CN103599769A - ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst - Google Patents
ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst Download PDFInfo
- Publication number
- CN103599769A CN103599769A CN201310586990.7A CN201310586990A CN103599769A CN 103599769 A CN103599769 A CN 103599769A CN 201310586990 A CN201310586990 A CN 201310586990A CN 103599769 A CN103599769 A CN 103599769A
- Authority
- CN
- China
- Prior art keywords
- znsn
- graphene
- sandwich structure
- cubic particle
- nano cubic
- 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
Abstract
The invention discloses a ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst and a preparation method and application thereof. The ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound material is prepared by compounding oxidized graphene and ZnSn (OH)6 nanometer cubic particles through auxiliary reduction of ultraviolet light. The preparation method of the ZnSn (OH)6 nanometer cubic particles is simple in process, convenient to operate, environment-friendly, efficient in synthesis and low in cost. The catalyst of the composite material is firmly bonded with the surface of graphene, separation of photon-generated carriers can be effectively improved and the recombination rate of carriers can be lowered to show a photocatalytic performance superior to nano particles. The photocatalytic activity of the compound light catalyst is 1.94 times of pure ZnSn (OH)6 and 1.74 times of commercial P25. The light catalyst is easy to separate from waste water and suitable for industrial production and application.
Description
Technical field
The invention belongs to photocatalysis field, be specifically related to a kind of ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst and its preparation method and application.
Background technology
Zinc hydroxyl stannate is a kind of many metal hydroxides of function perovskite structure.Be widely used in fire retardant and the smoke inhibitor of the macromolecular materials such as plastics, rubberbase paint.Recent research shows that it has superpower photocatalytic activity and photostability.Yet light induced electron-hole on quick compound be still the key factor that affects its photocatalytic activity.Therefore, effectively suppress the compound of photo-generated carrier, promote effective separation of electric charge, thereby improve the photocatalytic activity of zinc hydroxyl stannate, become the critical path that improves zinc hydroxyl stannate photocatalysis performance.
Graphene is as a kind of single electron layer Two-dimensional Carbon material, its theoretical specific area super large, and mechanical performance is strong, and chemical stability is good, and the large conjugated system in face has been given the electric conductivity of its excellence.Just because of these superior physical and chemical performances, enjoy researcher's favor.Emerge in recent years a large amount of graphene-based functional composite materials, in fields such as lithium battery, cathode material, nano-device, product hydrogen, Chu Qing, biological sensing material, catalysis, shown its wide application prospect.For photocatalytic semiconductor material, compound with graphene-based material fast and effeciently, has been the effective means of photo-generated carrier separation at present desirable promotion semiconductor.Method about synthesizing graphite alkene based composites has much at present, as the people such as Wang. (D. H. Wang, D. Choi, J. Li, Z. G. Yang, Z. M. Nie, R. Kou, D. H. Hu, C. M. Wang, L. V. Saraf, J. G. Zhang, I. A. Aksay, and J. Liu, ACS Nano, 2009,3,907-914.) under hydrothermal condition, adopt surfactant assisted self assembling method, prepared TiO
2/ graphene complex; Zhang. etc. (H.Zhang, X.Lv, Y.Li, Y.Wang, J. Li, ACSNano 2010,4,380 – 386.) adopt one step hydro thermal method to synthesize P25/ graphene complex.These methods often need hydrothermal condition, and the pattern of catalyst is difficult to control; Zhu. etc. (M. Zhu, P. Chen, and M. Liu, ACS Nano, 2011,5,4529 – 4536 .) at room temperature adopt two phase process to obtain Ag/AgX/ graphene oxide compound; JoonSeok Lee. etc. (J. S.Lee, K. H.You, C. B.Park, Adv. Mater., 2012,24,1084-1088.) first semiconductor is carried out to amino functional, then by electrostatic self-assembled, prepared TiO
2/ graphene complex etc.The end product that above-mentioned report is mentioned, composition and pattern are all different from the present invention.And, in above-mentioned compound preparation process, often needing to introduce some poisonous organic principles, cost is higher, post processing difficulty, process is comparatively loaded down with trivial details.
The disclosed patent about Graphene sandwich structure (comprise invention and utility model patent) nearly 3 (by the end of on November 13rd, 2013) at home, CN102583654A discloses a kind of preparation method of nanometer compounding capacitor type desalting electrode of carbon nanometer pipe/graphene sandwich structure, the method is passed through in the vapour deposition of Graphene surface chemistry, in-situ growing carbon nano tube obtains sandwich structure compound, but it is synthetic that its method needs under hot conditions, and 500 ~ 700 ℃ of reduction under reducing atmosphere; CN102765713A discloses a kind of fast preparation method of CNT/Graphene sandwich structure material, and the method also need to be calcined and reduce under hot conditions; CN103183889A discloses a kind of high heat conductive insulating polymer composites and preparation method, in this invention, in disclosed method, need to introduce some organic binder bonds, and reduction obtains its composite as reducing agent need to use hypertoxic hydrazine hydrate.And the composition that these patents relate to, preparation method are all different with the present invention from use field.
The disclosed patent about zinc hydroxyl stannate (comprise invention and utility model patent) nearly 11 (by the end of on November 13rd, 2013) at home, about 1st/2nd, monocomponent hydoxy zinc stannate preparation method.Comprising:
The precipitation method (CN1304880A, CN102515259A, CN1907862A): the method condition is large compared with gentle, small investment, output, but product purity is lower, size is larger, and the method is difficult to control the pattern of product;
Microemulsion method (CN103274450A): the method mild condition, equipment be simple, can control preferably product size and pattern, but in course of reaction, need a large amount of surfactants and organic solvents of using, and post processing bothers, unfavorable to environment.
CN101844798A discloses the hydro-thermal method of the controlled nano zinc hydroxyl stannate array of a kind of high dispersive size, its advantage is that technique is simple, can obtain the individual layer nano-crystal film of high-purity, high dispersive, but in building-up process, need to introduce tin element film synthetic as substrate induction, crystalline size is more than 400nm.
For other zinc hydroxyl stannate Patents, comprise:
CN101765629A discloses halogen-free flame-retardant; CN102515185A discloses Zinc hydroxystannate-palygorskite clay compound and preparation thereof and as the application of fire retardant; CN102627831A discloses a kind of zinc hydroxyl stannate/melamine-dicyandiamide formaldehyde resin phosphate composite granule and preparation method thereof; CN103254531A discloses a kind of flame-proof PVC composite and preparation method thereof; CN103102631A discloses based on supercritical CO
2cPVC/PVC heat-resisting composite and the preparation method of extrusion foaming; CN103318937A discloses the production method of the metal-doped zinc hydroxyl stannate microencapsulation of a kind of continuous industryization calcium carbonate.The preparation method of these inventions disclosed, end product and purposes etc. are all different from the present invention.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of simple, green, prepare ZnSn (OH) efficiently
6the method of nano cubic particle/Graphene sandwich structure composite photo-catalyst; The catalytic efficiency of gained composite is apparently higher than pure ZnSn (OH)
6, be 1.74 times of commodity P25, very easily separated.
For achieving the above object, the present invention adopts following technical scheme:
A kind of ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst is by graphene oxide and ZnSn (OH)
6nano cubic particle is compound, and make by ultraviolet light assisted Reduction.
In described composite, the mass fraction of Graphene is 0.2% ~ 20%.
ZnSn (OH)
6nano cubic particle is of a size of 20 ~ 100nm.
Graphene and ZnSn (OH) in described composite
6between nano cubic particle, be to be connected in chemical bonding mode.
Preparation method comprises the following steps:
(1) prepare ZnSn (OH)
6nano cubic particle
Under room temperature, zinc acetate is dissolved in deionized water, then the stannate of equimolar amounts is added in acetic acid zinc solution, stir, transfer in polytetrafluoroethylene (PTFE) reactor, be warming up to 120 ~ 200 ℃, be incubated 12 ~ 24h; Products therefrom naturally cools to room temperature, uses respectively the hydrochloric acid, deionized water, absolute ethanol washing of pH=2.5 repeatedly, centrifugal collecting precipitation, 60 ~ 80 ℃ of vacuum dryings;
(2) prepare graphene oxide colloidal sol
Take natural graphite powder as raw material, adopt improved Hummers method (Cote, L. J.; Kim, F.; Huang, J. J. Am. Chem. Soc.2008,131,1043-1049.) prepare graphene oxide; Be scattered in deionized water the graphene oxide making is ultrasonic, form graphene oxide colloidal sol;
(3) prepare ZnSn (OH)
6/ graphene oxide composite material
The ZnSn (OH) that step (1) is made
6nano cubic particle is ultrasonic to be scattered in weakly acidic solution, and the graphene oxide colloidal sol then step (2) being made dropwise adds, and ultrasonic dispersion 5 ~ 30min, stirs 2 ~ 6h, and after centrifugation, with deionized water washing, vacuum drying, makes ZnSn (OH)
6/ graphene oxide composite material;
(4) prepare ZnSn (OH)
6/ graphene composite material
By ZnSn (OH)
6/ graphene oxide composite material is scattered in absolute ethyl alcohol, and with the oxygen in inert gas venting suspension, and under inert atmosphere protection, with after UV-irradiation 10min ~ 300min, centrifugal, washing, dry, makes ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite.
Described stannate is potassium stannate or sodium stannate.
Described weakly acidic solution is HCl, H
2sO
4or HNO
3, pH=2 ~ 5.
The concentration of described graphene oxide colloidal sol is 0.5 ~ 10mg/mL.
Described inert atmosphere conditions is a kind of in nitrogen, helium, argon gas.
By ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst is put in the ratio of 0.1 ~ 1mg/mL in the methyl orange solution of 1 ~ 100mg/L and is carried out light degradation processing.
Remarkable advantage of the present invention is: the ZnSn (OH) that the present invention proposes
6/ Graphene sandwich structure composite photo-catalyst, production cost is low, and process is simple, and the cycle is short, and environmental friendliness, and very easily separated recovery, be applicable to industrialization promotion.The ZnSn (OH) that the present invention proposes
6/ graphene oxide sandwich structure composite catalyst photocatalysis effect is splendid, under the same terms, and ZnSn (OH)
6/ graphene oxide sandwich structure compound be photochemical catalyst in 15min catalytic degradation 86.5% methyl orange; And with pure ZnSn (OH)
6with commercial P25 be that catalyst has fallen respectively 62.6%, 69.8% in 15min.
Accompanying drawing explanation
Fig. 1 is graphene oxide (a) synthetic in embodiment 1, pure ZnSn (OH)
6nano cubic particle (b), ZnSn (OH)
6/ graphene oxide composite material (c) and ZnSn (OH)
6the X-ray powder diffraction figure (XRD) of/graphene composite material (d).
Fig. 2 is pure ZnSn (OH) synthetic in embodiment 1
6the field emission scanning electron microscope of nano cubic particle (FE-SEM) figure.
Fig. 3 is pure ZnSn (OH) synthetic in embodiment 1
6field emission scanning electron microscope (FE-SEM) figure that nano cubic particle/Graphene sandwich structure is compound.
Fig. 4 is pure ZnSn (OH)
6, P25, ZnSn (OH)
6/ graphene oxide and ZnSn (OH)
6the rate diagram of/graphene composite photocatalyst catalysis methyl orange degradation.
Fig. 5 is pure ZnSn (OH)
6nano cubic particle, ZnSn (OH)
6/ graphene oxide composite material and ZnSn (OH)
6sedimentation separation situation photo after the static 1min of/graphene composite material.
The specific embodiment
In order to describe more clearly and completely the present invention, below in conjunction with accompanying drawing of the present invention, the part embodiment enumerating is specifically described.
embodiment 1
Preparation:
The first step: preparation ZnSn (OH)
6nano cubic particle:
(1) preparation of reaction precursor liquid: under room temperature, the two hydration zinc acetates of 2mmol are dissolved in 80mL deionized water, then the potassium stannate of equimolar amounts are added to above-mentioned acetic acid zinc solution, stir, form reaction precursor liquid solution;
(2) hydro-thermal reaction: the precursor solution of gained is transferred in the polytetrafluoroethylene (PTFE) reactor of 100mL capacity, be warming up to 180 ℃, insulation 18h;
(3) washing and the collection of precipitation: products therefrom naturally cools to room temperature, use respectively hydrochloric acid, deionized water, the absolute ethanol washing 3 times of pH=2.5, centrifugal collecting precipitation, and 60 ℃ of vacuum dryings obtain ZnSn (OH)
6nano cubic particle.
Second step: prepare graphene oxide colloidal solution:
Take natural graphite powder as raw material, adopt improved Hummers legal system for graphite oxide; Be scattered in deionized water the graphene oxide colloidal sol that to form solubility be 4mg/mL by the graphene oxide of acquisition is ultrasonic.
The 3rd step: preparation ZnSn (OH)
6/ graphene oxide composite material:
The ZnSn that the first step is obtained (OH)
6nano cubic particle is ultrasonic to be scattered in the hydrochloric acid solution of pH=4, then graphene oxide colloidal solution second step being made dropwise adds, ultrasonic dispersion 30min, stir 4h, to after the product centrifugation obtaining, by deionized water, wash, 60 ℃ of vacuum drying, obtain the ZnSn that mass ratio is 100:2 (OH)
6/ graphene oxide composite material.
The 4th step: preparation ZnSn (OH)
6/ graphene composite material:
Take the ZnSn (OH) that 100mg the 3rd step obtains
6/ graphene oxide photochemical catalyst is scattered in 50mL absolute ethyl alcohol, with the oxygen in nitrogen venting suspension, and under nitrogen atmosphere protection, and with after 254nm UV-irradiation 40min, centrifugal, washing, the dry ZnSn (OH) that collects
6/ graphene composite material.
Application:
Take 20mgZnSn (OH)
6/ graphene composite photocatalyst, joins 80ml, in the methyl orange solution of 10mg/L, constantly stirs, and under 254nm UV-irradiation, the degraded situation of research methyl orange.As shown in Figure 4, under the same terms, ZnSn (OH)
6/ Graphene sandwich structure compound be photochemical catalyst in 15min catalytic degradation 86.5% methyl orange; And with pure ZnSn (OH)
6with commercial P25 be that catalyst has only fallen respectively 62.6%, 69.8% in 15min.
embodiment 2
The first step: preparation ZnSn (OH)
6nano cubic particle:
(1) preparation of reaction precursor liquid: under room temperature, 2mmol bis-hydration zinc acetates are dissolved in 80mL deionized water, then the potassium stannate of equimolar amounts are added to above-mentioned acetic acid zinc solution, stir, form reaction precursor liquid solution;
(2) hydro-thermal reaction: the precursor solution of gained is transferred in the polytetrafluoroethylene (PTFE) reactor of 100mL capacity, be warming up to 180 ℃, insulation 18h;
(3) washing and the collection of precipitation: products therefrom naturally cools to room temperature, use respectively hydrochloric acid, deionized water, the absolute ethanol washing 3 times of pH=2.5, centrifugal collecting precipitation, and 60 ℃ of vacuum dryings obtain ZnSn (OH)
6nano cubic particle.
Second step: prepare graphene oxide colloidal solution:
Take natural graphite powder as raw material, adopt improved Hummers legal system for graphite oxide; Be scattered in deionized water the graphene oxide colloidal sol that to form solubility be 3mg/mL by the graphene oxide of acquisition is ultrasonic.
The 3rd step: preparation ZnSn (OH)
6/ graphene oxide composite material:
The ZnSn that the first step is obtained (OH)
6nano cubic particle is ultrasonic to be scattered in weakly acidic solution, then graphene oxide colloidal solution second step being made dropwise adds, ultrasonic dispersion 30min, stir 4h, to after the product centrifugation obtaining, by deionized water, wash, 60 ℃ of vacuum drying, obtain the ZnSn that mass ratio is 100:2 (OH)
6/ graphene oxide composite material.
The 4th step: preparation ZnSn (OH)
6/ graphene composite material:
Take the ZnSn (OH) that 100mg the 3rd step obtains
6/ graphene oxide photochemical catalyst is scattered in 50mL absolute ethyl alcohol, with the oxygen in nitrogen venting suspension, and under nitrogen atmosphere protection, and with after 254nm UV-irradiation 40min, centrifugal, washing, the dry ZnSn (OH) that collects
6/ graphene composite material.
embodiment 3
The first step: preparation ZnSn (OH) 6 nano cubic particles:
(1) preparation of reaction precursor liquid: under room temperature, the two hydration zinc acetates of 2mmol are dissolved in 80mL deionized water, then the potassium stannate of equimolar amounts are joined to above-mentioned acetic acid zinc solution, stir, form reaction precursor liquid solution;
(2) hydro-thermal reaction: gained precursor solution is transferred in the polytetrafluoroethylene (PTFE) reactor of 100mL capacity, be warming up to 180 ℃, insulation 18h.
(3) washing and the collection of precipitation: products therefrom naturally cools to room temperature, use respectively hydrochloric acid, deionized water, the absolute ethanol washing 3 times of pH=2.5, centrifugal collecting precipitation, and 60 ℃ of vacuum dryings obtain ZnSn (OH)
6nano cubic particle.
Second step: prepare graphene oxide colloidal solution:
Take natural graphite powder as raw material, adopt improved Hummers legal system for graphite oxide; Be scattered in deionized water the graphene oxide colloidal sol that to form solubility be 2mg/mL by the graphene oxide of acquisition is ultrasonic.
The 3rd step: preparation ZnSn (OH)
6/ graphene oxide composite material:
The ZnSn that the first step is obtained (OH)
6nano cubic particle is ultrasonic to be scattered in the hydrochloric acid solution of pH=4, then graphene oxide colloidal solution second step being made dropwise adds, ultrasonic dispersion 30min, stir 4h, to after the product centrifugation obtaining, by deionized water, wash, 60 ℃ of vacuum drying, obtain the ZnSn that mass ratio is 100:2 (OH)
6/ graphene oxide composite material.
The 4th step: preparation ZnSn (OH)
6/ graphene composite material:
Take the ZnSn (OH) that 100mg the 3rd step obtains
6/ graphene oxide photochemical catalyst is scattered in 50mL absolute ethyl alcohol, with the oxygen in nitrogen venting suspension, and under nitrogen atmosphere protection, and with after 254nm UV-irradiation 40min, centrifugal, washing, the dry ZnSn (OH) that collects
6/ graphene composite material.
embodiment 4
By the graphene oxide of embodiment 1 gained, pure ZnSn (OH)
6, ZnSn (OH)
6/ graphene oxide and ZnSn (OH)
6/ graphene composite material, carries out respectively X-ray diffraction analysis, and result is as Fig. 1.The quick complex method that proof the present invention proposes does not change ZnSn (OH)
6crystal formation.
By the pure ZnSn (OH) of embodiment 1 gained
6and ZnSn (OH)
6/ graphene composite material carries out respectively field emission scanning electron microscope sign, and result is as Fig. 2, and 3.The quick recombination process that proof proposes in the present invention can not change original ZnSn (OH)
6the pattern of nanocube, and successfully prepared ZnSn (OH)
6/ Graphene sandwich structure photochemical catalyst.
Take respectively the pure ZnSn (OH) of 5mg embodiment 1 gained
6, ZnSn (OH)
6/ graphene oxide and ZnSn (OH)
6/ graphene complex is dispersed in 1mL deionized water, after standing 1min, observes its standing separation situation, and result is as Fig. 5.Show ZnSn disclosed by the invention (OH)
6the photocatalysis of/Graphene sandwich structure is very easily in sedimentation separation.
The foregoing is only preferred embodiment of the present invention, only, for the present invention is described, be not used in and limit the scope of the invention.In the situation that not paying creative work, the equalization of doing according to the present patent application the scope of the claims changes and modifies, and all should belong to covering scope of the present invention.
Claims (10)
1. a ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: by graphene oxide and ZnSn (OH)
6nano cubic particle is compound, and makes ZnSn (OH) by ultraviolet light assisted Reduction
6nano cubic particle/Graphene sandwich structure composite.
2. ZnSn according to claim 1 (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: in described composite, the mass fraction of Graphene is 0.2% ~ 20%.
3. ZnSn according to claim 1 (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: ZnSn (OH)
6nano cubic particle is of a size of 20 ~ 100nm.
4. ZnSn according to claim 1 (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: Graphene and ZnSn (OH) in described composite
6between nano cubic particle, be to be connected in chemical bonding mode.
5. prepare ZnSn as claimed in claim 1 (OH) for one kind
6the method of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: comprise the following steps:
(1) prepare ZnSn (OH)
6nano cubic particle
Under room temperature, zinc acetate is dissolved in deionized water, then the stannate of equimolar amounts is added in acetic acid zinc solution, stir, transfer in polytetrafluoroethylene (PTFE) reactor, be warming up to 120 ~ 200 ℃, be incubated 12 ~ 24h; Products therefrom naturally cools to room temperature, uses respectively the hydrochloric acid, deionized water, absolute ethanol washing of pH=2.5 repeatedly, centrifugal collecting precipitation, vacuum drying;
(2) prepare graphene oxide colloidal sol
Take natural graphite powder as raw material, adopt improved Hummers legal system for graphene oxide; Be scattered in deionized water the graphene oxide making is ultrasonic, form graphene oxide colloidal sol;
(3) prepare ZnSn (OH)
6/ graphene oxide composite material
The ZnSn (OH) that step (1) is made
6nano cubic particle is ultrasonic to be scattered in weakly acidic solution, and the graphene oxide colloidal sol then step (2) being made dropwise adds, and ultrasonic dispersion 5 ~ 30min, stirs 2 ~ 6h, and after centrifugation, with deionized water washing, vacuum drying, makes ZnSn (OH)
6/ graphene oxide composite material;
(4) prepare ZnSn (OH)
6/ graphene composite material
By ZnSn (OH)
6/ graphene oxide composite material is scattered in absolute ethyl alcohol, and with the oxygen in inert gas venting suspension, and under inert atmosphere protection, with after UV-irradiation 10min ~ 300min, centrifugal, washing, dry, makes ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite.
6. ZnSn according to claim 5 (OH)
6the preparation method of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: described stannate is potassium stannate or sodium stannate.
7. ZnSn according to claim 5 (OH)
6the preparation method of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: described weakly acidic solution is HCl, H
2sO
4or HNO
3, pH=2 ~ 5.
8. ZnSn according to claim 5 (OH)
6the preparation method of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: the concentration of described graphene oxide colloidal sol is 0.5 ~ 10mg/mL.
9. ZnSn according to claim 5 (OH)
6the preparation method of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: described inert atmosphere conditions is a kind of in nitrogen, helium, argon gas.
10. a ZnSn as claimed in claim 1 (OH)
6the application of nano cubic particle/Graphene sandwich structure composite photo-catalyst, is characterized in that: by ZnSn (OH)
6nano cubic particle/Graphene sandwich structure composite photo-catalyst is put in the ratio of 0.1 ~ 1mg/mL in the methyl orange solution of 1 ~ 100mg/L and is carried out light degradation processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310586990.7A CN103599769B (en) | 2013-11-21 | 2013-11-21 | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310586990.7A CN103599769B (en) | 2013-11-21 | 2013-11-21 | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103599769A true CN103599769A (en) | 2014-02-26 |
| CN103599769B CN103599769B (en) | 2015-04-15 |
Family
ID=50118068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310586990.7A Expired - Fee Related CN103599769B (en) | 2013-11-21 | 2013-11-21 | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103599769B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098088A (en) * | 2014-06-17 | 2014-10-15 | 华南理工大学 | Preparation method for nano-zinc oxide modified graphene hybrid material |
| CN104479339A (en) * | 2014-12-22 | 2015-04-01 | 东莞市安高瑞新材料科技有限公司 | Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof |
| CN104855419A (en) * | 2015-04-17 | 2015-08-26 | 河南大学 | Nano-grade mesoporous zinc hydroxystannate-modified graphene oxide hybrid antibacterial agent and preparation method thereof |
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN105295100A (en) * | 2015-09-28 | 2016-02-03 | 河南大学 | Preparation method of surface modification and flame retardance enhancement dual-function nano hydroxyl zinc stannate flame retardant |
| CN105489890A (en) * | 2015-11-30 | 2016-04-13 | 许昌学院 | Copper hydroxystannate micro-nano particles for lithium ion battery negative electrode and preparation method |
| CN106009036A (en) * | 2016-07-04 | 2016-10-12 | 沈阳化工大学 | Preparation method for nanometer composite flame retardant |
| CN106564935A (en) * | 2016-11-09 | 2017-04-19 | 陕西科技大学 | ZnSn(OH)<6> powder, and preparation method and application thereof |
| CN106750545A (en) * | 2017-01-11 | 2017-05-31 | 山东欧铂新材料有限公司 | A kind of zinc stearate/graphene oxide composite material and preparation method thereof |
| CN107224978A (en) * | 2017-07-24 | 2017-10-03 | 福州大学 | The preparation method and applications of hydroxyl stannate cobalt/graphene composite photocatalyst |
| CN107321359A (en) * | 2017-07-24 | 2017-11-07 | 福州大学 | A kind of hydroxyl stannate iron/graphene composite photocatalyst and preparation method thereof |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
| CN108976588A (en) * | 2018-08-02 | 2018-12-11 | 福州大学 | A kind of flame-retardant and anti-static eva foam composite material and preparation method |
| CN111632590A (en) * | 2020-06-15 | 2020-09-08 | 福州大学 | Supported ZnSn (OH)6Glass pearly-lustre catalyst and preparation method and application thereof |
| CN113697847A (en) * | 2021-08-05 | 2021-11-26 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN113930029A (en) * | 2021-10-25 | 2022-01-14 | 云南锡业集团（控股）有限责任公司研发中心 | Halogen-free nano composite flame retardant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342874A (en) * | 1989-07-21 | 1994-08-30 | Alcan International Limited | Flame retardant polymer formulation |
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
-
2013
- 2013-11-21 CN CN201310586990.7A patent/CN103599769B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342874A (en) * | 1989-07-21 | 1994-08-30 | Alcan International Limited | Flame retardant polymer formulation |
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| XIANLIANG FU ET AL: ""Hydroxide ZnSn(OH)6: A promising new photocatalyst for benzene degradation"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 91, 13 May 2009 (2009-05-13), pages 67 - 72, XP026393320 * |
| 徐杨帆等: ""一步水热法制备高催化活性锡酸锌-还原石墨烯复合材料"", 《2013广东材料发展论坛－战略性新兴材料发展与新材料科技创新研讨会》, 1 November 2013 (2013-11-01), pages 72 - 73 * |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098088B (en) * | 2014-06-17 | 2016-04-13 | 华南理工大学 | The preparation method of the grapheme modified hybrid material of a kind of nano zine oxide |
| CN104098088A (en) * | 2014-06-17 | 2014-10-15 | 华南理工大学 | Preparation method for nano-zinc oxide modified graphene hybrid material |
| CN104479339A (en) * | 2014-12-22 | 2015-04-01 | 东莞市安高瑞新材料科技有限公司 | Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof |
| CN104855419B (en) * | 2015-04-17 | 2017-07-07 | 河南大学 | A kind of Zinc modified graphene oxide hydridization antiseptic of mesoporous nano hydroxyl stannate and preparation method thereof |
| CN104855419A (en) * | 2015-04-17 | 2015-08-26 | 河南大学 | Nano-grade mesoporous zinc hydroxystannate-modified graphene oxide hybrid antibacterial agent and preparation method thereof |
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN104893248B (en) * | 2015-05-27 | 2017-01-11 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN105295100A (en) * | 2015-09-28 | 2016-02-03 | 河南大学 | Preparation method of surface modification and flame retardance enhancement dual-function nano hydroxyl zinc stannate flame retardant |
| CN105295100B (en) * | 2015-09-28 | 2017-10-17 | 河南大学 | A kind of surface modified flame-retardant strengthens the preparation method of dual-functional nanometer hydroxyl stannate zinc flame retardant |
| CN105489890A (en) * | 2015-11-30 | 2016-04-13 | 许昌学院 | Copper hydroxystannate micro-nano particles for lithium ion battery negative electrode and preparation method |
| CN106009036A (en) * | 2016-07-04 | 2016-10-12 | 沈阳化工大学 | Preparation method for nanometer composite flame retardant |
| CN106564935A (en) * | 2016-11-09 | 2017-04-19 | 陕西科技大学 | ZnSn(OH)<6> powder, and preparation method and application thereof |
| CN106564935B (en) * | 2016-11-09 | 2018-04-13 | 陕西科技大学 | A kind of ZnSn (OH)6Powder and its preparation method and application |
| CN106750545A (en) * | 2017-01-11 | 2017-05-31 | 山东欧铂新材料有限公司 | A kind of zinc stearate/graphene oxide composite material and preparation method thereof |
| CN107224978A (en) * | 2017-07-24 | 2017-10-03 | 福州大学 | The preparation method and applications of hydroxyl stannate cobalt/graphene composite photocatalyst |
| CN107321359A (en) * | 2017-07-24 | 2017-11-07 | 福州大学 | A kind of hydroxyl stannate iron/graphene composite photocatalyst and preparation method thereof |
| CN107224978B (en) * | 2017-07-24 | 2019-08-09 | 福州大学 | Hydroxyl stannate cobalt/graphene composite photocatalyst preparation method and applications |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
| CN108288693B (en) * | 2017-12-22 | 2020-07-10 | 天津师范大学 | Zinc-tin bimetallic sulfide as negative electrode material of sodium-ion battery and preparation method and application thereof |
| CN108976588A (en) * | 2018-08-02 | 2018-12-11 | 福州大学 | A kind of flame-retardant and anti-static eva foam composite material and preparation method |
| CN108976588B (en) * | 2018-08-02 | 2020-11-03 | 福州大学 | Flame-retardant antistatic EVA foam composite material and preparation method thereof |
| CN111632590A (en) * | 2020-06-15 | 2020-09-08 | 福州大学 | Supported ZnSn (OH)6Glass pearly-lustre catalyst and preparation method and application thereof |
| CN111632590B (en) * | 2020-06-15 | 2022-12-09 | 福州大学 | Loaded ZnSn (OH) 6 Glass pearly-lustre catalyst and preparation method and application thereof |
| CN113697847A (en) * | 2021-08-05 | 2021-11-26 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN113697847B (en) * | 2021-08-05 | 2022-04-01 | 湖北工程学院 | ZnSnO3Preparation method of nanorod/RGO composite material and energy storage application thereof |
| CN113930029A (en) * | 2021-10-25 | 2022-01-14 | 云南锡业集团（控股）有限责任公司研发中心 | Halogen-free nano composite flame retardant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103599769B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103599769B (en) | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst | |
| Li et al. | Photocatalyst design based on two-dimensional materials | |
| Wang et al. | The precursor-guided hydrothermal synthesis of CuBi2O4/WO3 heterostructure with enhanced photoactivity under simulated solar light irradiation and mechanism insight | |
| Song et al. | Construction of 2D SnS2/g-C3N4 Z-scheme composite with superior visible-light photocatalytic performance | |
| Zhao et al. | MXenes as co-catalysts for the solar-driven photocatalytic reduction of CO 2 | |
| Lin et al. | Highly efficient photocatalytic activity of g-C3N4 quantum dots (CNQDs)/Ag/Bi2MoO6 nanoheterostructure under visible light | |
| Liu et al. | In-situ ion-exchange synthesis Ag2S modified SnS2 nanosheets toward highly photocurrent response and photocatalytic activity | |
| Zhao et al. | Preparation of direct Z-scheme Bi2Sn2O7/g-C3N4 composite with enhanced photocatalytic performance | |
| CN103787348B (en) | The preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite | |
| Zhou et al. | Oxygen vacancy engineering of BiOBr/HNb3O8 Z-scheme hybrid photocatalyst for boosting photocatalytic conversion of CO2 | |
| CN104815637A (en) | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material | |
| Shui et al. | Green sonochemical synthesis of cupric and cuprous oxides nanoparticles and their optical properties | |
| CN106622324A (en) | Graphite-phase nitrogen carbide nanosheet/cobaltosic oxide nanosheet composite nanomaterial of scale-shaped structure and preparation method and application thereof | |
| Xia et al. | Novel 2D Zn-porphyrin metal organic frameworks revived CdS for photocatalysis of hydrogen production | |
| CN102633303B (en) | Three-dimensional graded titanium dioxide hollow nanometer box and preparation method of same | |
| Cao et al. | A novel Bi12TiO20/g-C3N4 hybrid catalyst with a bionic granum configuration for enhanced photocatalytic degradation of organic pollutants | |
| He et al. | Fabrication of two-dimensional porous CdS nanoplates decorated with C3N4 nanosheets for highly efficient photocatalytic hydrogen production from water splitting | |
| Lei et al. | Low-dimensional MXenes as noble metal-free co-catalyst for solar-to-fuel production: Progress and prospects | |
| Zhang et al. | Macroporous ZnO/ZnS/CdS composite spheres as efficient and stable photocatalysts for solar-driven hydrogen generation | |
| Dai et al. | ZnIn2S4 modified CaTiO3 nanocubes with enhanced photocatalytic hydrogen performance | |
| Zhang et al. | Building {0001} and {101 1} facet heterojunctions on hexagonal pyramid CdS single crystals with high photoactivity and photostability for hydrogen evolution | |
| Muhmood et al. | Enhanced photo-electrochemical, photo-degradation and charge separation ability of graphitic carbon nitride (g-C3N4) by self-type metal free heterojunction formation for antibiotic degradation | |
| Zhai et al. | A review of phosphorus structures as CO2 reduction photocatalysts | |
| Abdellatif et al. | A highly efficient dual-phase GaN (O)/Nb2O5 (N) photocatalyst prepared through nitridation and reoxidation process for NO removal | |
| Chang et al. | Microwave solvothermal synthesis of cubic MnS@ Ag2S core-shell photocatalysts with improved charge separation and photocatalytic activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20171121 |