CN104307536A - Ternary Z-type visible light water-photocatalytic hydrogen making catalyst and preparation method - Google Patents
Ternary Z-type visible light water-photocatalytic hydrogen making catalyst and preparation method Download PDFInfo
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- CN104307536A CN104307536A CN201410565993.7A CN201410565993A CN104307536A CN 104307536 A CN104307536 A CN 104307536A CN 201410565993 A CN201410565993 A CN 201410565993A CN 104307536 A CN104307536 A CN 104307536A
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- graphene
- indium sulfide
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- 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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Abstract
The invention relates to a ternary Z-type visible light water-photocatalytic hydrogen making catalyst and a preparation method. The catalyst uses graphene as a matrix, and is loaded with nanometer tungsten trioxide in a linear structure and nanometer indium sulfide in a sheet structure at the same time, wherein the mass ratio of the nanometer tungsten trioxide to the nanometer indium sulfide is 3:1-1:3, the amount of the added graphene is 1%-10% of the total mass, and the nanowire diameter of the nanometer tungsten trioxide is not more than 5nm, and the size of the nanometer indium sulfide is 20-100nm. The invention hydrothermally synthesizes a catalyst loaded with two WO3 and In2S3 incapable of independently catalyzing water for making hydrogen under the visible light effect on the graphene surface which is large in specific area and strong in electron transmission capacity, the prepared graphene/ tungsten trioxide/ indium sulfide ternary catalyst has good catalytic hydrogen making performance, the synthesis method is simple and easy to control.
Description
Technical field
The present invention relates to
onethe ternary Z-type visible ray photolytic hydrogen production catalyst and preparation method thereof of kind of visible ray photolytic hydrogen production catalyst, particularly a kind of Graphene loaded tungsten trioxide nano wire and indium sulfide nanometer sheet simultaneously.
Background technology
Solar radiation arrives the far super necessary for human of energy of the earth every year, and is effectively utilize solar energy and one of method being translated into hydrogen energy source with semiconductor catalyst photochemical catalyzing generation hydrogen.As far back as 1972, the TiO such as Honda
2making electrode with Pt, by applying a drift potential, under ultra violet lamp, achieving photocatalysis Decomposition aquatic products hydrogen first.Through the continuous research and probe of many decades, photochemical catalyst as photochemical catalyzing has reached hundreds of, but because response wave length is short, less stable and the factor such as solar absorption transformation efficiency is low, also do not have a kind of gratifying photochemical catalyst can be used for actual large-scale photodissociation aquatic products hydrogen.In order to improve photocatalytic water efficiency, various countries researcher have extensively studied the reaction principle of the photochemical catalyzing of the semi-conducting material possessing different level structure, and the wave-length coverage of response incident light is extended by methods such as noble metal loading, transition cations doping, dye sensitization, composite semiconductors, the compound of retardance Pair production improves the utilization rate to sunlight.Nature Z-type photosynthesis provides new approaches for improving photocatalysis efficiency, and be namely coupled by the level structure of two kinds of different photocatalytic semiconductor materials, the generation of the compound that retardance photo-generate electron-hole is right and back reaction, improves the utilization ratio to sunlight.Simultaneously the decomposition of water needs semi-conducting material to meet at the bottom of conduction band to compare H
+/ H
2redox potential (0v take hydrogen electrode as reference electrode) is more negative, and top of valence band compares O
2/ H
2o redox potential (1.23eV) is corrected.But most semiconductor can only meet a condition, half reaction of the decomposition of water namely can only be realized: 2H
2o → 2H
++ O
2or 2e
-+ 2H
+→ H
2.Because often kind of material only needs to prepare one of hydrogen or oxygen, therefore only need meet respective photoexcitation process respectively, so just for design of material provides very large space, make the range of choice expanded of material.Simultaneous hydrogen production is separated with product oxygen process, effectively can suppress the generation of back reaction in photocatalytic water process.Therefore, Z-type light-catalyzed reaction system becomes the important system of photolysis water hydrogen research in recent years.
WO
3that a kind of outstanding photocatalytic water catalysis produces oxygen material, with TiO
2the same, stability is strong, and photoetch is strong, but band gap 2.7eV compares TiO
23.2eV compares low, E
cB(VS.NHE) 0.74eV, E
vB(VS.NHE) 3.44eV, can absorb more visible ray in sunshine.But, regardless of under ultraviolet light or the irradiation of visible ray, WO
3all can not photocatalytic water hydrogen making, because WO
3higher than H at the bottom of conduction band
+/ H
2reduction potential.At present to WO
3the research of hydrogen making mainly concentrates on and usually replaces WO with one or more yuan
3in W, O, thus lower than H
+/ H
2reduction potential reach the object of hydrogen manufacturing.
In
2s
3bandwidth is 2.0-2.3 eV, E
cB(vs. NHE)-0.8eV, E
vB(VS .NHE) 1.2eV is that a kind of good energy replaces poisonous CdS under visible light.In
2s
3crystal has three kinds of lattice α-In
2s
3(defect cube), β-In
2s
3(cube or tetragonal defect spinelle), γ-In
2s
3(layer structure).In these three kinds of crystal structures, β-In
2s
3due to it, defect spinelle shape is the most potential is applied in light, sound, electrical domain.So researcher is to In
2s
3research concentrate on β-In
2s
3on, β-In
2s
3there are cube or tetragonal defect spinelle shape, cubic β-In
2s
3meet two half-reactions of catalytic water photodissociation, can photodissociation aquatic products hydrogen.But the easy compound of electronics and hole in its reaction, causes hydrogen generation efficiency low and unstable, be difficult to synthesize, so β-In simultaneously
2s
3be more tetragonal defect spinelle shape, but it can not the decomposition of catalytic water under visible ray effect.Because its top of valence band compares O
2/ H
2o redox potential (1.23 eV) is lower.
WO
3with tetragonal defect spinelle β-In
2s
3can visible ray be absorbed, but independent WO
3, tetragonal defect spinelle β-In
2s
3under visible light all can not photocatalytic water.
Summary of the invention
An object of the present invention is to provide a kind of ternary Z-type visible ray photolytic hydrogen production catalyst.
Two of object of the present invention is the preparation method providing this catalyst.
Z-type light-catalyzed reaction system becomes the important system of photolysis water hydrogen research in recent years.Z-type photochemical catalyst is coupled by the level structure of two kinds of different photocatalytic semiconductor materials, and the generation of the compound that retardance photo-generate electron-hole is right and back reaction, improves the utilization ratio to sunlight.Because often kind of material only needs to prepare one of hydrogen or oxygen, therefore only need meet respective photoexcitation process respectively, like this for design of material provides very large space, make the range of choice expanded of material.Simultaneous hydrogen production is separated with product oxygen process, effectively can suppress the generation of back reaction in photocatalytic water process.But Z-type photocatalysis system is limited to complexity, the uncontrollability of catalyst synthesis itself, the selection of co-catalyst simultaneously and the level structure coupled problem of two kinds of different photocatalytic semiconductor materials all have impact on the development of Z-type catalyst system.Main thought of the present invention: on the graphenic surface that, electron transport ability large at surface area is strong, simultaneously load by force but all can not the WO of catalysis product hydrogen separately to visible absorption
3and In
2s
3, by level-density parameter, the transfer in electronics and hole be separated, make the three-way catalyst obtained under visible light can photolysis water hydrogen.
The present invention utilizes the WO of load simultaneously on a kind of, Graphene that electron transport ability is strong large in specific area of a step Hydrothermal Synthesis
3, quadrangle lack spar shape β-In
2s
3simple visible ray Z-type photolysis water hydrogen tri compound semi-conducting material.Under the irradiation of visible ray, WO
3electronics on conduction band transfers to In under the migration of Graphene
2s
3on, In
2s
3hole in valence band is transferred to WO under the migration of Graphene
3on, two kinds of semi-conducting materials all reach being separated of electronics and hole, make at the bottom of conduction band lower than H
+/ H
2reduction potential, top of valence band is higher than O
2/ H
2o oxidation-reduction potential, thus product hydrogen that under visible light can be stable.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of ternary Z-type visible ray photolytic hydrogen production catalyst, it is characterized in that this catalyst take Graphene as substrate, load simultaneously has the nano tungsten trioxide of linear structure and the nanometer indium sulfide of laminated structure, wherein the mass ratio of nano tungsten trioxide and nanometer indium sulfide is 3:1 ~ 1:3, added Graphene amount is between 1% to 10% of gross mass, the nanowire diameter of described nano tungsten trioxide is no more than 5 nm, and described nanometer indium sulfide size is 20 ~ 100 nm.
A kind of method preparing above-mentioned ternary Z-type visible ray photolytic hydrogen production catalyst, it is characterized in that the concrete steps of the method are: the mass fraction generating product in reasonable opinion is in the solution of 1 ~ 10% graphene oxide, the ratio being 1:3 ~ 3:1 in the ratio of W atomicity and In atomicity adds tungsten source and indium source, then add the excessive sulphur source of produced indium sulfide, then regulate pH to 1 ~ 7; At temperature is 120 ~ 200 DEG C, react 8 ~ 24 hours; After stopping reaction, question response still is cooled to room temperature, and washing sample, to neutral, obtains ternary Z-type visible ray photolytic hydrogen production catalyst.
Above-mentioned tungsten source is sodium tungstate or potassium tungstate; Described indium source is: inidum chloride, indium sulfate or indium nitrate; Described sulphur source is: thioacetamide, thiocarbamide or vulcanized sodium.
The present invention adds indium source, sulphur source, tungsten source in graphene oxide solution, by controlling reaction condition, realizes
threetungsten oxide nano and the load of indium sulfide nanometer sheet are on monolithic graphite alkene, now graphite oxide is reduced into the Graphene with better performance, and single step reaction obtains the efficient ternary Z-type visible ray photocatalytic water hydrogen making catalyst of graphene-supported upper tungsten trioxide nanowires and indium sulfide nanometer sheet.
Compared with other visible ray Z-type photolytic hydrogen production catalyst, the present invention has following remarkable advantage: on the graphenic surface that the present invention one step Hydrothermal Synthesis is large in specific area, transmission electronic ability is strong, load two kinds can not the WO of catalysis aquatic products hydrogen separately under visible ray effect
3, In
2s
3, obtained Graphene/tungstic acid/indium sulfide three-way catalyst has good catalyzing manufacturing of hydrogen performance.Synthetic method is simple, easy to control.
Accompanying drawing explanation
Fig. 1 is that the present invention obtains Graphene/tungstic acid/indium sulfide X-ray diffraction (XRD) figure.
Fig. 2 is that the present invention obtains Graphene/tungstic acid/indium sulfide transmission electron microscope(TEM) (TEM) figure.
Fig. 3 is that the present invention obtains Graphene/tungstic acid/indium sulfide photocatalytic water hydrogen making Yield mapping.
Detailed description of the invention
Below in conjunction with accompanying drawing, the process of specific embodiment of the invention and step and interpretation of result as follows:
embodiment 1:get 1 mg/mL ultrasonic oxidation graphene solution 10.4 mL, add 165 mg sodium tungstates, 147 mg inidum chlorides, 56.25 mg thioacetamides, add distilled water to 75 mL, react 12 hours at being transferred to polytetrafluoroethylene (PTFE) 160 DEG C.After stopping reaction, question response still is cooled to room temperature, repeatedly washes sample to neutral, obtains product.Accompanying drawing 1 is X-ray diffraction (XRD) figure of product.In figure, 2 θ 22.718 correspond to WO
3(001) crystal face, 28.172 correspond to WO
3(200) crystal face, 33.235 correspond to In
2s
3(400) crystal face, 47.711 correspond to In
2s
3(440) crystal face, 55.33 correspond to WO
3(202) crystal face.Accompanying drawing 2 is electronic diffraction (TEM) figure of product, clearly can see that graphene film has the dimetric In of thin slice greatly from figure
2s
3and the WO of nano wire
3existence.
Sample thief, test light hydrogen manufacturing performance.Accompanying drawing 3 is the photodissociation aquatic products hydrogen design sketch of Graphene/tungstic acid/indium sulfide, Graphene/tungsten oxide, Graphene/indium sulfide.Can learn Graphene/tungstic acid from figure, Graphene/indium sulfide do not have hydrogen to produce substantially, and Graphene/tungstic acid/indium sulfide hydrogen output is higher.
embodiment 2:can change the sodium tungstate in the Graphene/tungstic acid/indium sulfide system of synthesis in embodiment 1 into potassium tungstate, additive method is with reference to embodiment 1, and the three-way catalyst that also can obtain similar Graphene/tungstic acid/indium sulfide realizes the object of producing hydrogen.
embodiment 3:can change the inidum chloride in the Graphene/tungstic acid/indium sulfide system of synthesis in embodiment 1 into indium sulfate, additive method is with reference to embodiment 1, and the three-way catalyst that also can obtain similar Graphene/tungstic acid/indium sulfide realizes the object of producing hydrogen.
embodiment 4:can change the inidum chloride in the Graphene/tungstic acid/indium sulfide system of synthesis in embodiment 1 into indium nitrate, additive method is with reference to embodiment 1, and the three-way catalyst that also can obtain similar Graphene/tungstic acid/indium sulfide realizes the object of producing hydrogen.
embodiment 5:can change the thioacetamide in the Graphene/tungstic acid/indium sulfide system of synthesis in embodiment 1 into thiocarbamide, additive method is with reference to embodiment 1, and the three-way catalyst that also can obtain similar Graphene/tungstic acid/indium sulfide realizes the object of producing hydrogen.
Claims (3)
1. a ternary Z-type visible ray photolytic hydrogen production catalyst, it is characterized in that this catalyst take Graphene as substrate, load simultaneously has the nano tungsten trioxide of linear structure and the nanometer indium sulfide of laminated structure, wherein the mass ratio of nano tungsten trioxide and nanometer indium sulfide is 3:1 ~ 1:3, added Graphene amount is between 1% to 10% of gross mass, the nanowire diameter of described nano tungsten trioxide is no more than 5 nm, and described nanometer indium sulfide size is 20 ~ 100 nm.
2. prepare the method for ternary Z-type visible ray photolytic hydrogen production catalyst according to claim 1 for one kind, it is characterized in that the concrete steps of the method are: the mass fraction generating product in reasonable opinion is in the solution of 1 ~ 10% graphene oxide, the ratio being 1:3 ~ 3:1 in the ratio of W atomicity and In atomicity adds tungsten source and indium source, then add the excessive sulphur source of produced indium sulfide, then regulate pH to 1 ~ 7; At temperature is 120 ~ 200 DEG C, react 8 ~ 24 hours; After stopping reaction, question response still is cooled to room temperature, and washing sample, to neutral, obtains ternary Z-type visible ray photolytic hydrogen production catalyst.
3. method according to claim 2, is characterized in that described tungsten source is sodium tungstate or potassium tungstate; Described indium source is: inidum chloride, indium sulfate or indium nitrate; Described sulphur source is: thioacetamide, thiocarbamide or vulcanized sodium.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457658A (en) * | 2015-12-08 | 2016-04-06 | 哈尔滨工业大学深圳研究生院 | Z-type catalyst capable of simulating photosynthesis to degrade pollutants and generate hydrogen simultaneously, and preparation method of Z-type catalyst |
| CN109317157A (en) * | 2018-11-26 | 2019-02-12 | 辽宁大学 | A kind of ternary Z-type complex sound catalyst and its preparation method and application for antibiotic waste water of degrading |
| CN109926080A (en) * | 2018-12-04 | 2019-06-25 | 山东科技大学 | A kind of visible light-responded production hydrogen photochemical catalyst GO/SiC/WO3Preparation method and application |
| CN111215095A (en) * | 2018-11-23 | 2020-06-02 | 中国科学院金属研究所 | Metallic compound/oxide/sulfide three-phase heterojunction photocatalytic material and preparation method thereof |
| CN112028116A (en) * | 2020-07-14 | 2020-12-04 | 西南大学 | Metal-doped indium sulfide and photoelectric biosensor thereof |
-
2014
- 2014-10-22 CN CN201410565993.7A patent/CN104307536B/en not_active Expired - Fee Related
Non-Patent Citations (3)
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| MIN-QUAN YANG ET AL.: "《Improving the Visible Light Photoactivity of In2S3−Graphene Nanocomposite via a Simple Surface Charge Modification Approach》", 《LANGMUIR》, no. 29, 31 December 2013 (2013-12-31) * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457658A (en) * | 2015-12-08 | 2016-04-06 | 哈尔滨工业大学深圳研究生院 | Z-type catalyst capable of simulating photosynthesis to degrade pollutants and generate hydrogen simultaneously, and preparation method of Z-type catalyst |
| CN111215095A (en) * | 2018-11-23 | 2020-06-02 | 中国科学院金属研究所 | Metallic compound/oxide/sulfide three-phase heterojunction photocatalytic material and preparation method thereof |
| CN109317157A (en) * | 2018-11-26 | 2019-02-12 | 辽宁大学 | A kind of ternary Z-type complex sound catalyst and its preparation method and application for antibiotic waste water of degrading |
| CN109317157B (en) * | 2018-11-26 | 2021-08-24 | 辽宁大学 | Ternary Z-shaped composite acoustic catalyst for degrading antibiotic wastewater and preparation method and application thereof |
| CN109926080A (en) * | 2018-12-04 | 2019-06-25 | 山东科技大学 | A kind of visible light-responded production hydrogen photochemical catalyst GO/SiC/WO3Preparation method and application |
| CN109926080B (en) * | 2018-12-04 | 2021-08-27 | 山东科技大学 | Visible light response hydrogen production photocatalyst GO/SiC/WO3Preparation method and application of |
| CN112028116A (en) * | 2020-07-14 | 2020-12-04 | 西南大学 | Metal-doped indium sulfide and photoelectric biosensor thereof |
| CN112028116B (en) * | 2020-07-14 | 2022-08-19 | 西南大学 | Metal-doped indium sulfide and photoelectric biosensor thereof |
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| CN104307536B (en) | 2016-12-07 |
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