CN103736501A - Sulfur-indium-zinc composite material with homogeneous heterogeneous knot, as well as preparation method and application of material - Google Patents
Sulfur-indium-zinc composite material with homogeneous heterogeneous knot, as well as preparation method and application of material Download PDFInfo
- Publication number
- CN103736501A CN103736501A CN201410005878.4A CN201410005878A CN103736501A CN 103736501 A CN103736501 A CN 103736501A CN 201410005878 A CN201410005878 A CN 201410005878A CN 103736501 A CN103736501 A CN 103736501A
- Authority
- CN
- China
- Prior art keywords
- zinc composite
- indium zinc
- knot
- isomerism
- sulphur indium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a sulfur-indium-zinc composite material with a homogeneous heterogeneous knot, as well as a preparation method and an application of the material and belongs to the technical field of material preparation and photocatalysis. The sulfur-indium-zinc composite material disclosed by the invention has a high specific surface area; the phase knot composed of a hexagonal phase and a cubic phase can be used for effectively increasing the separation efficiency of photon-generated carriers of a system, so that the light catalytic activity of visible light of ZnIn2S4 is improved and the sulfur-indium-zinc composite material can be used for efficiently degrading organic pollutants, carrying out photocatalytic sterilization, photolyzing water to prepare hydrogen and carrying out the photocatalysis to selectively oxidize alcohols. The preparation process of a catalyst is simple and low in cost; during the production processing, the green and environment-friendly effects can be realized and the stability of the catalyst is high; the actual production requirements are met and the application potential is great.
Description
Technical field
The invention belongs to material preparation and photocatalysis technology field, be specifically related to a kind of sulphur indium zinc composite with isomerism knot and its preparation method and application.
Background technology
Environmental pollution and energy crisis are 21 century mankind face and key subjects urgently to be resolved hurrily.And photocatalysis technology due to its reaction thoroughly, reaction condition is gentle, have redox ability concurrently, have the advantages such as energy-efficient, non-secondary pollution, develop in recent years the new technology of utilizing solar energy to carry out the depollution of environment and energy conversion for a kind of rapidly, become study hotspot of greatest concern at present.
At present, with TiO
2be that main semiconductor light-catalyst exists the scientific and technical difficult problem that photo-quantum efficiency is low and the low grade of solar energy utilization ratio is crucial, make its development be subject to very big restriction.And the key solving is still on photochemical catalyst, therefore, Chinese scholars is being done a large amount of exploration work aspect the photo-quantum efficiency of raising photochemical catalyst: as, at aspects such as the modification of titanium dioxide optical catalyst, modifications, done a large amount of explorations and obtained certain progress, simultaneously the also novel non-titanium dioxide optical catalyst of active development.Although these research work have promoted photocatalysis development greatly, photochemical catalyst increases for its quantum efficiency of specific reaction, but still has some problems, as the ion of doping easily forms the new complex centre in light induced electron and hole; Modify the dyestuff of sensitization unstable etc.Therefore, researchers focus on the synthetic energy-efficient non-TiO that directly utilizes visible ray of design by sight
2based photocatalyst.
Wherein, multi-element metal sulfide semiconductor photochemical catalyst is because good absorbing properties and adjustable energy gap are widely studied.In numerous visible-light photocatalysis materials of having reported, ZnIn
2s
4because its unique structure and physicochemical properties have shown good visible light photocatalysis performance, overcome again the shortcoming of the easy photoetch of traditional sulfide, in photocatalysis technology, have a good application prospect.At present, ZnIn
2s
4research mainly concentrate on regulate shape, crystalline phase adjusting, doping vario-property, exploitation new preparation process, compound etc. with other semi-conducting materials, to expect effectively to improve its photocatalysis performance.Yet these research effects are unsatisfactory, be therefore badly in need of a kind of effective means of development in order to strengthen ZnIn
2s
4photocatalysis performance.Between the semiconductor that can be with coupling, build hetero-junctions, be proved to be to promote a kind of effective ways of the photodetachment of electric charge.But the Lattice Matching degree of dissimilar materials is low, be difficult to the stable formation hetero-junctions of combining closely.Consider ZnIn
2s
4have Emission in Cubic, three kinds of typical structures of Liu Fangxiangyu oblique parallelepiped, between its different crystalline phases, have the band structure matching, the present invention is first at out of phase ZnIn
2s
4middle structure isomerism knot, lattice matched, has realized the efficient separation of photo-generated carrier, thereby under radiation of visible light ZnIn
2s
4show high photocatalysis performance.
Summary of the invention
The object of the present invention is to provide a kind of sulphur indium zinc composite with isomerism knot and its preparation method and application.This catalyst preparation process is simple, and cost is low, production process environmental protection, and catalyst stability is high, and realistic need of production has larger application potential.
For achieving the above object, the present invention adopts following technical scheme:
The specific area with the sulphur indium zinc composite of isomerism knot of the present invention is 50-300 m
2/ g, its pattern is nano-sheet, in high-resolution-ration transmission electric-lens, can observe lattice fringe clearly.
The present invention utilizes hydro-thermal method to prepare isomerism ZnIn in conjunction with after-baking process first
2s
4compound, the isomerism making knot can improve the separative efficiency of the photo-generated carrier of system effectively.Specifically comprise the following steps:
(1) respectively by the ZnCl of the certain mass calculating according to stoichiometric equation
2(10-20 mmol), In (NO
3)
34.5H
2o(20-40 mmol), thioacetamide (40-80 mmol), polyvinylpyrrolidone (0-2 g) joins in polytetrafluoroethylene (PTFE) reactor, then in reactor, add in 70 mL distilled water/ethanol/tetrachloromethane (volume ratio 1:1:0.2) mixed liquors, reactor is placed on magnetic stirring apparatus, regulate pH value 1-13, stir after 120 min, be placed in the baking oven of 80-160 ℃ and react 2-36 h, question response still is cooled to after room temperature, mixture in reactor is taken out, centrifugation, the sediment obtaining is with after distilled water and ethanol washing for several times, in the baking oven of 60 ℃, dry, obtain the Powdered presoma of crocus,
(2) the above-mentioned sulphur indium zinc precursor body preparing is placed in to tube furnace and calcines under nitrogen atmosphere, temperature is controlled at 200-450 ℃, and insulation 2-8 h, obtains isomerism sulphur indium zinc complexes.
Remarkable advantage of the present invention is:
(1) the present invention adopts hydro-thermal method to prepare isomerism ZnIn in conjunction with after-baking process first
2s
4compound, prepared isomerism knot can improve the separative efficiency of the photo-generated carrier of system effectively, thereby has improved ZnIn
2s
4visible light photocatalysis active.
(2) the single-phase ZnIn preparing with additive method
2s
4, and the common photochemical catalyst of bibliographical information is (as TiO
2, Bi
2wO
6deng) compare, under radiation of visible light, its performance is more excellent.
(3) whole technical process of the present invention is simple and easy to control, production process environmental protection, and energy consumption is low, does not need equipment, the synthesis condition gentleness of complex and expensive, and cost is low, and catalyst stability is good, has larger application potential.
(3) prepared isomerism ZnIn
2s
4compound can be under solar light irradiation photocatalysis treatment dyeing waste water, photo-catalyst, photodissociation aquatic products hydrogen and selective oxidation alcohols etc. efficiently, there is good stability simultaneously.In light-catalyzed reaction system, photochemical catalyst renewable is strong, and recycling rate of waterused is high, has very high practical value and application prospect.
Accompanying drawing explanation
Fig. 1 is the isomerism ZnIn of embodiment 1 gained
2s
4the x-ray photoelectron energy spectrogram (XPS) of compound.
Fig. 2 is the isomerism ZnIn of embodiment 1 gained
2s
4the X-ray powder diffraction figure (XRD) of compound.
Fig. 3 is the isomerism ZnIn of embodiment 1 gained
2s
4the transmission electron microscope picture of compound (TEM).
Fig. 4 is the isomerism ZnIn of embodiment 1 gained
2s
4the ZnIn of compound, pure phase
2s
4and Bi
2wO
6degradation effect comparison diagram to MO.
The specific embodiment
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1
Respectively by ZnCl
2(10 mmol), In (NO
3)
34.5H
2o(20 mmol), thioacetamide (40 mmol), polyvinylpyrrolidone (2 g) joins in polytetrafluoroethylene (PTFE) reactor, then in reactor, add in 70 ml distilled water/ethanol/tetrachloromethane (volume ratio 1:1:0.2) mixed liquors, reactor is placed on magnetic stirring apparatus, regulate pH value 2.3, stir after 120 min, be placed in the baking oven of 120 ℃ and react 6 h, question response still is cooled to after room temperature, mixture in reactor is taken out, centrifugation, the sediment obtaining is with after distilled water and ethanol washing for several times, in the baking oven of 60 ℃, dry, obtain the Powdered presoma of crocus, the sulphur indium zinc precursor body preparing is placed in to tube furnace and under nitrogen atmosphere, calcines, temperature is controlled at 400 ℃, and insulation 4 h, obtain isomerism sulphur indium zinc complexes.
embodiment 2
Respectively by ZnCl
2(20 mmol), In (NO
3)
34.5H
2o(40 mmol), thioacetamide (80 mmol), polyvinylpyrrolidone (0.2 g) joins in polytetrafluoroethylene (PTFE) reactor, then in reactor, add in 70 ml distilled water/ethanol/tetrachloromethane (volume ratio 1:1:0.2) mixed liquors, reactor is placed on magnetic stirring apparatus, regulate pH value 2.3, stir after 120 min, be placed in the baking oven of 120 ℃ and react 6 h, question response still is cooled to after room temperature, mixture in reactor is taken out, centrifugation, the sediment obtaining is with after distilled water and ethanol washing for several times, in the baking oven of 60 ℃, dry, obtain the Powdered presoma of crocus, the sulphur indium zinc precursor body preparing is placed in to tube furnace and under nitrogen atmosphere, calcines, temperature is controlled at 400 ℃, and insulation 4 h, obtain isomerism sulphur indium zinc complexes.
embodiment 3
Respectively by ZnCl
2(10 mmol), In (NO
3)
34.5H
2o(20 mmol), thioacetamide (40 mmol), polyvinylpyrrolidone (1 g) joins in polytetrafluoroethylene (PTFE) reactor, then in reactor, add in 70 ml distilled water/ethanol/tetrachloromethane (volume ratio 1:1:0.2) mixed liquors, reactor is placed on magnetic stirring apparatus, regulate pH value 6, stir after 120 min, be placed in the baking oven of 120 ℃ and react 6 h, question response still is cooled to after room temperature, mixture in reactor is taken out, centrifugation, the sediment obtaining is with after distilled water and ethanol washing for several times, in the baking oven of 60 ℃, dry, obtain the Powdered presoma of crocus, the sulphur indium zinc precursor body preparing is placed in to tube furnace and under nitrogen atmosphere, calcines, temperature is controlled at 300 ℃, and insulation 4 h, obtain isomerism sulphur indium zinc complexes.
As can be seen from Figure 1 Zn exists with+divalent form, In exists with+3 forms, and S exists with-divalent form, and Zn/In/S all exists two kinds in conjunction with can simultaneously, this is corresponding with the sulphur indium zinc of Emission in Cubic and six side's phases respectively, and the photochemical catalyst of synthesized is Emission in Cubic and six side's phase sulphur indium zinc complexes.
Fig. 2 is different ZnIn
2s
4the XRD figure of sample, comparing known (a) with standard diagram is six side's phase ZnIn
2s
4, (b) be the ZnIn of Emission in Cubic
2s
4, (c) be cube/six side's phase ZnIn
2s
4compound, is sample of the present invention.
Fig. 3 (a) is the transmission electron microscope picture of sample, and as can be seen from the figure, sample mainly consists of nanometer sheet; Fig. 3 (b) is the electron diffraction diagram of choosing of sample, and point diffraction is to form circle shape, can judgement sample be polycrystalline; Fig. 3 (c) is the high-resolution transmission electron microscope picture of sample, from figure, can be observed lattice fringe clearly, the ZnIn of interplanar distance d=0.33 nm and Emission in Cubic
2s
4(012) crystal face match, interplanar distance d=0.20nm and six side's phase ZnIn
2s
4(0110) crystal face match, and between two-phase, form one significantly mutually knot.In other words, the present invention successfully prepares the ZnIn with out-phase knot
2s
4compound.Knot both sides, due to band structure different in kind, can form space potential poor.The having of this electrical potential difference is beneficial to the separated of electronics and hole, can improve light-catalysed efficiency.
The test of isomerism sulphur indium zinc complexes photocatalysis performance characterizes the degraded of MO under irradiating at xenon lamp.Adopt batch reactor, the MO that the concentration of take is about 20 ppm is reaction substrate.Using the xenon lamp of 300 W as light source, and the consumption of catalyst is 0.04 g.Before the reaction of turning on light, absorption in advance makes the MO illumination of turning on light after adsorption-desorption balance on catalyst.As can be seen from Figure 4, after illumination 30 min that turn on light, isomerism sulphur indium zinc complexes photochemical catalyst to the degradation rate of MO up to 100%.By contrast, the ZnIn of pure phase
2s
4catalyst is relatively low to the degradation efficiency of MO in 60 min light application times.Meanwhile, under the same conditions with at present to photochemical catalyst Bi visible light-responded and that development is more ripe
2wO
6more also can obviously find out that the isomerism sulphur indium zinc complexes performance that the present invention prepares is more excellent.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. a sulphur indium zinc composite with isomerism knot, is characterized in that: described sulphur indium zinc composite is non-TiO
2based photocatalyst, chemical formula is ZnIn
2s
4.
2. the sulphur indium zinc composite with isomerism knot according to claim 1, is characterized in that: described sulphur indium zinc composite is by the ZnIn of Emission in Cubic
2s
4znIn with six side's phases
2s
4by tying and connect and compose mutually, utilize knot mutually to realize out of phase ZnIn
2s
4the quick separation of upper photo-generated carrier, thus photocatalysis performance improved.
3. the sulphur indium zinc composite with isomerism knot according to claim 1, is characterized in that: the specific area of described sulphur indium zinc composite is 50-300 m
2/ g, its pattern is nano-sheet.
4. prepare a method with the sulphur indium zinc composite of isomerism knot as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) at 10-20 mmol ZnCl
2, 20-40 mmol In (NO
3)
34.5H
2in O, 40-80 mmol thioacetamide and 0-2 g polyvinylpyrrolidone, add 70 mL mixed solvents, regulate pH value=1-13, after magnetic agitation 120 min, 80-160 ℃ of reaction 2-36 h, be cooled to room temperature, centrifugal, sediment, with after distilled water and ethanol washing for several times, is dried to obtain presoma for 60 ℃; The volume ratio 1:1:0.2 of distilled water, ethanol and tetrachloromethane in described mixed solvent;
(2) presoma step (1) being obtained is placed in tube furnace 200-450 ℃ of calcining 2-8 h under nitrogen atmosphere, obtains the described sulphur indium zinc composite with isomerism knot.
5. an application with the sulphur indium zinc composite of isomerism knot as claimed in claim 1, is characterized in that: the described sulphur indium zinc composite with isomerism knot is for degradable organic pollutant, photo-catalyst, photolysis water hydrogen and photocatalysis to selectively oxidize alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410005878.4A CN103736501B (en) | 2014-01-07 | 2014-01-07 | A kind of sulphur indium zinc composite and Synthesis and applications thereof with isomerism knot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410005878.4A CN103736501B (en) | 2014-01-07 | 2014-01-07 | A kind of sulphur indium zinc composite and Synthesis and applications thereof with isomerism knot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103736501A true CN103736501A (en) | 2014-04-23 |
| CN103736501B CN103736501B (en) | 2015-11-18 |
Family
ID=50493608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410005878.4A Expired - Fee Related CN103736501B (en) | 2014-01-07 | 2014-01-07 | A kind of sulphur indium zinc composite and Synthesis and applications thereof with isomerism knot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103736501B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971762A (en) * | 2015-07-16 | 2015-10-14 | 华南理工大学 | Preparation method and application of g-C3N4/CaIn2S4 visible light compound photocatalyst |
| CN108499577A (en) * | 2018-05-04 | 2018-09-07 | 华北理工大学 | One kind is in carbon fiber surface load sandwich type TiO2Based photocatalyst and its application |
| CN109589989A (en) * | 2018-12-19 | 2019-04-09 | 江苏大学 | ZnIn2S4Nanometer sheet wraps up β-Bi2O3Nucleocapsid Heterogeneous Composite photochemical catalyst and its preparation method and application |
| CN111617778A (en) * | 2020-05-27 | 2020-09-04 | 南昌航空大学 | Preparation method of hydrothermally synthesized flower-rod-shaped sulfur indium zinc photocatalyst |
| CN112774695A (en) * | 2021-01-28 | 2021-05-11 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN113996323A (en) * | 2021-11-24 | 2022-02-01 | 新乡学院 | Indium-zinc sulfide composite visible light catalyst and preparation method and application thereof |
| CN116899589A (en) * | 2023-06-09 | 2023-10-20 | 常州大学 | Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884090A (en) * | 2006-05-23 | 2006-12-27 | 南开大学 | ZnIn2S4 nano materials and their synthesis method and application |
| CN102249288A (en) * | 2011-03-31 | 2011-11-23 | 中国科学院研究生院 | Preparation method for hexagonal phase zinc sulfate nano-crystal coating |
-
2014
- 2014-01-07 CN CN201410005878.4A patent/CN103736501B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884090A (en) * | 2006-05-23 | 2006-12-27 | 南开大学 | ZnIn2S4 nano materials and their synthesis method and application |
| CN102249288A (en) * | 2011-03-31 | 2011-11-23 | 中国科学院研究生院 | Preparation method for hexagonal phase zinc sulfate nano-crystal coating |
Non-Patent Citations (1)
| Title |
|---|
| 单雯妍 等: "《ZnIn2 S4半导体催化剂的制备、表征及产氢性能研究》", 《黑龙江科学》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971762A (en) * | 2015-07-16 | 2015-10-14 | 华南理工大学 | Preparation method and application of g-C3N4/CaIn2S4 visible light compound photocatalyst |
| CN108499577A (en) * | 2018-05-04 | 2018-09-07 | 华北理工大学 | One kind is in carbon fiber surface load sandwich type TiO2Based photocatalyst and its application |
| CN108499577B (en) * | 2018-05-04 | 2020-12-11 | 华北理工大学 | Load sandwich type TiO on carbon fiber surface2Base photocatalyst and application thereof |
| CN109589989A (en) * | 2018-12-19 | 2019-04-09 | 江苏大学 | ZnIn2S4Nanometer sheet wraps up β-Bi2O3Nucleocapsid Heterogeneous Composite photochemical catalyst and its preparation method and application |
| CN109589989B (en) * | 2018-12-19 | 2021-11-23 | 江苏大学 | ZnIn2S4Nanosheet-wrapped beta-Bi2O3Core-shell heterogeneous composite photocatalyst and preparation method and application thereof |
| CN111617778A (en) * | 2020-05-27 | 2020-09-04 | 南昌航空大学 | Preparation method of hydrothermally synthesized flower-rod-shaped sulfur indium zinc photocatalyst |
| CN111617778B (en) * | 2020-05-27 | 2021-10-22 | 南昌航空大学 | Preparation method of hydrothermally synthesized flower-rod-shaped sulfur indium zinc photocatalyst |
| CN112774695A (en) * | 2021-01-28 | 2021-05-11 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN112774695B (en) * | 2021-01-28 | 2021-12-17 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
| CN113996323A (en) * | 2021-11-24 | 2022-02-01 | 新乡学院 | Indium-zinc sulfide composite visible light catalyst and preparation method and application thereof |
| CN113996323B (en) * | 2021-11-24 | 2023-11-17 | 新乡学院 | Indium zinc sulfide composite visible light catalyst and preparation method and application thereof |
| CN116899589A (en) * | 2023-06-09 | 2023-10-20 | 常州大学 | Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103736501B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mei et al. | Step-scheme porous g-C3N4/Zn0. 2Cd0. 8S-DETA composites for efficient and stable photocatalytic H2 production | |
| Hou et al. | Variable dimensional structure and interface design of g-C3N4/BiOI composites with oxygen vacancy for improving visible-light photocatalytic properties | |
| Wang et al. | Fabrication of the flower-flake-like CuBi2O4/Bi2WO6 heterostructure as efficient visible-light driven photocatalysts: Performance, kinetics and mechanism insight | |
| Zeng et al. | Phase transformation and microwave hydrothermal guided a novel double Z-scheme ternary vanadate heterojunction with highly efficient photocatalytic performance | |
| CN103736501A (en) | Sulfur-indium-zinc composite material with homogeneous heterogeneous knot, as well as preparation method and application of material | |
| Kumar et al. | Noble metal-free metal-organic framework-derived onion slice-type hollow cobalt sulfide nanostructures: Enhanced activity of CdS for improving photocatalytic hydrogen production | |
| Zhang et al. | Construction of a novel BON-Br-AgBr heterojunction photocatalysts as a direct Z-scheme system for efficient visible photocatalytic activity | |
| CN104525226B (en) | A kind of photocatalyst Bi4o5br2synthesis and application process | |
| CN108686665B (en) | Preparation method of nanorod zinc ferrite in-situ composite lamellar titanium dioxide photocatalytic material | |
| CN105289689A (en) | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material | |
| Li et al. | In situ reorganization of Bi3O4Br nanosheet on the Bi24O31Br10 ribbon structure for superior visible-light photocatalytic capability | |
| Liu et al. | S-scheme heterojunction based on ZnS/CoMoO4 ball-and-rod composite photocatalyst to promote photocatalytic hydrogen production | |
| CN110344029B (en) | Preparation method of surface hydroxylated iron oxide film photo-anode material | |
| CN104511293A (en) | Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof | |
| CN103708559A (en) | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof | |
| CN102974373A (en) | Visible-light photocatalytic material and preparation method thereof | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN104001519B (en) | A kind of Room Temperature Solid State one-step method prepares Cu 2o/Bi 2o 3the method of nano composite photo-catalyst | |
| CN106076364A (en) | A kind of efficiently CdS CdIn2s4the preparation method of superstructure photocatalyst | |
| Liao et al. | Water hyacinth powder-assisted preparation of defects-rich and flower-like BiOI/Bi5O7I heterojunctions with excellent visible light photocatalytic activity | |
| CN106807411B (en) | A kind of preparation method of ferrous acid La doped silver bromide compound photocatalyst | |
| CN105195131A (en) | Preparation method of graphene quantum dot/vanadium-doped mesoporous titanium dioxide composite photocatalyst | |
| Du et al. | Black lead molybdate nanoparticles: facile synthesis and photocatalytic properties responding to visible light | |
| CN104043471A (en) | Preparation method of graphene/Ta3N5 composite photo-catalyst | |
| CN102234133B (en) | Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151118 Termination date: 20220107 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |