CN103100398B - Preparation method of natural zeolite loaded one-dimensional TiO2 nanowire with high catalytic activity - Google Patents

Preparation method of natural zeolite loaded one-dimensional TiO2 nanowire with high catalytic activity Download PDF

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CN103100398B
CN103100398B CN201110350957.5A CN201110350957A CN103100398B CN 103100398 B CN103100398 B CN 103100398B CN 201110350957 A CN201110350957 A CN 201110350957A CN 103100398 B CN103100398 B CN 103100398B
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tio
natural zeolite
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zeolite
catalytic activity
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CN103100398A (en
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鄂磊
刘志锋
雅菁
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Tianjin Chengjian University
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Abstract

The invention belongs to the technical field of photocatalysis, and in particular to a preparation method of natural zeolite loaded one-dimensional TiO2 nanowire with high catalytic activity and related technological parameters. The preparation method is a sol-gel / hydrothermal synthesis method and comprises steps of: first preparing a TiO2 sol from a precursor butyl titanate (Ti (OC4H9) 4), a complexing agent diethanol amine and a solvent absolute ethyl ethanol; then, loading the TiO2 sol on acid treated natural zeolite by an immersion method, drying and calcining; and finally, placing the zeolite loaded with TiO2 in a NaOH aqueous solution, and conducting a hydrothermal reaction at a certain temperature; washing the obtained product with deionized water, and dipping the product in a dilute HCl solution for a while; and then washing, drying and calcining the obtained product to obtain a natural zeolite loaded one-dimensional nano TiO2 composite material. The invention also discusses influence of technological parameters including sol precursor concentration, TiO2 loading amount and calcination time on the structure and properties of the composite material, and acquires the optimum technological parameters for preparation of the natural zeolite loaded one-dimensional TiO2 nanowire with high catalytic activity.

Description

One prepares high catalytic activity natural zeolite load one dimension TiO 2the method of nano wire
Technical field
The invention belongs to photocatalysis technology field, be specially one and prepare high catalytic activity natural zeolite load one dimension TiO 2the method of nanowire composite and related process parameters.
Technical background
Water is lifespring, is the necessary condition that life exists.Human lives, industrial production, agricultural irrigation etc. all be unable to do without water.Along with developing rapidly of modern economy, many mankind's activities make a large amount of industry, agricultural and domestic refuse enter in water, and water body is polluted.The pollution of water resource not only worsens whole earth ecology, returns human health and constitutes huge harm.Therefore, water pollution control is subject to the attention of global range as the important topic of field of Environment Protection.And the main method of existing solution water pollutions, as: biological degradation method, active carbon adsorption, filtration, chemical oxidization method etc. can not fundamentally make pollutant innoxious.Just because of this, the research of people to the method for novel pollution administration is facilitated.
TiO has been found from Fujishima and Houda in 1972 2since electrode can carry out the discovery of light decomposition water, TiO 2catalysis material is the focus of many scholar's research always.Nano-TiO 2because surperficial photohole has very strong oxidability, energy is degradation of organic substances thoroughly, and there is the advantages such as chemical stability is good, specific area is large, nontoxic, photocatalytic activity is high, applicable pollutant is wide, cheap and easy to get and extremely people's concern, be widely used in the improvement of polluting, particularly as photocatalyst for degrading trade effluent, under the irradiation of ultraviolet light, the organic matter in sewage in the short time, can be made thoroughly to be converted into CO 2, H 2o and other organic matter.
Nano-TiO 2the application of photochemical catalyst mainly contains two kinds of forms: floating type and support type.But common suspended phase photocatalytic method also exists catalyst easy in inactivation, reclaims the shortcomings such as difficult, expense is high, and supported titanium 2catalyst is easily separated, be convenient to reclaim, can repeat to be suitable for, and is one of focus of current semiconductor field of photocatalytic material research.Loaded nano TiO 2the carrier that photochemical catalyst is conventional has: clay, glass fibre, SiO 2, activated carbon, zeolite etc.
Although load TiO 2carrier numerous, but experiment show most of loaded nano TiO 2the simple nano-TiO of specific activity of photochemical catalyst 2particle has reduction in various degree.Zeolite is a kind of moisture rack-like structure, porous aluminosilicate mineral, there is larger specific area, strong ion-exchange capacity and absorption property, can form semiconductor nanoclusters that is stable, molecular dimension in its structure, thus zeolite-loaded type photochemical catalyst demonstrates the work higher than other carrier.And natural zeolite abundant raw material source, cheap, having the ion-exchange absorption performance not second to synthetic zeolite, is the very promising carrier of photocatalyst of one.
The subject matter of current existence is: at traditional zeolite-loaded TiO 2in nano particle photocatalysis system, organic degraded is mainly come to suction-operated and the TiO of zeolite 2photocatalysis, and zeolite surface load TiO 2after nano particle, the specific area of compound often reduces, and is unfavorable for organic absorption and degraded.And research shows, one-dimensional nano line (pipe) material specific surface area high and be easy to electron hole be separated, demonstrate good development prospect in photocatalysis field.In order to improve zeolite-loaded TiO further 2the photocatalytic activity of nano composite material, the present invention prepares natural zeolite load one dimension TiO to adopt collosol and gel/hydrothermal synthesis method 2nanowire composite, makes full use of absorption property and the TiO of natural zeolite 2the specific area that nano wire is high and photocatalytic activity, improve the catalytic performance of composite, and solve Conventional nano TiO 2photochemical catalyst reclaims the problems such as difficult.
Summary of the invention
The object of the invention is to propose a kind of high catalytic activity natural zeolite load one dimension TiO 2the preparation method of nanowire composite and related process parameters.
One is applicable to preparing natural zeolite load one dimension TiO 2the method of nanowire composite.This preparation method is collosol and gel/hydrothermal synthesis method.First, with butyl titanate (Ti (OC 4h 9) 4) be presoma, diethanol amine is complexing agent, and absolute ethyl alcohol is solvent, preparation TiO 2colloidal sol; Then, infusion process is adopted, at load TiO on acid-treated natural zeolite 2colloidal sol, dry, calcining; Finally, by load TiO 2zeolite place in the NaOH aqueous solution, carry out hydro-thermal reaction at a certain temperature; Products therefrom spends deionized water and is placed in rare HCl solution and floods certain hour; Again products therefrom washed, dry, calcine, natural zeolite load 1-dimention nano TiO can be obtained 2composite.
The mechanism of action of the present invention is: by sol gel process at zeolite surface load TiO 2; Then utilize hydro-thermal reaction, make TiO 2with high concentration NaOH effect, generate sodium titanate; Again by zeolite/sodium titanate compound and rare HCl effect, displacement sodium ion; Finally, products therefrom is fully washed, dry, calcine, natural zeolite load one dimension TiO can be obtained 2nanowire composite.Natural zeolite load one dimension TiO 2nanowire composite, can make full use of absorption property and the TiO of natural zeolite 2the specific area that nano wire is high and photocatalysis performance, and solve Conventional nano TiO 2photochemical catalyst reclaims the problems such as difficult.
The present invention also proposes the related process parameters of above-mentioned preparation method, specific as follows:
TiO 2in colloidal sol configuration, the concentration of butyl titanate is 0.5 ~ 0.7 ± 0.02mol/L, and the mol ratio of diethanol amine and butyl titanate is 1: 1.In the acid treatment of natural zeolite, the concentration of HCl is 0.3mol/L, and bath temperature is 93 DEG C ± 2 DEG C, and mixing time is 4h, and product is dry 12h at 110 DEG C ± 5 DEG C, then 550 ± 5 DEG C of calcinings 4 hours.Natural zeolite loaded with nano TiO 2preparation in, zeolite puts into TiO 2in colloidal sol, stirring in water bath at 70 DEG C ± 5 DEG C, by load TiO 2zeolite dry 12h at 90 DEG C ± 5 DEG C, repeat aforesaid operations load TiO again 2, by load 2 TiO 2zeolite 500 DEG C ± 5 DEG C heat treatments 2 hours.At natural zeolite load one dimension TiO 2in the preparation of nanowire composite, by zeolite-loaded nano-TiO 2be scattered in the NaOH aqueous solution of 10mol/L ± 0.2mol/L, hydro-thermal reaction 4h at 180 DEG C ± 5 DEG C, by products therefrom deionized water centrifuge washing 5 times, the rare HCl solution being placed in 0.1mol/L ± 0.02mol/L floods 8h, excessive HCl is washed away afterwards by deionized water, use absolute ethanol washing again 5 times, products therefrom is dried at 60 DEG C ± 5 DEG C, then 500 DEG C ± 5 DEG C heat treatments 3 hours.
Feature of the present invention:
1, absorption property and the TiO of natural zeolite is made full use of 2the specific area that nano wire is high and photocatalysis performance, improve the catalytic activity of composite, and solve Conventional nano TiO 2photochemical catalyst reclaims the problems such as difficult.
2, collosol and gel/hydro-thermal synthesis process process is comparatively simple, is easy to realize, and is convenient to control.
3, load TiO 2colloidal sol is easy to control, and composite photocatalytic activity is high.
4, natural zeolite load one dimension TiO can be obtained 2nanowire composite (nanowire diameter scope: 100nm ± 50nm's), improves its photocatalytic activity.
The using method of this preparation technology is as follows:
1, typical TiO 2technological parameter prepared by colloidal sol: the concentration of butyl titanate is 0.6mol/L, the mol ratio of diethanol amine and butyl titanate is 1: 1, and the ratio of water and absolute ethyl alcohol is 1: 10, and anhydrous ethanol solvent is 50ml.
2, the technological parameter of the acid treatment technology of typical natural zeolite: concentration of hydrochloric acid is 0.3mol/L, bath temperature 93 DEG C, mixing time 4h, baking temperature and time are 110 DEG C/12h, and final calcining heat is 550 DEG C/4h.
3, typical natural zeolite loaded with nano TiO 2technological parameter: bath temperature 70 DEG C, baking temperature and time are 90 DEG C/12h, and final calcining heat is 500 DEG C/2h.
4, typical natural zeolite load one dimension TiO 2the technological parameter of nanowire composite: NaOH concentration is 10mol/L, hydrothermal temperature 180 DEG C, time 4h, watery hydrochloric acid concentration is 0.1mol/L, and dip time is 8h, and baking temperature is 60 DEG C, and final calcining heat is 500 DEG C/3h.
5, wherein TiO 2process parameters range prepared by colloidal sol: butyl titanate (Ti (OC 4h 9) 4) concentration be 0.5 ~ 0.7 ± 0.02mol/L, the mol ratio of diethanol amine and butyl titanate is 1: 1, and the ratio of water and absolute ethyl alcohol is 1: 10.
6, the process parameters range of the wherein acid treatment technology of natural zeolite: bath temperature 93 DEG C ± 2 DEG C, mixing time 4h, baking temperature and time are 110 DEG C ± 5 DEG C/12h, and final calcining heat is 550 DEG C ± 5 DEG C/4h.。
7, wherein natural zeolite loaded with nano TiO 2process parameters range: bath temperature 70 DEG C ± 5 DEG C, baking temperature and time are 90 DEG C ± 5 DEG C/12h, and final calcining heat is 500 DEG C ± 5 DEG C/2h.
8, wherein natural zeolite load one dimension TiO 2the process parameters range of nanowire composite: NaOH concentration is 10mol/L ± 0.2mol/L, hydrothermal temperature 180 DEG C ± 5 DEG C, time 4h, watery hydrochloric acid concentration is 0.1mol/L ± 0.02mol/L, dip time is 8h, baking temperature is 60 DEG C ± 5 DEG C, and final calcining heat is 500 DEG C ± 5 DEG C/3h.
Detailed description of the invention
The invention is further illustrated by the following examples.
Embodiment
TiO 2the preparation of colloidal sol, the concentration of butyl titanate is 0.6, and the mol ratio of diethanol amine and butyl titanate is 1: 1, and the ratio of water and absolute ethyl alcohol is 1: 10, and anhydrous ethanol solvent is 50ml.The acid treatment of natural zeolite, by deionized water by natural zeolite cyclic washing, till upper liquid is limpid, clean zeolite is added in the hydrochloric acid of 0.3mol/L, under 93 DEG C of water bath condition, stir 4h, wash to remove Cl to through acid-treated zeolite by deionized water -, by gains dry 12h at 110 DEG C, then 550 calcining 4 hours.Natural zeolite loaded with nano TiO 2preparation, puts into TiO by acid-treated zeolite 2in colloidal sol, stirring in water bath at 70 DEG C, to TiO 2till colloidal sol becomes gel, by load TiO 2zeolite dry 12h at 90 DEG C, repeat aforesaid operations load TiO again 2, by load 2 TiO 2zeolite 500 DEG C of heat treatments 2 hours.Natural zeolite load one dimension TiO 2prepared by nanowire composite, by zeolite-loaded nano-TiO 2be scattered in the NaOH aqueous solution of 10mol/L, hydro-thermal reaction 4h at 180 DEG C, by products therefrom deionized water centrifuge washing 5 times, the rare HCl solution being placed in 0.1mol/L floods 8h, excessive HCl is washed away afterwards by deionized water, use absolute ethanol washing again 5 times, products therefrom is dried at 60 DEG C, then 500 DEG C of heat treatments 3 hours.
Prepare by preceding method.
Catalytic activity can be obtained higher than zeolite, TiO 2nano powder, zeolite/TiO 2the natural zeolite load one dimension TiO of nano particle 2nanowire composite, wherein TiO 2nanowire diameter scope is 100nm ± 50nm.

Claims (6)

1. one kind is applicable to preparing high catalytic activity natural zeolite load one dimension TiO 2the method of nanowire composite, the method is collosol and gel/hydrothermal synthesis method, first, with butyl titanate (Ti (OC 4h 9) 4) be presoma, diethanol amine is complexing agent, and absolute ethyl alcohol is solvent, preparation TiO 2colloidal sol; Then, infusion process is adopted, at load TiO on acid-treated natural zeolite 2colloidal sol, dry, calcining; Finally, by load TiO 2zeolite place in 10mol/L ± 0.2mol/LNaOH aqueous solution, at 180 DEG C ± 5 DEG C temperature, carry out hydro-thermal reaction; Products therefrom spends deionized water and is placed in rare HCl solution and floods certain hour; Again products therefrom washed, dry, calcine, natural zeolite load one dimension TiO can be obtained 2nanowire composite.
2. prepare high catalytic activity natural zeolite load one dimension TiO with according to claim 1 being applicable to for one kind 2the method of nanowire composite, is characterized in that TiO 2the preparation detailed process of colloidal sol and technological parameter as follows: join in ethanol solution by butyl titanate, diethanol amine, normal temperature lower magnetic force stirs 2 hours, then adds a small amount of water and absolute ethyl alcohol mixture, continues stirring 2 hours, obtains TiO 2colloidal sol; The concentration of butyl titanate is 0.5 ~ 0.7 ± 0.02mol/L, and the mol ratio of diethanol amine and butyl titanate is 1: 1.
3. prepare high catalytic activity natural zeolite load one dimension TiO with according to claim 1 being applicable to for one kind 2the method of nanowire composite, it is characterized in that the acid treatment technology detailed process of natural zeolite and related process parameters as follows: first, by deionized water by natural zeolite cyclic washing, till upper liquid is limpid; Then, clean zeolite is added in the hydrochloric acid of 0.3mol/L, under 93 DEG C ± 2 DEG C water bath condition, stir 4h; Finally, wash to remove Cl to through acid-treated zeolite by deionized water -, by gains dry 12h at 110 DEG C ± 5 DEG C, then 550 ± 5 DEG C of calcinings 4 hours.
4. prepare high catalytic activity natural zeolite load one dimension TiO with according to claim 1 being applicable to for one kind 2the method of nanowire composite, it is characterized in that detailed process and related process parameters as follows: first, acid-treated zeolite is put into TiO 2in colloidal sol, stirring in water bath at 70 DEG C ± 5 DEG C, to TiO 2till colloidal sol becomes gel, by load TiO 2zeolite dry 12h at 90 DEG C ± 5 DEG C; Then, aforesaid operations load TiO is again repeated 2; Finally, by load 2 TiO 2zeolite 500 DEG C ± 5 DEG C heat treatments 2 hours.
5. prepare high catalytic activity natural zeolite load one dimension TiO with according to claim 1 being applicable to for one kind 2the method of nanowire composite, it is characterized in that detailed process and related process parameters as follows: first, by zeolite-loaded nano-TiO 2be scattered in the NaOH aqueous solution of 10mol/L ± 0.2mol/L, hydro-thermal reaction 4h at 180 DEG C ± 5 DEG C; Then, by products therefrom deionized water centrifuge washing 5 times, the rare HCl solution being placed in 0.1mol/L ± 0.02mol/L floods 8h, and rear deionized water washes away excessive HCl, then uses absolute ethanol washing 5 times; Finally, products therefrom is dried at 60 DEG C ± 5 DEG C, then 500 DEG C ± 5 DEG C heat treatments 3 hours, obtain the one dimension TiO of natural zeolite load diameter at 100nm ± 50nm of high catalytic activity 2nanowire composite.
6. prepare high catalytic activity natural zeolite load one dimension TiO with according to claim 1 being applicable to for one kind 2the method of nanowire composite, is characterized in that TiO 2be wrapped in carrier surface, form firmly TiO 2layer, then change TiO by hydrothermal treatment consists 2pattern, forms carrier loaded one dimension TiO 2nanowire composite.
CN201110350957.5A 2011-11-09 2011-11-09 Preparation method of natural zeolite loaded one-dimensional TiO2 nanowire with high catalytic activity Expired - Fee Related CN103100398B (en)

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