CN108686662A - Nano TiO 2-amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes - Google Patents

Nano TiO 2-amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes Download PDF

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Publication number
CN108686662A
CN108686662A CN201810524139.4A CN201810524139A CN108686662A CN 108686662 A CN108686662 A CN 108686662A CN 201810524139 A CN201810524139 A CN 201810524139A CN 108686662 A CN108686662 A CN 108686662A
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China
Prior art keywords
base alloy
nano
titanium dioxide
amorphous zirconium
composite photocatalyst
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Application number
CN201810524139.4A
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Chinese (zh)
Inventor
陈素红
龙明策
郭凯
吴苏清
张经祯
范春贞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
Original Assignee
Shanghai Jiaotong University
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
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Application filed by Shanghai Jiaotong University, State Grid Corp of China SGCC, Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd filed Critical Shanghai Jiaotong University
Priority to CN201810524139.4A priority Critical patent/CN108686662A/en
Publication of CN108686662A publication Critical patent/CN108686662A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/004Photocatalysts
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

Abstract

This application provides a kind of nano-TiOs2Amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes, the application be combined with each other each autocatalytic characteristics of micron order amorphous zirconium-base alloy and nano-titanium dioxide, ingredient reinforcing and process strengthening have been carried out to photochemical catalyst, ingredient, which strengthens combined process reinforcing, realizes combination among the strong ones, to improve the photocatalysis performance of photochemical catalyst, quality and efficiency of the photochemical catalyst to the photocatalytic degradation of organic pollution are improved.

Description

Nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes
Technical field
The present invention relates to composite photocatalyst material technical fields, more particularly, to a kind of nano-TiO2Amorphous zirconium-base alloy Composite photocatalyst material and preparation method thereof and purposes.
Background technology
In recent years, the report about the photocatalytic degradation research to organic pollution gradually increased.
Anatase tio2 is a kind of good photochemical catalyst, stablizes in water, is nontoxic, its photohole can aoxidize point The most harmful organic substances of solution, and they are finally decomposed into harmless inorganic matter.It has the following advantages:When It can be such that in waste water contained Some Organic Pollutants are completely degraded for CO2, H2O etc., and inorganic pollution is oxidated or reduced For harmless object;Second is that reaction condition is mild, low energy consumption, can react in ultraviolet light or under being exposed to sunlight;Three It is it to have many advantages, such as cheap, nontoxic, stable and may be reused, fourth, required device structure is simple, operating condition is easy Control, non-secondary pollution;Fifth, following can be using inexhaustible, nexhaustible solar energy as the light of activation photochemical catalyst Source.Many scholars handle organic pollution in laboratory study nano TiO 2 both at home and abroad at present, and obtain certain progress, but The density of TiO2 powder is far longer than water, and (density of anatase type tio2 is 3.84g/cm3, and the density of rutile TiO_2 is 4.26g/cm3), it can be sunken to the bottom, cannot be contacted with the oil on the water surface, and diameter of particle is smaller, is not easily recycled and causes two Secondary pollution.
The characteristics of atomic arrangement shortrange order longrange disorder of amorphous alloy make its at structure uniformly with extreme defect Entity, atomic arrangement extreme disordered state be at height coordination undersaturated condition thus there are more catalysis work Property center, therefore become a kind of preferable catalysis material.Due to the height unsaturation of the Atomic Arrangement in amorphous alloy, make It has more catalytic active center evenly, substantially increases catalytic effect, while amorphous during the reaction is microcosmic Structure change has facilitation to degradation process.
Therefore, the photocatalysis performance of photochemical catalyst how is improved, photochemical catalyst is improved and the photocatalysis of organic pollution is dropped The technical issues of quality of solution and efficiency are current those skilled in the art's urgent need to resolve.
Invention content
The purpose of the embodiment of the present invention is to provide a kind of nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material, to carry The photocatalysis performance of high catalyst improves quality and efficiency of the catalyst to the photocatalytic degradation of organic azo dyestuff contaminant. Another purpose of the embodiment of the present invention is to provide a kind of above-mentioned nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material Preparation method.Another purpose of the embodiment of the present invention is to provide a kind of above-mentioned nano-TiO2Amorphous zirconium-base alloy complex light The purposes of catalysis material.
In order to solve the above technical problems, technical solution provided by the invention is:
A kind of nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material, which is characterized in that by following masses percentage Raw material is made:10%~25% nano titanium dioxide powder, 25%~45% amorphous zirconium-base alloy particle, the dioxy of surplus SiClx powder;
The amorphous zirconium-base alloy particle includes the component of following mass percent:10%~30% Cu, 2%~5% Ni, 3%~10% Al, the Zr of surplus and inevitable impurity;
The grain size of the amorphous zirconium-base alloy particle is 200 μm~800 μm.
Preferably, the grain size of the nano titanium dioxide powder is 10nm~30nm.
A kind of above-mentioned nano-TiO2The preparation method of amorphous zirconium-base alloy composite photocatalyst material, includes the following steps:
1) negated brilliant zirconium-base alloy raw material carries out cutting process under gas shield, and it is 200 μm~800 μm that grain size, which is made, Amorphous zirconium-base alloy particle;
2) nano titanium dioxide powder is prepared, then carries out nano titanium dioxide powder at roasting under nitrogen protection Reason;
3) by amorphous zirconium-base alloy particle made from step 1), the nano titanium dioxide powder and two after step 2) roasting Ball-milling treatment is carried out after silicon oxide powder mixing, nano-TiO is made after the completion2Amorphous zirconium-base alloy composite photocatalyst material.
Preferably, nano titanium dioxide powder is prepared using sol-gal process:Butyl titanate is dissolved in first and is equipped with In the beaker of ethanol solution, glacial acetic acid solution is then added and carries out preliminary stirring;
Then it adds distilled water to be stirred, and simultaneously controls temperature at 75 DEG C;
It filters after completion of the reaction, then filter residue is placed at 80 DEG C and keeps 32h;Nanometer titanium dioxide titanium valve is made after the completion End.
Preferably, nano titanium dioxide powder is roasted into 3h at 500 DEG C under nitrogen protection in step 2).
Above-mentioned nano-TiO2Preparation described in amorphous zirconium-base alloy composite photocatalyst material or any one among the above Nano-TiO prepared by method2Amorphous zirconium-base alloy composite photocatalyst material is used for the use of photocatalysis degradation organic contaminant On the way.
Preferably, the organic pollution is azo dyes solution.
This application provides a kind of nano-TiOs2Amorphous zirconium-base alloy composite photocatalyst material, by following masses percentage Raw material be made:10%~25% nano titanium dioxide powder, 25%~45% amorphous zirconium-base alloy particle, the two of surplus Silicon oxide powder;The amorphous zirconium-base alloy particle includes the component of following mass percent:10%~30% Cu, 2%~ 5% Ni, 3%~10% Al, the Zr of surplus and inevitable impurity;
The application be combined with each other each autocatalytic characteristics of micron order amorphous zirconium-base alloy and nano-titanium dioxide, in day Under the conditions of light, even in natural environment, the two synergistic effect quickly, efficient process high concentration azo dyes, pass through micron order The combination of amorphous zirconium-base alloy and nano-titanium dioxide plays respective feature and advantage, and the composite photocatalyst material is made to have more Add excellent catalytic performance and the room for promotion of bigger;
Present invention also provides a kind of nano-TiOs based on said components formula2Amorphous zirconium-base alloy composite photocatalyst material The preparation method and its usage of material;
The application has carried out ingredient reinforcing and process strengthening to the catalyst of photocatalysis degradation organic contaminant, and ingredient is strengthened Combined process reinforcing realizes combination among the strong ones, to improve the photocatalysis performance of catalyst, improves catalyst to organic dirt Contaminate the quality and efficiency of the photocatalytic degradation of object.
Description of the drawings
Fig. 1 is the nano-TiO that the embodiment of the present invention provides2Amorphous zirconium-base alloy composite photocatalyst material photocatalysis is dropped The treatment effect figure of solution processing ice color solution.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that feature and advantage that these descriptions only further illustrate the present invention, rather than to the limit of the claims in the present invention System.
This application provides a kind of nano-TiOs2Amorphous zirconium-base alloy composite photocatalyst material, by following masses percentage Raw material be made:10%~25% nano titanium dioxide powder, 25%~45% amorphous zirconium-base alloy particle, the two of surplus Silicon oxide powder;
The amorphous zirconium-base alloy particle includes the component of following mass percent:10%~30% Cu, 2%~5% Ni, 3%~10% Al, the Zr of surplus and inevitable impurity;
The grain size of the amorphous zirconium-base alloy particle is 200 μm~800 μm.
In one embodiment of the application, the grain size of the nano titanium dioxide powder is 10nm~30nm.
Present invention also provides a kind of above-mentioned nano-TiOs2The preparation side of amorphous zirconium-base alloy composite photocatalyst material Method includes the following steps:
1) negated brilliant zirconium-base alloy raw material carries out cutting process under gas shield, and it is 200 μm~800 μm that grain size, which is made, Amorphous zirconium-base alloy particle;
2) nano titanium dioxide powder is prepared, then carries out nano titanium dioxide powder at roasting under nitrogen protection Reason;
3) by amorphous zirconium-base alloy particle made from step 1), the nano titanium dioxide powder and two after step 2) roasting Ball-milling treatment is carried out after silicon oxide powder mixing, nano-TiO is made after the completion2Amorphous zirconium-base alloy composite photocatalyst material.
In one embodiment of the application, nano titanium dioxide powder is prepared using sol-gal process:First by metatitanic acid Four butyl esters are dissolved in the beaker equipped with ethanol solution, and glacial acetic acid solution is then added and carries out preliminary stirring;
Then it adds distilled water to be stirred, and simultaneously controls temperature at 75 DEG C;
It filters after completion of the reaction, then filter residue is placed at 80 DEG C and keeps 32h;Nanometer titanium dioxide titanium valve is made after the completion End.
In one embodiment of the application, by nano titanium dioxide powder under nitrogen protection at 500 DEG C in step 2) Lower roasting 3h.
In one embodiment of the application, the grain size of above-mentioned SiO 2 powder is 10 μm~100 μm.
Above-mentioned nano-TiO2Preparation described in amorphous zirconium-base alloy composite photocatalyst material or any one among the above Nano-TiO prepared by method2Amorphous zirconium-base alloy composite photocatalyst material is used for the use of photocatalysis degradation organic contaminant On the way.
In one embodiment of the application, the organic pollution is azo dyes solution.
For a further understanding of the present invention, with reference to embodiment to a kind of nano-TiO provided by the invention2Amorphous zirconium Based alloy composite photocatalyst material and preparation method thereof is described in detail with purposes, and protection scope of the present invention is not by following reality Apply the limitation of example.
Embodiment 1
A kind of nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material, is made of the raw material of following masses percentage: 25% nano titanium dioxide powder, 45% amorphous zirconium-base alloy particle, the SiO 2 powder of surplus;
The amorphous zirconium-base alloy particle includes the component of following mass percent:20% Cu, 3.5% Ni, 6.5% Al, the Zr of surplus and inevitable impurity;
The grain size of the amorphous zirconium-base alloy particle is 500 μm;
The grain size of the nano titanium dioxide powder is 20nm;
The grain size of above-mentioned SiO 2 powder is 50 μm.
The nano-TiO that the present embodiment 1 provides2Amorphous zirconium-base alloy composite photocatalyst material photocatalytic degradation handles azo The treatment effect of fuel solution is shown in the broken line of 0.7mol/L composite powders and 1.5mol/L composite powders in Fig. 1.
Comparative example 1
Comparative example 1 is not add nano-TiO2The light degradation of the ice color of amorphous zirconium-base alloy composite photocatalyst material Processing, treatment effect are shown in the broken line of the filled square of the top in Fig. 1.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. A variety of modifications for these embodiments are it will be apparent that as defined herein one for those skilled in the art As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein Widest range.

Claims (7)

1. a kind of nano-TiO2Amorphous zirconium-base alloy composite photocatalyst material, which is characterized in that by the original of following masses percentage Material is made:10%~25% nano titanium dioxide powder, 25%~45% amorphous zirconium-base alloy particle, the titanium dioxide of surplus Si powder;
The amorphous zirconium-base alloy particle includes the component of following mass percent:10%~30% Cu, 2%~5% Ni, 3%~10% Al, the Zr of surplus and inevitable impurity;
The grain size of the amorphous zirconium-base alloy particle is 200 μm~800 μm.
2. nano-TiO according to claim 12Amorphous zirconium-base alloy composite photocatalyst material, which is characterized in that described to receive The grain size of rice titania powder is 10nm~30nm.
3. a kind of nano-TiO described in claim 12The preparation method of amorphous zirconium-base alloy composite photocatalyst material, feature It is, includes the following steps:
1) negated brilliant zirconium-base alloy raw material carries out cutting process under gas shield, and the amorphous that grain size is 200 μm~800 μm is made Zirconium-base alloy particle;
2) nano titanium dioxide powder is prepared, nano titanium dioxide powder is then subjected to calcination process under nitrogen protection;
3) by amorphous zirconium-base alloy particle made from step 1), the nano titanium dioxide powder after step 2) roasting and titanium dioxide Ball-milling treatment is carried out after Si powder mixing, nano-TiO is made after the completion2Amorphous zirconium-base alloy composite photocatalyst material.
4. preparation method according to claim 3, which is characterized in that prepare nanometer titanium dioxide titanium valve using sol-gal process End:Butyl titanate is dissolved in the beaker equipped with ethanol solution first, glacial acetic acid solution is then added and is carried out tentatively Stirring;
Then it adds distilled water to be stirred, and simultaneously controls temperature at 75 DEG C;
It filters after completion of the reaction, then filter residue is placed at 80 DEG C and keeps 32h;Nano titanium dioxide powder is made after the completion.
5. preparation method according to claim 3, which is characterized in that by nano titanium dioxide powder in nitrogen in step 2) Under protection 3h is roasted at 500 DEG C.
6. nano-TiO as claimed in claim 1 or 22In amorphous zirconium-base alloy composite photocatalyst material or claim 3~5 The nano-TiO prepared by preparation method described in any one2Amorphous zirconium-base alloy composite photocatalyst material is dropped for photocatalysis Solve the purposes of organic pollution.
7. purposes according to claim 6, which is characterized in that the organic pollution is azo dyes solution.
CN201810524139.4A 2018-05-28 2018-05-28 Nano TiO 2-amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes Pending CN108686662A (en)

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