CN103521205A - A method for preparing high photocatalytic activity core-shell structure TiO2 material - Google Patents

A method for preparing high photocatalytic activity core-shell structure TiO2 material Download PDF

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CN103521205A
CN103521205A CN201310467746.9A CN201310467746A CN103521205A CN 103521205 A CN103521205 A CN 103521205A CN 201310467746 A CN201310467746 A CN 201310467746A CN 103521205 A CN103521205 A CN 103521205A
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tio
shell structure
crystalline
core
tio2
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曹傲能
张新
韩凯
王海芳
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

本发明涉及一种制备高光催化活性核壳结构TiO2材料的方法，通过超声、加热或微波处理晶态TiO2材料（如商业二氧化钛纳米材料P25）的悬浮液，一步将其转换成具有晶体内核和无定型壳层的核壳结构TiO2材料。反应过程中，反应物TiO2材料表面吸附溶剂中的羟基，在超声、加热或微波的作用下，TiO2晶体表面部分Ti4+被还原成Ti3+，同时在表面形成一个非晶态壳层。本发明操作方法简单新颖可行，不利用其他贵重金属元素，对环境无污染，耗能低，绿色环保、生产成本低，具有比未处理的晶态TiO2材料高数倍到数十倍的光催化分解水制备氢气和光催化降解有机污染物的活性，具有商业规模化生产潜力。

The present invention relates to a method for preparing a highly photocatalytically active core-shell structure TiO2 material, by ultrasonically, heating or microwave treating a suspension of crystalline TiO2 material (such as commercial titanium dioxide nanomaterial P25) to convert it into one with a crystalline core in one step and amorphous shell core-shell structure TiO 2 materials. During the reaction process, the reactant TiO 2 material surface adsorbs hydroxyl groups in the solvent, and under the action of ultrasound, heating or microwave, Ti 4+ on the surface of TiO 2 crystals is reduced to Ti 3+ , and an amorphous shell is formed on the surface layer. The operation method of the present invention is simple, novel and feasible, does not use other precious metal elements, has no pollution to the environment, low energy consumption, green environmental protection, low production cost, and has a light intensity several to dozens of times higher than that of untreated crystalline TiO2 materials. The activity of catalytic water splitting to produce hydrogen and photocatalytic degradation of organic pollutants has the potential of commercial scale production.

Description

A kind of highlight catalytic active nucleocapsid structure TiO for preparing 2the method of material
Technical field
The present invention relates to a kind of highlight catalytic active nucleocapsid structure TiO for preparing 2the method of material, belongs to nano inorganic material and actinic material field.
Background technology
TiO 2in photochemistry field, there is application very widely, especially, in photochemical catalyst, be subject to the attention of numerous researchers.Along with the development of 21 century economy, environment and energy bottleneck problem more become outstanding, and it is more urgent that the research of environmentally friendly shaped material and new forms of energy also becomes.In all energy, hydrogen is as unique pollution-free reproducible energy, the energy that after the non-renewable energies such as oil, coal and natural gas that continue beyond doubt, a new generation is widely adopted.Hydrogen Energy specific energy density is high, and the product of burning is water, can not produce environmental pollution.
At numerous catalysis materials, (comprise ZnO, SnO 2, WO 3deng oxide and CdS, ZnS sulfides) in, TiO 2have nontoxic, stable performance, cheap, highlight catalytic active can decomposition goal thing etc. feature, be considered to a kind of good photochemical catalyst, be widely used in photocatalysis, light reaction variable color, photovoltage and electrochromics field.Effectively utilize the energy crisis that clean, safe and abundant solar energy can not only solve facing mankind, and will solve day by day serious problem of environmental pollution.
TiO 2the practical subject matter of base optic catalytic material is: TiO 2forbidden band is wider, and the efficiency of light energy utilization is lower, and the absorption of sunshine is confined to ultra-violet (UV) band, and the efficiency of light energy utilization is less than 3%.For this problem, domestic and international researcher has done a large amount of research work, by exploring catalytic process mechanism, has developed multiple method of modifying, to TiO 2carry out modification, comprise reduction Ti(IV) generate Ti(III), all expansion in various degree TiO 2photoresponse scope, improved its visible light photocatalysis active.But correlation technique relates to high temperature, high pressure, consuming time longer, needs the unfavorable factors such as precious metal.
Summary of the invention
The defect existing for prior art, the object of this invention is to provide a kind of highlight catalytic active nucleocapsid structure TiO for preparing 2the method of material.Utilize a kind of method of operating of simple possible, by TiO 2plane of crystal part Ti 4+be reduced into Ti 3+, form one deck amorphous state simultaneously, obtain having the TiO of high catalytic activity 2catalyst material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of highlight catalytic active nucleocapsid structure TiO for preparing 2the method of material, by ultrasonic, heating or microwave treatment crystalline state TiO 2the suspension of material, a step converts thereof into the nucleocapsid structure TiO with crystal kernel and unformed shell 2material; There is following preparation process and step: by reactant crystalline state TiO 2even with solvent, reaction system is solid phase-liquid-phase system, and reaction system is carried out to ultrasonic, heating or microwave treatment; In course of reaction, reactant TiO 2hydroxyl in material surface adsorption solvent, under the effect of ultrasonic, heating or microwave, TiO 2plane of crystal part Ti 4+be reduced into Ti 3+, form one deck amorphous state simultaneously, obtain having high catalytic activity nucleocapsid structure TiO 2material.
Described solvent is that pH value is 3 ~ 14 the aqueous solution or alcoholic solution or its mixed solution.
Reactant feed adopts crystalline state TiO 2material (as business titanium dioxide nano material P25, being to utilize anatase that vapour deposition process obtains and rutile to take the mixed crystal that 80:20 is ratio, excellent performance).In preparation process, just utilize some simple solvents, some heavy metal ion of not adulterating reach modification object.Therefore after modification, still keep pollution-free, environmental protection excellent specific property.The nucleocapsid structure TiO obtaining 2photocatalyst material, has unformed amorphous state shell and coated crystallization TiO 2kernel, before and after reaction, particle diameter is without obvious change.After reaction, color is become the dark colours such as lark from white, has the features such as oxygen room and trivalent titanium ion simultaneously, and visible region is widened by ultraviolet region in extinction region, has greatly improved light utilization efficiency, has very outstanding catalytic activity simultaneously.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and significant advantage:
The present invention adopts the simple operations modes such as microwave technology, ultrasonic technique and direct baking oven heating in preparation process; in conjunction with solid phase-liquid phase reactor; method of operating is very simple novel feasible; do not utilize other precious metal elements; environmentally safe; consume energy low, environmental protection, production cost are low, have commercial size productive potentialities.
Accompanying drawing explanation
Fig. 1 is gained nucleocapsid structure TiO of the present invention 2high power transmission electron microscope (HR-TEM) the photo figure of photocatalyst material.
Fig. 2 is gained nucleocapsid structure TiO of the present invention 2electron paramagnetic resonance power spectrum (EPR) analysis chart of photocatalyst material.
Fig. 3 is gained nucleocapsid structure TiO of the present invention 2the photocatalysis hydrogen production performance map of photocatalyst material.
Fig. 4 is gained nucleocapsid structure TiO of the present invention 2the photocatalytic degradation rhodamine B performance comparison figure of photocatalyst material and untreated P25.
Fig. 5 is that the present invention processes gained nucleocapsid structure TiO under condition of different pH 2the photocatalytic degradation rhodamine B performance comparison figure of photocatalyst material and untreated P25.
Fig. 6 is that the present invention uses ethylene glycol solution microwave treatment P25 gained nucleocapsid structure TiO 2the photocatalytic degradation rhodamine B performance comparison figure of photocatalyst material and untreated P25.
Fig. 7 is that the present invention uses the aqueous solution and the ultrasonic processing of ethanolic solution P25 gained nucleocapsid structure TiO 2the photocatalytic degradation rhodamine B performance comparison figure of photocatalyst material and untreated P25.
Fig. 8 is that the present invention uses the aqueous solution and volume fraction 50% ethanol water high-temperature heat treatment P25 gained nucleocapsid structure TiO 2the photocatalytic degradation rhodamine B performance comparison figure of photocatalyst material and untreated P25.
The specific embodiment
After now specific embodiments of the invention being discussed in.
embodiment 1
Process and step in the present embodiment are as follows:
By P25 mass concentration, be the P25 that 1 mg/ ml weighs 50 mg, measure deionized water 50 ml, mix.Mixed liquor is put into 30 seconds of micro-wave oven microwave treatment, and cooling rear centrifugal drying, obtains having very highly active nucleocapsid structure TiO 2photocatalyst material.This material is carried out to structure and performance characterization, and the high-resolution-ration transmission electric-lens that Fig. 1 is resulting materials (HRTEM) is schemed, and can clearly see the nucleocapsid structure of crystalline nucleation in shell amorphous from figure.Fig. 2 is electron paramagnetic power spectrum (EPR) figure, and wherein P25 is untreated business titanium dioxide P25, m-TiO 2for this method, process the material obtaining, from figure, can be clear that the difference of the two, and m-TiO 2the peak type and the peak position that occur are Ti 3+characteristic peak, proved Ti 3+existence.Fig. 3 is photocatalysis hydrogen production performance test, and wherein P25 is untreated business titanium dioxide P25, m-TiO 2for the inventive method is processed the material obtaining, the relatively untreated P25 hydrogen manufacturing performance of material that as can be seen from the figure this method processing obtains is significantly improved.Fig. 4 is the performance test of photocatalytic degradation rhodamine B, and wherein P25 is untreated business titanium dioxide P25, m-TiO 2for this method is processed the material obtaining, the relatively untreated P25 light degradation property of material that as can be seen from the figure this method processing obtains is significantly improved.
embodiment 2
By P25 mass concentration, be the P25 that 1 mg/ ml weighs 50 mg, measure respectively deionized water 50 ml, mix, and regulate pH of mixed to be respectively 4.8,6.7,9.1.Mixed liquor is put into micro-wave oven microwave treatment 1 minute, cooling rear centrifugal drying.Different: to regulate aqueous solution pH to be respectively 4.8,6.7,9.1.Resulting materials is carried out to performance characterization.Fig. 5 is the performance test that different pH process photocatalytic degradation rhodamine B, and wherein P25 is untreated business titanium dioxide P25, m-TiO 2for this method is processed the material obtaining.As can be seen from the figure under different pH, process the relatively untreated P25 performance of material light catalysis property obtaining and be significantly improved, and increase with pH rising catalytic degradation activity.
embodiment 3
By P25 mass concentration, be the P25 that 1 mg/ ml weighs 50 mg, measure ethylene glycol 50 ml, mix, mixed liquor is put into micro-wave oven microwave treatment 1 minute, cooling rear centrifugal drying.The performance test of Fig. 6 photocatalytic degradation rhodamine B, the relatively untreated P25 catalytic performance of P25 that ethylene glycol is processed is as we can see from the figure significantly improved.
embodiment 4
By P25 mass concentration, be the P25 that 0.5mg/ ml weighs respectively 25 mg, measure deionized water 50 ml and ethanol 50ml, mix respectively, by the ultrasonic processing of the mixed solution obtaining a hour, centrifugal rear dry.The bi-material that ultrasonic method is obtained carries out performance characterization.The performance test of this bi-material of Fig. 7 and untreated P25 photocatalytic degradation rhodamine B, as can be seen from the figure adopts the method to process the TiO obtaining 2the relatively untreated P25 catalytic activity of material is significantly improved.
embodiment 6
By P25 mass concentration, be the P25 that 0.25mg/ ml weighs respectively 25 mg, the ethanol water 100ml that measures deionized water 100ml and volume fraction 50% mixes with it respectively, after mixing in 180 ℃ of baking ovens heat treatment 3h, cooling rear centrifugal drying.Fig. 8 is the performance test of this bi-material and untreated P25 photocatalytic degradation rhodamine B, as can be seen from the figure adopts the method to process the TiO obtaining 2the relatively untreated P25 catalytic activity of material is significantly improved.

Claims (3)

1.一种制备高光催化活性核壳结构TiO2材料的方法，其特征在于，通过超声、加热或微波处理晶态TiO2材料的悬浮液，一步将其转换成具有晶体内核和无定型壳层的核壳结构TiO2材料；具有以下制备过程和步骤：将反应物晶态TiO2与溶剂混合均匀，反应体系为固相-液相体系，对反应体系进行超声、加热或微波处理；反应过程中，反应物TiO2材料表面吸附溶剂中的羟基，在超声、加热或微波的作用下，TiO2晶体表面部分Ti4+被还原成Ti3+，同时形成一层非晶态，得到具有高催化活性核壳结构TiO2材料。 1. A method for preparing highly photocatalytically active core-shell structure TiO 2 materials, characterized in that, through ultrasonication, heating or microwave treatment of the suspension of crystalline TiO 2 materials, it is converted into a layer with a crystalline core and an amorphous shell in one step The core-shell structure TiO2 material; has the following preparation process and steps: mix the reactant crystalline TiO2 with the solvent evenly, the reaction system is a solid-liquid phase system, and the reaction system is subjected to ultrasonic, heating or microwave treatment; the reaction process In this process, the reactant TiO 2 material surface adsorbs hydroxyl groups in the solvent, under the action of ultrasound, heating or microwave, Ti 4+ on the surface of TiO 2 crystals is reduced to Ti 3+ , and a layer of amorphous state is formed at the same time, resulting in a high Catalytically active core-shell structured TiO2 materials. 2.根据权利要求1所述的制备高催化活性核壳结构TiO2材料的方法，其特征在于，所述反应物晶态TiO2材料为商业TiO2材料P25。 2. The method for preparing highly catalytically active core-shell structure TiO 2 material according to claim 1, characterized in that, the reactant crystalline TiO 2 material is commercial TiO 2 material P25. 3.根据权利要求1所述的制备高催化活性核壳结构TiO2材料的方法，其特征在于，所述溶剂为pH值为3~14的水溶液或醇溶液或其混合溶液。 3. The method for preparing a highly catalytically active core-shell structure TiO2 material according to claim 1, wherein the solvent is an aqueous solution or an alcoholic solution or a mixed solution thereof with a pH value of 3 to 14.
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN105013462A (en) * 2015-07-01 2015-11-04 宁波工程学院 Application of TiO2 Hollow Mesoporous Nanofibers in Photocatalysts
CN106745282A (en) * 2016-11-11 2017-05-31 北京理工大学 A kind of preparation method with yolk eggshell structure manganese sesquioxide managnic oxide
CN106902795A (en) * 2017-02-15 2017-06-30 上海应用技术大学 A kind of core shell structure TiO2Raw powder's production technology
CN107876034A (en) * 2017-11-17 2018-04-06 中原工学院 A kind of Ti2O@TiO2Composite photo-catalyst and preparation method thereof
CN114496444A (en) * 2022-03-04 2022-05-13 Oppo广东移动通信有限公司 Soft magnetic composite material and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105013462A (en) * 2015-07-01 2015-11-04 宁波工程学院 Application of TiO2 Hollow Mesoporous Nanofibers in Photocatalysts
CN106745282A (en) * 2016-11-11 2017-05-31 北京理工大学 A kind of preparation method with yolk eggshell structure manganese sesquioxide managnic oxide
CN106902795A (en) * 2017-02-15 2017-06-30 上海应用技术大学 A kind of core shell structure TiO2Raw powder's production technology
CN107876034A (en) * 2017-11-17 2018-04-06 中原工学院 A kind of Ti2O@TiO2Composite photo-catalyst and preparation method thereof
CN114496444A (en) * 2022-03-04 2022-05-13 Oppo广东移动通信有限公司 Soft magnetic composite material and preparation method thereof

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Application publication date: 20140122