figure of composite material photoelectric, it is observed that apparent layer structure.The structure of the present embodiment synthesis
Sulfide/graphene complex preparation method is simple, using metal ion as the interface bridging agent of sulfide and graphene surface
And the seed layer of sulfide growth, on the one hand promote sulfide lamella evenly dispersed, inhibits the stacking of graphene sheet layer, another party
The big specific surface area in face can provide more active site, then effectively improve the catalytic performance of composite material.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 3, a kind of preparation method of sulfide-graphene composite material photoelectric, packet
Include following steps：
(1) 1g graphene oxides are dissolved in 1000mL deionized waters, and carry out ultrasonic disperse, obtain graphene oxide point
Dispersion liquid；1g Nickel dichloride hexahydrate soluble metallic salts are dissolved in above-mentioned dispersion liquid, graphene oxide-is stood after being sufficiently stirred 1h
Nickel chloride mixed liquor, it is primary to remove layer washing of precipitate, is put into vacuum drying oven and is dried at 45 DEG C, is then ground to powder
Shape obtains the graphene oxide powder of metallic nickel ions doping；
(2) by prepared in the step (1) nickel ion doping graphene oxide powder ultrasonic disperse 100mL go from
In sub- water, sodium molybdate solutions of the 2g containing molybdenum element is added, and 1h is stirred to mixed liquor, add 4g after thorough mix-ing
Thiocarbamide is made reactant mixed solution, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed, and at 200 DEG C
Lower progress hydro-thermal reaction 16h, obtains black precipitate product；
(3) black solid will be dried to obtain after the middle preparation black precipitate water of the step (2) and ethyl alcohol washed once
Powder, as molybdenum sulfide/graphene (RGO-Ni-MoS2) composite material photoelectric.
The present embodiment experimental test and analysis：
To molybdenum sulfide manufactured in the present embodiment/graphene (RGO-Ni-MoS2) composite material photoelectric is detected,
The pattern that material surface is observed using scanning electron microscope, referring to Fig. 3.Fig. 3 is sulfide-graphene manufactured in the present embodiment
Scanning electron microscope (SEM) figure of composite material photoelectric, it is observed that apparent layer structure.The structure of the present embodiment synthesis
Sulfide/graphene complex preparation method is simple, using metal ion as the interface bridging agent of sulfide and graphene surface
And the seed layer of sulfide growth, on the one hand promote sulfide lamella evenly dispersed, inhibits the stacking of graphene sheet layer, another party
The big specific surface area in face can provide more active site, then effectively improve the catalytic performance of composite material.
The η tests of liberation of hydrogen HER overpotential：
Glass carbon (the Glass of above-described embodiment sulfide-graphene composite material photoelectric sample will be coated respectively with
Carbon) it is used as working electrode, platinum filament to be used as to electrode, Ag/AgCl electrodes are as reference electrode；In 0.5M H2SO4Electrolyte
In, between sweep speed 5mV/s, test voltage ranging from 0V to -0.5V；Sample preparation：A certain amount of sample to be tested is weighed,
It is separately added into the water of 70% volume, the mass fraction of the isopropanol of 25% volume, 5% volume is 5%Nafion solution, and ultrasound is extremely
Then dispersion is taken out 10 μ L dispersant liquid drops with liquid-transfering gun and is coated on glass-carbon electrode, tested after natural drying, obtain contrast experiment's sample
Product are respectively pure MoS2, undoped with metal ion MoS2RGO-Cu-MoS prepared by/RGO, embodiment one2, embodiment two prepare
RGO-Zn-MoS2And RGO-Ni-MoS prepared by embodiment three2Liberation of hydrogen (HER) overpotential η, referring to such as following table 1.
Table 1. sample liberation of hydrogen (HER) overpotential compares
| Sample (Materials) | η(J=10mA cm -2)/mV(vs.NHE) | η(J=10mA cm -2)/mV(vs.NHE) |
| It is unglazed | Illumination (150W Xe light source) | |
| MoS2 | 341 | 341 |
| MoS2/RGO | 253 | 251 |
| RGO-Cu-MoS2 | 240 | 227 |
| RGO-Ni-MoS2 | 208 | 198 |
| RGO-Zn-MoS2 | 229 | 220 |
By above-described embodiment and contrast experiment it is found that the preparation side of sulfide of the present invention/graphene complex catalyst
Method.Using metal ion as interface bridging agent by electronics supplier metal sulfide and the organic knot of electron acceptor receptor graphene
It closes, and using graphene there is big specific surface area can provide the characteristic of a large amount of active points, prepare efficient, stably catalyzed
Agent.The inventive method is simple, of low cost, and gained catalyst activity is high, and applicable elements are loose, are widely used.
Example IV：
In the present embodiment, the preparation method of a kind of sulfide-graphene composite material photoelectric, including walk as follows
Suddenly：
(1) 1g graphene oxides are dissolved in 1000mL deionized waters, and carry out ultrasonic disperse, obtain graphene oxide point
Dispersion liquid；0.1g Copper dichloride dihydrate soluble metallic salts are dissolved in above-mentioned dispersion liquid, graphite oxide is stood after being sufficiently stirred 1h
Alkene-copper chloride mixed liquor, it is primary to remove layer washing of precipitate, is put into vacuum drying oven and is dried at 45 DEG C, is then ground to powder
Last shape obtains the graphene oxide powder of metal copper ion doping；
(2) will prepare in the step (1) copper ion doped graphene oxide powder ultrasonic disperse 100mL go from
In sub- water, sodium molybdate solutions of the 1g containing molybdenum element is added, and 1h is stirred to mixed liquor, add 4g after thorough mix-ing
Thiocarbamide is made reactant mixed solution, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed, and at 100 DEG C
Lower progress hydro-thermal reaction 16h, obtains black precipitate product；
(3) this step is identical as embodiment one.
The present embodiment experimental test and analysis：
Structure sulfide/graphene complex preparation method of the present embodiment synthesis is simple, using metal ion as vulcanization
The seed layer of the interface bridging agent and sulfide of object and graphene surface growth, on the one hand promotes sulfide lamella evenly dispersed,
Inhibit the stacking of graphene sheet layer, on the other hand big specific surface area can provide more active site, then effectively improve
The catalytic performance of composite material.
Embodiment five：
In the present embodiment, the preparation method of a kind of sulfide-graphene composite material photoelectric, including walk as follows
Suddenly：
(1) 1g graphene oxides are dissolved in 1000mL deionized waters, and carry out ultrasonic disperse, obtain graphene oxide point
Dispersion liquid；0.1g Copper dichloride dihydrate soluble metallic salts are dissolved in above-mentioned dispersion liquid, graphite oxide is stood after being sufficiently stirred 1h
Alkene-copper chloride mixed liquor, it is primary to remove layer washing of precipitate, is put into vacuum drying oven and is dried at 45 DEG C, is then ground to powder
Last shape obtains the graphene oxide powder of metal copper ion doping；
(2) will prepare in the step (1) copper ion doped graphene oxide powder ultrasonic disperse 100mL go from
In sub- water, sodium molybdate solutions of the 10g containing molybdenum element is added, and 1h is stirred to mixed liquor, added after thorough mix-ing
4g thiocarbamides are made reactant mixed solution, then reactant mixed solution are transferred in polytetrafluoroethylkettle kettle and is sealed, and 250
Hydro-thermal reaction 16h is carried out at DEG C, obtains black precipitate product；
(3) this step is identical as embodiment one.
The present embodiment experimental test and analysis：
The preparation method of a kind of sulfide of the above embodiment of the present invention-graphene composite material photoelectric, first by oxygen
Graphite alkene powder disperses in water, obtains graphene oxide dispersion；Soluble metallic salt is added into dispersion liquid again, stands
Later, sediment is washed with deionized several times, dry, grinding obtains the graphene oxide powder of metal ion mixing；Again
The graphene oxide powder of above-mentioned metal ion mixing is dispersed again in deionized water, after stirring, sulfide forerunner is added
Body salting liquid stirs and a certain amount of thiocarbamide ((NH is added2)2CS it) and stirs.Mixed raw material is put into close in polytetrafluoroethylkettle kettle
Envelope obtains reaction product by one step hydro thermal method, after cooled to room temperature, is centrifuged reaction product with deionized water and ethyl alcohol
After washing several times, it is dried to obtain solid powder.Structure sulfide/graphene complex system of the above embodiment of the present invention synthesis
Preparation Method is simple, the seed layer that metal ion is grown as the interface bridging agent and sulfide of sulfide and graphene surface,
On the one hand promote sulfide lamella evenly dispersed, inhibit the stacking of graphene sheet layer, on the other hand big specific surface area can carry
For more active site, the catalytic performance of composite material is then effectively improved.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from the technical principle and invention structure of the preparation method of sulfide of the present invention-graphene composite material photoelectric
Think, belongs to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfide-graphene composite material photoelectric, which is characterized in that include the following steps：
(1) graphene oxide is dissolved in deionized water, and carries out ultrasonic disperse, obtain graphene oxide dispersion；It will be solvable
Property metal salt be dissolved in above-mentioned dispersion liquid, graphene oxide-soluble metallic salt mixed liquor is stood after being sufficiently stirred, it is heavy to remove layer
Washing form sediment at least once, dry, grinding obtains the graphene oxide powder of metal ion mixing；
(2) the graphene oxide powder ultrasonic disperse of metal ion mixing will be prepared in the step (1) in deionized water,
Sulfide precursor salt solution is added, and mixed liquor is stirred, thiocarbamide is added after thorough mix-ing, reactant is made
Mixed solution, then reactant mixed solution is transferred in polytetrafluoroethylkettle kettle and is sealed, and progress hydro-thermal is anti-at 100-250 DEG C
Should be at least 16 hours, obtain black precipitate product；
(3) black solid will be dried to obtain after the middle preparation black precipitate water of the step (2) and ethyl alcohol wash at least once
Powder, as sulfide-graphene composite material photoelectric.
2. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (1), the soluble metallic salt using soluble molysite, cobalt salt, nickel salt, mantoquita,
Any one salt in zinc salt, manganese salt, silver salt, titanium salt, platinum salt, gold salt, cadmium salt and chromic salts or arbitrary several salt-mixture.
3. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (1), the mass ratio of graphene oxide and soluble metallic salt is 1:1~10:1.
4. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (2), the mass ratio of graphene oxide and dissolvable sulfide precursor salt is 1:1~
1:10。
5. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (2), the sulfide precursor salt is using molybdate salt, iron cyanogen root salt, cobalt acid group
Salt, hexacyanocobaltate acid root salt, sulphur molybdate salt, tungstate radicle salt, titanate radical salt and any one soluble-salt in mangaic acid root salt or
Arbitrary several soluble salt-mixtures.
6. the preparation method of sulfide-graphene composite material photoelectric according to claim 5, which is characterized in that
Include the following steps：In the step (2), thiocarbamide and the S in the metal M in sulfide precursor salt：The molar concentration rate of M
It is 6:1~2:1.
7. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (2), in reactant mixed solution, the molar concentration of dissolvable sulfide precursor salt
For 0.015~0.15mol/L.
8. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (1), in graphene oxide-soluble metallic salt mixed liquor, concentration of metal ions is
4×10-4~7 × 10-3mol/L。
9. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (1), in graphene oxide dispersion, graphene oxide a concentration of 0.5~
1.5mg·mL-1。
10. the preparation method of sulfide-graphene composite material photoelectric according to claim 1, which is characterized in that
Include the following steps：In the step (1), in graphene oxide-soluble metallic salt mixed liquor, metal salt and oxidation stone
The total concentration of black alkene is 1~5mgmL-1。
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