CN102553562A - Multiple modified composite photocatalyst and preparation method thereof - Google Patents

Multiple modified composite photocatalyst and preparation method thereof Download PDF

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CN102553562A
CN102553562A CN2012100225985A CN201210022598A CN102553562A CN 102553562 A CN102553562 A CN 102553562A CN 2012100225985 A CN2012100225985 A CN 2012100225985A CN 201210022598 A CN201210022598 A CN 201210022598A CN 102553562 A CN102553562 A CN 102553562A
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tio
sno
catalyst
transition metal
multiple modified
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CN102553562B (en
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陆金东
张哲�
马磊
何洪波
曾炽涛
陈爱平
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WUXI DIFAN LEIPU HIGH-NEW MATERIALS CO LTD
East China University of Science and Technology
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WUXI DIFAN LEIPU HIGH-NEW MATERIALS CO LTD
East China University of Science and Technology
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Abstract

The invention discloses a multiple modified composite photocatalyst and a preparation method thereof. A matrix of the composite photocatalyst is a compound semiconductor SnO2-TiO2 of SnO2 and TiO2, wherein the atomic ratio of Sn to Ti is (0.1-10.0):1. The preparation method comprises the following steps of: preparing a SnO2-TiO2 catalyst containing transition metals, namely Co, Mo, Cu, Pt, Au, Pd and Ag, or synthesizing the compound semiconductor matrix SnO2-TiO2 of the photocatalyst and impregnating in a solution containing transition metal elements, drying, grinding, and finally growing carbon nano-tubes (CNTs) on the surface of the transition metal doped and modified SnO2-TiO2 catalyst in situ by a vapor deposition method. The preparation method for the composite photocatalyst is suitable for large-scale production.

Description

Multiple modified composite photo-catalyst and preparation method thereof
[technical field]
The present invention relates to fine chemistry industry and green technology technical field, specifically, is a kind of multiple modified composite photo-catalyst and preparation method thereof.
[background technology]
Nano-TiO 2Photochemical catalyst is by the scientist of various countries institute broad research.Under the irradiation of ultraviolet light, electronics is from TiO 2Valence band be excited to conduction band, on valence band, produce the hole of positively charged.But electronics and hole-recombination speed in that optical excitation produces are very fast, and be approximately 10 its recombination time -9Second, and TiO 2With being adsorbed on its surperficial required time of organic pollution generation chemical action is 10 -8-10 -3Second.Both gaps cause TiO 2Photocatalysis efficiency lower.On the other hand, titanium dioxide is a kind of semiconductor of broad stopband, and only absorbing ultraviolet light influences its utilization to solar energy, limits its practical application.A large amount of research is attempted through the doping ion, semiconductor is compound and above-mentioned these problems of visible light photoactivated solution.The present invention is with SnO 2With TiO 2Composite semiconductor SnO 2-TiO 2For carrying out the MULTIPLE COMPOSITE modification in the basis.
CNT is a kind of monodimension nanometer material with stable chemical property, good mechanics, electricity, optical property and unique absorption property; Came to light with rice from 1991, this novel carbon materials causes people's very big concern with its particular performances and potential using value.
In the carbon nano-tube/titanic oxide composite catalyst, be commonly considered as CNTs and TiO 2Between the cooperative effect that produces of strong interaction not only make CNTs/TiO 2The photocatalysis performance of composite catalyst has improved greatly, and CNT can also make CNTs/TiO as sensitising agent 2Composite photo-catalyst has visible light activity.Most of at present report is with nano-TiO with the sol-gel method 2Be coated on the CNT tube wall.Usually, CNT need pass through strong acid treatment usually and make its tube wall band grafting group, is convenient to and TiO 2Combination, but performances such as structure that strong acid treatment can destroying carbon nanometer tube itself and conduction, the group skewness causes nano-TiO after the while CNTs surface modification 2Particle is difficult for being attached to the tube wall of CNTs and self reunites.The present invention adopts the transient metal doped SnO of preparation earlier 2-TiO 2Catalyst matrix under the reducing atmosphere of vapor phase method growth CNTs, makes at least a containing transition metal element be reduced into metallic state then, becomes the catalytic active center of CNTs growth, then at the SnO that contains the metallic state catalyst 2-TiO 2In-situ chemical vapor deposition growth CNTs on the matrix not only can keep the excellent properties of CNT and CNT and matrix SnO 2-TiO 2In conjunction with firmly, help CNTs and SnO 2-TiO 2Between the electronics transmission.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of multiple modified composite photo-catalyst and preparation method thereof be provided, through chemical vapour deposition technique with the composite semiconductor SnO of CNTs growth in situ in the transition metal modification 2-TiO 2On the matrix, obtain having highly active multiple modified composite photo-catalyst.
The objective of the invention is to realize through following technical scheme:
A kind of multiple modified composite photo-catalyst, its matrix is SnO 2With TiO 2Composite semiconductor SnO 2-TiO 2, wherein the atomic ratio of Sn and Ti is 0.1～10.0: 1.
The doping vario-property of transition metal is at SnO 2-TiO 2Composite semiconductor prepares in the process and carries out, perhaps the SnO to having prepared 2-TiO 2Carrying out modification handles.
To SnO 2-TiO 2The transition metal of matrix doping vario-property is one or more the composition among Co, Mo, Cu, Pt, Au, Pd, the Ag, with SnO 2-TiO 2Be benchmark, the quality percentage mark of containing transition metal element is 0.01～0.9%.
A kind of preparation method of multiple modified composite photo-catalyst at first prepares the SnO that contains transition metal Co, Mo, Cu, Pt, Au, Pd, Ag 2-TiO 2Catalyst, perhaps earlier synthetic composite semiconductor light-catalyst matrix SnO 2-TiO 2, containing the solution of transition metal again through dipping, oven dry is then ground, at last through the SnO of vapour deposition process in transient metal doped modification 2-TiO 2Catalyst surface growth in situ CNTs.
Composite semiconductor SnO in the transition metal modification 2-TiO 2Through chemical vapor deposition method growth in situ CNTs, chemical vapor deposition adopts fluidized bed process or adopts fixed bed process on the matrix.
Fluidized bed process: the SnO that will be mixed with transition metal 2-TiO 2Catalyst places fluidized-bed reactor, in high-purity N 2Under the air-flow, make catalyst fines reach desirable fluidized state, then reactor is carried out temperature programming, when reactor temperature reaches the required preference temperature of growth CNTs, feed C 2H 4, growth CNTs; Through control N 2With C 2H 4Volume flow ratio 10～100: 1, the growth of factor such as 400～750 ℃ of growth temperatures, growth time 2～60 minutes control CNT.
Fixed bed process: filling is mixed with the SnO of transition metal in fixed bed reactors 2-TiO 2Catalyst is in high-purity N 2Under the air-flow, reactor is carried out temperature programming; When reactor temperature reaches the required preference temperature of growth CNTs, feed C 2H 4, growth CNTs; Through control N 2With C 2H 4Flow-rate ratio 10～100: 1, the growth of factor such as 400～750 ℃ of growth temperatures, growth time 2～60 minutes control CNT.
In the reducing atmosphere of carbon nano-tube, be entrained in SnO 2-TiO 2In at least a element of transistion metal compound can be reduced into metallic state, like CoO 2Can be reduced into Co, play the effect of the catalytic active center of growth CNTs.
Compared with prior art, good effect of the present invention is:
The present invention provides two-step method to prepare multiple modified composite catalyst; The SnO that at first prepares transient metal doped modification 2-TiO 2Catalyst matrix adopts the SnO of vapor phase method at doping vario-property then 2-TiO 2Growth in situ CNTs on the matrix; Reached transient metal doped and the purpose modification of CNT composite multiple; The preparation method of composite photo-catalyst provided by the invention is suitable for large-scale production.
[specific embodiment]
The specific embodiment of a kind of multiple modified composite photo-catalyst of the present invention and preparation method thereof below is provided.
Embodiment 1
Take by weighing 17.0g SnCl 45H 2O and 68.0g butyl titanate solution add 377ml absolute ethyl alcohol and 26.75g nitric acid, and stirring obtains solution A, with 0.25g Co (NO 3) 26H 2O is dissolved in the 215ml deionized water, obtains solution B.Solution B is added drop-wise in the solution A, stirred 2 hours; Left standstill 10～48 hours, and in 60～120 ℃ of baking ovens, dried, be warming up to 400 ℃ with the heating rate of 3 ℃/min, roasting 2～6 hours is taken out subsequent usely, and the SnO that obtains transition metal cobalt doping vario-property is ground in cooling 2-TiO 2Catalyst.
SnO with above-mentioned transition metal cobalt doping vario-property 2-TiO 2Catalyst places fluidized-bed reactor, and loaded catalyst is 10g, and granularity is 100～200 orders.At flow is 0.25～0.4m 3/ h high-purity N 2Under the air-flow, reactor is carried out temperature programming.When reactor temperature is 600 ℃, feed C 2H 4, at N 2And C 2H 4Flow-rate ratio is 25: 1, and total tolerance is 3.5m 3Under/h the condition, fluid bed CVD growth CNTs20 minute, reaction naturally cools to room temperature after finishing, and takes out product, promptly obtains cobalt and mixes and the compound dual modified SnO of CNT 2-TiO 2Base composite photocatalyst.With the methylene blue is model pollutant, and sunshine is a light source, and 90 minutes cobalts that record mix and the compound dual modified SnO of CNT 2-TiO 2Base composite photocatalyst is 92% to the degradation rate of methylene blue, and unmodified semiconductor SnO 2-TiO 2Photochemical catalyst matrix degradation rate is 26%.
Embodiment 2
Use earlier Prepared by Sol Gel Method SnO 2-TiO 2Catalyst (Sn: Ti=0.5, mol ratio) is got SnO then 2-TiO 2Catalyst fines 20 gram is scattered in that (molar concentration of ammonium molybdate is 1.0mol/L in 500 milliliters of ammonium molybdates and the copper chloride mixed solution; The molar concentration of copper chloride is 2.2mol/L); Stirred 2～4 hours; Flooded 10～48 hours, and can obtain the SnO of transition metal copper and the modification of molybdenum co-doped then 40～120 ℃ of following oven dry 2-TiO 2Catalyst
SnO with above-mentioned transition metal copper and the modification of molybdenum co-doped 2-TiO 2Catalyst is filled in the fixed bed reactors.In high-purity N 2Under the air-flow, reactor is carried out temperature programming.When reactor temperature is 550 ℃, feed C 2H 4, at N 2And C 2H 4Flow-rate ratio is 15: 1, growth CNTs 15 minutes, and reaction naturally cools to room temperature after finishing, and takes out product, promptly obtains transition metal copper and the modification of molybdenum co-doped and the composite modified SnO of CNT 2-TiO 2Composite photo-catalyst.With the methylene blue is model pollutant, and sunshine is a light source, 90 minutes transition metal coppers that record and modification of molybdenum co-doped and the composite modified SnO of CNT 2-TiO 2Composite photo-catalyst is 94% to the degradation rate of methylene blue, and unmodified semiconductor SnO 2-TiO 2Photochemical catalyst matrix degradation rate is 22%.
The present invention at first prepares transient metal doped SnO 2-TiO 2Catalyst adopts vapor phase method at SnO then 2-TiO 2Catalyst surface in-situ growing carbon nano tube (CNTs) is prepared the compound and transient metal doped multiple modified composite photo-catalyst of CNT, and transition metal ions can be used as base light catalyst S nO in the compound system 2-TiO 2The element of doping vario-property, the transition metal that is reduced simultaneously is as the catalytic active center of CNTs growth.CNTs and transition metal with light induced electron rapidly from SnO 2-TiO 2The middle derivation reduced the recombination probability in light induced electron and hole, and multiple modified synergy has promoted composite semiconductor SnO greatly 2-TiO 2Photocatalytic activity.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.

Claims (6)

1. a multiple modified composite photo-catalyst is characterized in that, its matrix is SnO 2With TiO 2Composite semiconductor SnO 2-TiO 2, wherein the atomic ratio of Sn and Ti is 0.1～10.0: 1.
2. a kind of multiple modified composite photo-catalyst as claimed in claim 1 is characterized in that, the doping vario-property of transition metal is at SnO 2-TiO 2Composite semiconductor prepares in the process and carries out, perhaps the SnO to having prepared 2-TiO 2Carrying out modification handles.
3. like claim 1 or 2 described a kind of multiple modified composite photo-catalysts, it is characterized in that, SnO 2-TiO 2The transition metal of matrix doping vario-property is one or more the composition among Co, Mo, Cu, Pt, Au, Pd, the Ag, with SnO 2-TiO 2Be benchmark, the quality percentage mark of containing transition metal element is 0.01～0.9%.
4. the preparation method of a multiple modified composite photo-catalyst is characterized in that, at first, prepares the SnO that contains transition metal Co, Mo, Cu, Pt, Au, Pd, Ag 2-TiO 2Catalyst, perhaps earlier synthetic composite semiconductor light-catalyst matrix SnO 2-TiO 2, containing the solution of transition metal again through dipping, oven dry is then ground, at last through the SnO of vapour deposition process in transient metal doped modification 2-TiO 2Catalyst surface growth in situ CNTs.
5. the preparation method of a kind of multiple modified composite photo-catalyst as claimed in claim 4 is characterized in that, at the composite semiconductor SnO of transition metal modification 2-TiO 2Through chemical vapor deposition method growth in situ CNTs, the chemical vapor deposition method adopts fluidized bed process or adopts fixed bed process on the matrix.
6. the preparation method of a kind of multiple modified composite photo-catalyst as claimed in claim 5 is characterized in that, in the reducing atmosphere of the carbon nano-tube in the chemical vapor deposition method, is entrained in SnO 2-TiO 2In at least a element of transistion metal compound can be reduced into metallic state.
CN2012100225985A 2012-02-01 2012-02-01 Multiple modified composite photocatalyst and preparation method thereof Expired - Fee Related CN102553562B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055873A (en) * 2013-01-04 2013-04-24 华东理工大学 Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof
CN105312090A (en) * 2015-12-07 2016-02-10 福州大学 Preparation of (C5H5) Ru/TiO2 organic-inorganic hybrid photocatalyst
CN105618103A (en) * 2016-02-25 2016-06-01 济南大学 Method for preparing two-dimensional magnetic photocatalyst
CN106582631A (en) * 2016-12-28 2017-04-26 盐城工学院 Titanium stannate photocatalyst and preparation method and application thereof
CN109126772A (en) * 2018-09-25 2019-01-04 天津科技大学 A kind of photocatalysis composite and preparation method thereof
CN110038546A (en) * 2019-04-03 2019-07-23 中国环境科学研究院 One kind is for light-catalysed nanocomposite and the preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李爱昌等: "Ag改性TiO2/SnO2纳米薄膜及光催化降解甲基橙的性能", 《中国有色金属学报》 *
马磊等: "流化床-化学气相沉积法制备CNT/Fe-Ni/TiO2及其光催化性能研究", 《无机材料化学》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055873A (en) * 2013-01-04 2013-04-24 华东理工大学 Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof
CN103055873B (en) * 2013-01-04 2015-04-08 华东理工大学 Composite photocatalyst membrane material with hierarchical pore structure and preparation method thereof
CN105312090A (en) * 2015-12-07 2016-02-10 福州大学 Preparation of (C5H5) Ru/TiO2 organic-inorganic hybrid photocatalyst
CN105312090B (en) * 2015-12-07 2017-09-15 福州大学 One kind (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst
CN105618103A (en) * 2016-02-25 2016-06-01 济南大学 Method for preparing two-dimensional magnetic photocatalyst
CN105618103B (en) * 2016-02-25 2018-05-11 济南大学 A kind of preparation method of two-dimensional magnetic photochemical catalyst
CN106582631A (en) * 2016-12-28 2017-04-26 盐城工学院 Titanium stannate photocatalyst and preparation method and application thereof
CN106582631B (en) * 2016-12-28 2019-05-21 盐城工学院 A kind of stannic acid titanium photochemical catalyst and preparation method thereof, application
CN109126772A (en) * 2018-09-25 2019-01-04 天津科技大学 A kind of photocatalysis composite and preparation method thereof
CN109126772B (en) * 2018-09-25 2022-01-04 天津科技大学 Composite photocatalyst material and preparation method thereof
CN110038546A (en) * 2019-04-03 2019-07-23 中国环境科学研究院 One kind is for light-catalysed nanocomposite and the preparation method and application thereof

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