CN100411731C - Method for preparing nano powder photocatalyst - Google Patents

Method for preparing nano powder photocatalyst Download PDF

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CN100411731C
CN100411731C CNB200610069077XA CN200610069077A CN100411731C CN 100411731 C CN100411731 C CN 100411731C CN B200610069077X A CNB200610069077X A CN B200610069077XA CN 200610069077 A CN200610069077 A CN 200610069077A CN 100411731 C CN100411731 C CN 100411731C
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nano
preparation
nano powder
powder
temperature oxidation
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CN1935362A (en
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徐海波
王伟
王佳
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Ocean University of China
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Ocean University of China
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention relates to a preparation method of nano powder body photocatalyst. It is characterized by that it uses an inorganic compound nano powder body of titanium as precursor reactant, can make it directly undergo the process of high-temperature oxidation treatment, or make it be soaked in an organic solution or aqueous solution, then undergone the processes of drying treatment and high-temperature oxidation treatment so as to obtain an anatase phase or rutile phase or anatase phase and rutile phase composite phase or anion-doped tilanium dioxide contained nano powder body.

Description

A kind of preparation method of nano powder photocatalyst
Technical field
The present invention relates to a kind of preparation method of nano powder photocatalyst.
Background technology
The relevant TiO that uses 2Prepare H as the photochemical catalyst decomposition water 2Report see 1972 the earliest, this indicates the beginning of multiphase photocatalysis research.Serious day by day along with problem of environmental pollution, the multiphase photocatalysis process of utilizing semi-conductive photocatalysis to handle all contaminations has become a kind of ideal environment improvement technology.In the semiconductor light-catalyst of present broad research, TiO 2Application potential is arranged most, having that chemical property is stable, advantages such as high and very strong oxidation of the electromotive force in the burn into resistance to acids and bases is good, the source is abundant, reserves are big, semiconductor energy gap is big, illumination produces light induced electron and hole and reproducibility do not take place after the illumination, is the focus that photochemical catalyst is studied.TiO 2Have 3 kinds of crystal structures: brookite type, Detitanium-ore-type and rutile-type.Wherein, Detitanium-ore-type and rutile-type are two kinds of stable crystal structures, and Detitanium-ore-type is lower than rutile-type crystal sintering temperature, particle diameter is little, be uniformly dispersed, so the photocatalytic activity height.Learn to have the TiO of highlight catalytic active according to people such as Bickley research 2Majority is the mixture of Detitanium-ore-type and rutile-type, i.e. the mixed crystal effect.This be because the superficial growth of Detitanium-ore-type crystal thin rutile-type crystallizing layer, can promote the separation of charge in light induced electron hole in the Detitanium-ore-type crystal effectively.People's such as Gao Wei experiment shows that the mass ratio of anatase and rutile is at 9: 1 o'clock, and the catalytic effect of sample is the most remarkable.The nineties in 20th century nanometer technology development, for the application of nano-photocatalyst provides fabulous opportunity.Nano-TiO 2Can be used to build, the antibacterial and deodouring in field such as coating, health care, decompose the organic matter in the sewage, reduction high price toxic metals ion or recovery precious metal ion, waste gas purification, photochemical catalyzing is produced hydrogen and oxygen and is made novel solar battery etc.
But TiO 2The greater band gap of photochemical catalyst can only be equal to or less than the 387.5nm ultraviolet excitation of (being equivalent to 312eV) by wavelength, and solar energy utilization rate is had only 3%～5%.In order to improve TiO 2Quantum yield, people attempt overcoming with means such as ion doping composite semiconductors its fault of construction, to improve photocatalytic activity.In order to improve TiO 2Photocatalytic activity with satisfy different instructions for uses, and TiO 2Characteristics such as nanometer powder exists easily and assembles, easy inactivation, more difficult recovery and reuse adopt the method for finishing and doping to come TiO usually 2Carry out modification.Report that more method of modifying has doping, precious metal surface deposition, the semiconductor of doping, the rare earth element of transition metal ions and metal oxide compound, method of modifying such as surface light sensitization, surface are super-strong acidified, surface reduction processing, chelated surface and derivatization.People such as calendar year 2001 Asahi find nitrogen doped Ti O 2Photochemical catalyst is not reducing TiO 2Under the photoactive condition of ultraviolet, also have visible light activity, and this nitrogen doped Ti O 2The good stability of photochemical catalyst has started N doped Ti O 2Research boom.
In addition, the photocatalytic activity of TiO2 also has confidential relation with factors such as its preparation method, particle diameter, surface areas.Nano-TiO 2Preparation generally can be divided into vapor phase method and liquid phase method, with TiCl 4, the alkoxide of titanium, Ti (SO 4) 2Or TiOSO 4Deng being raw material.Vapor phase method has quick formation Detitanium-ore-type, rutile-type or mixes crystal formation TiO 2Advantage, and post processing is simple, serialization degree height is particularly suitable for large-scale industrialization production, but it is to equipment and specification requirement height, the diameter of particle of producing is relatively large.Liquid phase method has simple to operate, to advantages such as equipment are less demanding, relatively is fit to the laboratory and prepares nano-TiO 2, but its cycle is long, and quantity of three wastes is big, is that raw material is then with high costs as if the alkoxide with titanium.Therefore, in order to improve nano-TiO 2Quantum yield, improve TiO 2Photocatalytic activity with satisfy different instructions for uses, the preparation method of nano powder photocatalyst that exploitation has low manufacturing cost becomes the key issue that present urgent need solves.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano powder photocatalyst, it can satisfy the demand of prior art.
A kind of preparation method of nano powder photocatalyst, it is characterized in that the inorganic compound nano-powder with titanium is a precursor reagent, directly carry out high temperature oxidation process, or impregnated in the organic solution or the aqueous solution, handle through super-dry, high temperature oxidation process again, obtain a kind of anatase mutually or rutile mutually anatase and rutile mutually compound phase or the anion doped nano-powder that contains titanium dioxide is arranged.
The present invention have make simple and easy, the photocatalytic activity height, stability is good, the advantage that production cost is low can obtain single-phase anatase mutually or rutile phase TiO by control technological process and parameter 2, anatase and rutile mixing crystal formation TiO mutually 2, the TiO of anion doped (N, C, B etc.) arranged 2Or the TiO that has platinum group metal or magnesium-yttrium-transition metal to mix 2Nano powder photocatalyst.
Description of drawings
Accompanying drawing 1 is anatase phase TiO 2Nano-powder is main transmission electron microscope photo.
Accompanying drawing 2 is anatase phase TiO 2Nano-powder is main X-ray diffraction spectrogram.
Accompanying drawing 3 is rutile phase TiO 2Nano-powder is main transmission electron microscope photo.
Accompanying drawing 4 is rutile phase TiO 2Nano-powder is main X-ray diffraction spectrogram.
Accompanying drawing 5 is SnO 2With the common rutile that mixes of platinum TiO mutually 2The transmission electron microscope photo of nano-powder.
Accompanying drawing 6 is SnO 2With the common rutile that mixes of platinum TiO mutually 2The X-ray diffraction spectrogram of nano-powder.
The specific embodiment
Embodiment one
According to the preparation method of nano powder photocatalyst of the present invention, with TiN nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 14nm, specific area 80m 2/ g, purity is greater than 97%), high-temperature oxydation is 4 hours in 500 ℃ and air atmosphere, makes with anatase phase TiO 2It is main nano-powder.Fig. 1 is anatase phase TiO 2Nano-powder is main transmission electron microscope photo, and yardstick is the spherical particle about 15nm as can see from Figure 1.Fig. 2 is anatase phase TiO 2Nano-powder is main X-ray diffraction spectrogram, and Dui Ying diffraction maximum mainly is anatase phase TiO as can see from Figure 2 2, a spot of rutile phase and nitrogen atom doping are also arranged.
Embodiment two
According to the preparation method of nano powder photocatalyst of the present invention, with TiC nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 12nm, specific area 120m 2/ g, purity is greater than 97%) at first impregnated in the organic solution of forming by n-butanol and oxalic acid, then in drying box in 120 ℃ of dry processing, high-temperature oxydation 4 hours in 250 ℃ and oxidizing atmosphere makes with rutile phase TiO at last 2It is main nano-powder.Fig. 3 is rutile phase TiO 2Nano-powder is main transmission electron microscope photo, and yardstick is the nearly spherical particle about 12nm as can see from Figure 3, and there is certain agglomeration in powder.Fig. 4 is rutile phase TiO 2Nano-powder is main X-ray diffraction spectrogram, and Dui Ying diffraction maximum mainly is rutile phase TiO as can see from Figure 4 2, a spot of anatase phase and nitrogen atom doping are also arranged.
Embodiment three
According to the preparation method of nano powder photocatalyst of the present invention, with TiB 2Nano-powder (Hefei Kaier Nano Technology Development Co., Ltd, particle mean size 14nm, specific area 100m 2/ g, purity is greater than 97%) at first impregnated in the aqueous solution of forming by water, hydrochloric acid, stannous chloride and chloroplatinic acid, in drying box, handle then in 60 ℃ of dryings, high-temperature oxydation 15 minutes in 800 ℃ and air atmosphere again, recycle above-mentioned dipping-drying-high temperature oxidation process process 5 times, make SnO 2With the common rutile that mixes of platinum TiO mutually 2Nano-powder.Fig. 5 is SnO 2With the common rutile that mixes of platinum TiO mutually 2The transmission electron microscope photo of nano-powder, yardstick is the strip bulky grain about wide 10nm as can see from Figure 5, large particle surface is attached with the spherical granule about 5nm.Fig. 6 is SnO 2With the common rutile that mixes of platinum TiO mutually 2The X-ray diffraction spectrogram of nano-powder, Dui Ying diffraction maximum mainly is rutile phase TiO as can see from Figure 6 2And platinum, SnO 2Solid solution is in rutile phase TiO 2In.
The inorganic compound of the titanium of the powdery described in the present invention can be the nitride of titanium or in boride or carbide or the low oxide one or more, and the granularity size is 1nm～100nm. Described organic solution can be the mixture of organic solvent and inorganic acid or organic acid formation, the aqueous solution can be the mixture of water and organic acid or inorganic acid formation, and can contain one or more platinums group metal in the organic solution or the aqueous solution or/and the compound of magnesium-yttrium-transition metal; The dry temperature of handling is 20 ℃～150 ℃; The temperature of high-temperature oxydation thermal decomposition process is 200 ℃～1000 ℃, and its processing procedure can be carried out in air, also can carry out in oxidizing atmosphere; The nano-powder that contains titanium dioxide, can by repeatedly the circulation: dipping-drying-high temperature oxidation process process makes.
The antibacterial and deodouring in fields such as the nano powder photocatalyst that utilizes preparation method of the present invention to obtain can be widely used in building, coating, health care, decompose the organic matter in the sewage, reduction high price toxic metals ion or recovery precious metal ion, waste gas purification, photochemical catalyzing are produced hydrogen and oxygen and are made novel solar battery etc.

Claims (7)

1. the preparation method of a nano powder photocatalyst, it is characterized in that the inorganic compound nano-powder with titanium is a precursor reagent, the inorganic compound of described titanium is the nitride of titanium, boride or carbide, the granularity size is 1nm～100nm, directly carry out high temperature oxidation process, the temperature of high temperature oxidation process is 200 ℃～1000 ℃, or impregnated in the organic solution or the aqueous solution, handle through super-dry, high temperature oxidation process again, the temperature of high temperature oxidation process is 200 ℃～1000 ℃, obtain a kind of anatase mutually or rutile mutually or the nano-powder that contains titanium dioxide of anatase and rutile compound phase mutually.
2. the preparation method of nano powder photocatalyst according to claim 1 is characterized in that described high temperature oxidation process carries out in oxidizing atmosphere.
3. the preparation method of nano powder photocatalyst according to claim 1 is characterized in that described organic solution is the mixture of organic solvent and inorganic acid or organic acid formation.
4. the preparation method of nano powder photocatalyst according to claim 1 is characterized in that the described aqueous solution is the mixture of water and organic acid or inorganic acid formation.
5. the preparation method of nano powder photocatalyst according to claim 1 is characterized in that containing the platinum group metal in the described organic solution or the aqueous solution or/and the compound of Sn.
6. the preparation method of nano powder photocatalyst according to claim 1 is characterized in that the described dry temperature of handling is 20 ℃～150 ℃.
7. the preparation method of nano powder photocatalyst according to claim 1, it is characterized in that the described nano-powder that contains titanium dioxide is by repeatedly circulation: dipping-drying-high temperature oxidation process process makes.
CNB200610069077XA 2006-09-22 2006-09-22 Method for preparing nano powder photocatalyst Expired - Fee Related CN100411731C (en)

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CN101743060B (en) * 2007-06-01 2014-03-12 微宏公司 Photodegradation catalyst and photodegradation catalyst precursor comprising metal halide or metal oxyhalide
CN108808029A (en) * 2016-04-06 2018-11-13 南通大学 Inexpensive N, C adulterate TiO2Nano-fibre supported Pd@Ni method for preparing anode catalyst of direct methanol
CN107649118B (en) * 2017-09-15 2021-03-02 青岛科技大学 BiVO4Supported mixed crystalline phase TiO2Preparation method of visible light composite photocatalyst
JP7410054B2 (en) * 2018-05-02 2024-01-09 コロロッビア コンサルティング ソチエタ レスポンサビリタ リミタータ Nitrogen-doped TiO2 nanoparticles and their use in photocatalysis

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CN1343530A (en) * 2000-09-21 2002-04-10 上海大学 Process for preparing TiO2 photocatalyst
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特开2003-119071A 2003.04.23

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