CN102989443A - High activity ZnO/SnO2 core-shell composite photocatalyst preparation method - Google Patents

High activity ZnO/SnO2 core-shell composite photocatalyst preparation method Download PDF

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CN102989443A
CN102989443A CN2011102738632A CN201110273863A CN102989443A CN 102989443 A CN102989443 A CN 102989443A CN 2011102738632 A CN2011102738632 A CN 2011102738632A CN 201110273863 A CN201110273863 A CN 201110273863A CN 102989443 A CN102989443 A CN 102989443A
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zno
preparation
sno
powder
catalyst
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刘志锋
李亚彬
雅菁
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Tianjin Urban Construction College
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Tianjin Urban Construction College
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Abstract

The invention belongs to the technical field of photocatalysis, and particularly relates to a high activity ZnO/SnO2 core-shell structure composite photocatalyst preparation method and related process parameters. The preparation method is a step-by-step precipitation method, and comprises: adopting SnCl4.5H2O as a precursor, and adopting ammonia water as a precipitating agent to prepare Sn(OH)4 powder; adding the prepared Sn(OH)4 to a Zn(NO3)2.6H2O solution with a certain concentration, uniformly stirring, adding ammonia water in a dropwise manner, and adjusting the PH value; carrying out washing, segregation and drying on the obtained product Zn(OH)2/Sn(OH)4; and finally carrying out calcinations on the Zn(OH)2/Sn(OH)4 composite powder to obtain the ZnO/SnO2 core-shell structure composite photocatalyst. According to the present invention, influence on a structure and performances of the ZnO/SnO2 composite photocatalyst by a precursor concentration, a pH value and other process parameters are investigated, and optimal process parameters for high activity ZnO/SnO2 core-shell structure composite photocatalyst preparation are obtained.

Description

A kind of high activity ZnO/SnO for preparing 2The method of nucleocapsid composite photo-catalyst
Technical field
The invention belongs to the photocatalysis technology field, be specially a kind of high activity ZnO/SnO for preparing 2The method of nucleocapsid structure composite photo-catalyst and related process parameter.
Technical background
Energy shortage and environmental pollution are the common issue with that this century, the whole mankind faced.How rationally utilizing the limited energy of occurring in nature, effectively controlling and solve problem of environmental pollution is the heat subject that new century various countries scientist studies.In recent years, the Photocatalytic Oxidation With Semiconductors technology of rising gradually is for we provide a kind of reasonable energy utilization and the Perfected process of curbing environmental pollution.Make us can really realize utilizing inexhaustible, nexhaustible solar energy to solve environmental pollution and energy shortage problem.
The Photocatalytic Oxidation With Semiconductors technique functions comes from the seventies in last century, from the TiO of Fujishima and Honda discovery illumination 2Single Crystalline Electrodes can decomposing H 2O utilizes semiconductor light-catalyst to become light energy conversion electric energy and chemical energy just to become one of the most popular research topic.Recently, constantly increase about the application study report that utilizes the aspects such as Photocatalytic Oxidation With Semiconductors degradable organic pollutant, reducing heavy metal ion, antifog, deodorizing, sterilization, automatically cleaning.The semi-conducting material that adopts at present mainly is the sulfur family oxide, such as TiO 2, ZnO, CdS, WO 3, SnO 2Deng.Semiconductor semiconductor absorbed energy under illumination is equal to or greater than energy gap (E g) photon, electronics will occur by the transition of valence band to conduction band, thereby generate hole h in valence band VB +, generate electronics e at conduction band CB -, this light induced electron-hole is to having very strong reduction and oxidation activity, can be with most oxidation operation, even also can thoroughly decompose some inorganic matters.
Main Problems is at present: in Photocatalytic Oxidation, and single semi-conducting material photochemical catalyst, band-gap energy is larger, and the hole is easy and electron recombination, causes photocatalysis performance not high.The compound of its carrier is the main cause that affects light-catalyzed reaction efficient.Therefore, how to reduce the compound of carrier, become the target of numerous scholar's research.Semiconductor is compound to be a kind of effective modification mode, and it utilizes the complementarity of difference on two or more semiconductor properties, improves the activity of catalyst.ZnO is a kind of efficient, avirulence, cheap important photochemical catalyst, receives much concern in degraded and pollutant process field.Semiconductor SnO 2Have different conduction bands and valence-band level with ZnO, when these two semiconductors carry out compound tense, SnO 2Conduction band be positioned under the conduction band of ZnO, can form the gradient energy level, the light induced electron on the ZnO conduction band enters SnO 2Conduction band, and the hole is opposite with the direction of motion of electronics, causes photohole to be caught by ZnO, this has stoped the compound of electronics and hole to a certain extent.The present invention adopts step-by-step precipitation method at SnO 2Outer cladding ZnO, making ZnO/SnO 2The nucleocapsid structure composite photo-catalyst utilizes nucleocapsid structure further to reduce the compound of light induced electron and hole, improves the catalytic performance of composite.
Summary of the invention
The object of the invention is to propose a kind of high activity ZnO/SnO for preparing 2The method of nucleocapsid structure composite photo-catalyst and related process parameter.
A kind of suitable preparation high activity ZnO/SnO 2The method of nucleocapsid structure composite photo-catalyst.This preparation method is step-by-step precipitation method.At first, with SnCl 45H 2O is presoma, and ammoniacal liquor is precipitating reagent, preparation Sn (OH) 4Powder; Then, with the Sn (OH) that makes 4Add certain density Zn (NO 3) 26H 2In the O solution, after stirring, drip ammoniacal liquor, regulate its pH value, with products therefrom Zn (OH) 2/ Sn (OH) 4Washing, segregation, drying; At last, with Zn (OH) 2/ Sn (OH) 4The composite granule calcining can obtain ZnO/SnO 2The nucleocapsid structure composite photo-catalyst.
The mechanism of action of the present invention is: with SnCl 45H 2O mixes with ammoniacal liquor, in 85 ℃ of lower reactions, generates Sn (OH) 4Precipitation; Then with the Sn (OH) that makes 4Powder adds Zn (NO 3) 26H 2In the O solution, regulate pH value by adding ammoniacal liquor, at Sn (OH) 4On can coat and be settled out Zn (OH) 2At last, with products therefrom Zn (OH) 2/ Sn (OH) 4Calcine, both can get the ZnO/SnO of nucleocapsid structure 2Composite granule.In photocatalytic degradation pollutant process, because SnO 2Conduction band be positioned under the conduction band of ZnO, the light induced electron on the ZnO conduction band enters SnO 2Conduction band, and the hole is opposite with the direction of motion of electronics, causes photohole to be caught by ZnO, thus this SnO 2The nucleocapsid structure of outer cladding ZnO can form the gradient energy level, and this has stoped the compound of electronics and hole to a certain extent, improves the photocatalytic activity of composite granule.
The present invention also proposes above-mentioned preparation method's related process parameter, and is specific as follows:
At first, with SnCl 45H 2O mixes with the ammoniacal liquor of 2mol/L, and the reactant liquor of preparation 0.04mol/L ± 0.001mol/L in 85 ℃ ± 2 ℃ lower reaction 4h, spends ion-cleaning with the gained sediment and removes Cl -, segregation again 100 ℃ of dryings, gets Sn (OH) 4Powder.Then, with the Sn (OH) that makes 4Zn (the NO that adds 0.02mol/L ± 0.001mol/L 3) 26H 2In the O solution, after stirring, drip the ammoniacal liquor of 2mol/L, regulating its pH value is 8 ± 0.1, fully after the reaction, the gained sediment is spent ion-cleaning, and segregation again 100 ℃ of dryings, gets Zn (OH) 2/ Sn (OH) 4Powder.At last, with Zn (OH) 2/ Sn (OH) 4Powder rises to 250 ℃ ± 10 ℃ insulation 0.5h with 2 ℃/min ± 0.05 ℃/min heating rate, rises to 500 ℃ ± 10 ℃ insulation 1h, namely gets ZnO/SnO with 2 ℃/min ± 0.05 ℃/min heating rate again 2The nucleocapsid structure composite photo-catalyst.
Characteristics of the present invention:
1, takes full advantage of SnO 2With ZnO conduction band and valence band location, construct the ZnO/SnO of nucleocapsid structure 2Composite photo-catalyst utilizes the gradient level structure, reduces the compound of light induced electron and hole, improves its photocatalytic activity.
2, the fractional precipitation synthesis process is comparatively simple, is easy to realize, is convenient to control.
3, can obtain more single ZnO and SnO 2Catalytic activity high, particle diameter is the ZnO/SnO of 25nm ± 5nm 2The nucleocapsid structure composite photo-catalyst.
This preparation technology's using method is as follows:
1, typical Sn (OH) 4The technological parameter of powder preparation: SnCl 45H 2The concentration 0.04mol/L of O, 85 ℃ of hydrothermal temperatures, reaction time 4h, the drying precipitate temperature is 100 ℃.
2, typical Zn (OH) 2/ Sn (OH) 4The technological parameter of preparation: Zn (NO 3) 26H 2The concentration of O is 0.02mol/L, and pH value is 8, and the drying precipitate temperature is 100 ℃.
3, typical ZnO/SnO 2The calcinating system of nucleocapsid structure composite photo-catalyst: rise to 250 ℃ of insulation 0.5h with 2 ℃/min heating rate, rise to 500 ℃ of insulation 1h with 2 ℃/min heating rate again.
4, Sn (OH) wherein 4The process parameters range of powder preparation: SnCl 45H 2The concentration 0.04mol/L of O ± 0.001mol/L, 85 ℃ ± 2 ℃ of hydrothermal temperatures, reaction time 4h, the drying precipitate temperature is 100 ℃.
5, day Zn (OH) wherein 2/ Sn (OH) 4The process parameters range of preparation: Zn (NO 3) 26H 2The concentration of O is 0.02mol/L ± 0.001mol/L, and pH value is 8 ± 0.1, and the drying precipitate temperature is 100 ℃.
6, ZnO/SnO wherein 2The calcinating system parameter area of nucleocapsid structure composite photo-catalyst: rise to 250 ℃ ± 10 ℃ insulation 0.5h with 2 ℃/min ± 0.05 ℃/min heating rate, rise to 500 ℃ ± 10 ℃ insulation 1h with 2 ℃/min ± 0.05 ℃/min heating rate again.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment
At first, with SnCl 45H 2O mixes with the ammoniacal liquor of 2mol/L, and the reactant liquor of preparation 0.04mol/L in 85 ℃ of lower reaction 4h, spends ion-cleaning with the gained sediment and removes Cl -, segregation again 100 ℃ of dryings, gets Sn (OH) 4Powder.Then, with the Sn (OH) that makes 4Zn (the NO that adds 0.02mol/L 3) 26H 2In the O solution, after stirring, drip the ammoniacal liquor of 2mol/L, regulating its pH value is 8, fully after the reaction, the gained sediment is spent ion-cleaning, and segregation again 100 ℃ of dryings, gets Zn (OH) 2/ Sn (OH) 4Powder.At last, with Zn (OH) 2/ Sn (OH) 4Powder rises to 250 ℃ of insulation 0.5h with 2 ℃/min heating rate, rises to 500 ℃ of insulation 1h with 2 ℃/min heating rate again, namely gets ZnO/SnO 2The nucleocapsid structure composite photo-catalyst.
Press the preceding method preparation.
Can get catalytic activity and be higher than single ZnO, the SnO that adopts identical precipitation method preparation 2The nucleocapsid structure ZnO/SnO of nano-photocatalyst 2Composite photo-catalyst, wherein particle size range is 25nm ± 5nm.

Claims (4)

1. one kind is fit to preparation high activity ZnO/SnO 2The method of nucleocapsid structure composite photo-catalyst.This preparation method is step-by-step precipitation method.At first, with SnCl 45H 2O is presoma, and ammoniacal liquor is precipitating reagent, preparation Sn (OH) 4Powder; Then, with the Sn (OH) that makes 4Add certain density Zn (NO 3) 26H 2In the O solution, after stirring, drip ammoniacal liquor, regulate its pH value, with products therefrom Zn (OH) 2/ Sn (OH) 4Washing, segregation, drying; At last, with Zn (OH) 2/ Sn (OH) 4The composite granule calcining can obtain ZnO/SnO 2The nucleocapsid structure composite photo-catalyst.
2. one kind to require 1 described Sn (OH) 4The preparation of powder.It is characterized in that detailed process and technological parameter are as follows: with SnCl 45H 2O mixes with the ammoniacal liquor of 2mol/L, and the reactant liquor of preparation 0.04mol/L ± 0.001mol/L in 85 ℃ ± 2 ℃ lower reaction 4h, spends ion-cleaning with the gained sediment and removes Cl -, segregation again 100 ℃ of dryings, gets Sn (OH) 4Powder.
3. one kind to require 1 described Zn (OH) 2/ Sn (OH) 4Preparation.It is characterized in that detailed process and related process parameter are as follows: with the Sn (OH) that makes 4Zn (the NO that adds 0.02mol/L ± 0.001mol/L 3) 26H 2In the O solution, after stirring, drip the ammoniacal liquor of 2mol/L, regulating its pH value is 8 ± 0.1, fully after the reaction, the gained sediment is spent ion-cleaning, and segregation again 100 ℃ of dryings, gets Zn (OH) 2/ Sn (OH) 4Powder.
4. one kind to require 1 described making ZnO/SnO 2The calcinating system of nucleocapsid structure composite photo-catalyst.It is characterized in that detailed process and related process parameter are as follows: with Zn (OH) 2/ Sn (OH) 4Powder rises to 250 ℃ ± 10 ℃ insulation 0.5h with 2 ℃/min ± 0.05 ℃/min heating rate, rises to 500 ℃ ± 10 ℃ insulation 1h, namely gets ZnO/SnO with 2 ℃/min ± 0.05 ℃/min heating rate again 2The nucleocapsid structure composite photo-catalyst.
CN2011102738632A 2011-09-16 2011-09-16 High activity ZnO/SnO2 core-shell composite photocatalyst preparation method Pending CN102989443A (en)

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Cited By (6)

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CN103274451A (en) * 2013-05-14 2013-09-04 东华大学 Synthesis and application of nanometer composite material with stannic oxide/zinc oxide core-shell structure
CN103389326A (en) * 2013-07-25 2013-11-13 中国科学院新疆理化技术研究所 Cadmium sulfide/zinc oxide nuclear shell nanowire nitrogen dioxide sensing material and preparation method thereof
CN104307503A (en) * 2014-10-28 2015-01-28 大连工业大学 Method for preparing SnO2/TiO2 compound micro-spheres with double-shell-layer core/shell structure
CN104316566A (en) * 2014-10-11 2015-01-28 武汉工程大学 Gas sensitive material and preparation method and application thereof
CN107570195A (en) * 2017-09-18 2018-01-12 天津城建大学 Hexagonal nano sheet ZnO g C for photoelectrocatalysis production hydrogen3N4The preparation method of film
CN113122261A (en) * 2019-12-30 2021-07-16 Tcl集团股份有限公司 Quantum dot crystal composite material and preparation thereof, quantum dot film and light-emitting diode

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274451A (en) * 2013-05-14 2013-09-04 东华大学 Synthesis and application of nanometer composite material with stannic oxide/zinc oxide core-shell structure
CN103274451B (en) * 2013-05-14 2016-01-06 东华大学 The synthesis of tindioxide/zinc oxide nuclear-shell structured nano-composite material and application
CN103389326A (en) * 2013-07-25 2013-11-13 中国科学院新疆理化技术研究所 Cadmium sulfide/zinc oxide nuclear shell nanowire nitrogen dioxide sensing material and preparation method thereof
CN103389326B (en) * 2013-07-25 2015-05-13 中国科学院新疆理化技术研究所 Cadmium sulfide/zinc oxide nuclear shell nanowire nitrogen dioxide sensing material and preparation method thereof
CN104316566A (en) * 2014-10-11 2015-01-28 武汉工程大学 Gas sensitive material and preparation method and application thereof
CN104307503A (en) * 2014-10-28 2015-01-28 大连工业大学 Method for preparing SnO2/TiO2 compound micro-spheres with double-shell-layer core/shell structure
CN104307503B (en) * 2014-10-28 2016-08-17 大连工业大学 One prepares the SnO of bivalve layer " core shell " structure2/ TiO2the method of compound micron ball
CN107570195A (en) * 2017-09-18 2018-01-12 天津城建大学 Hexagonal nano sheet ZnO g C for photoelectrocatalysis production hydrogen3N4The preparation method of film
CN107570195B (en) * 2017-09-18 2020-04-28 天津城建大学 Hexagonal nano flaky ZnO-g-C for producing hydrogen by photoelectrocatalysis3N4Method for producing thin film
CN113122261A (en) * 2019-12-30 2021-07-16 Tcl集团股份有限公司 Quantum dot crystal composite material and preparation thereof, quantum dot film and light-emitting diode
CN113122261B (en) * 2019-12-30 2022-06-10 Tcl科技集团股份有限公司 Quantum dot crystal composite material and preparation thereof, quantum dot film and light-emitting diode

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Application publication date: 20130327