CN102367180A - Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source - Google Patents

Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source Download PDF

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CN102367180A
CN102367180A CN2011100638682A CN201110063868A CN102367180A CN 102367180 A CN102367180 A CN 102367180A CN 2011100638682 A CN2011100638682 A CN 2011100638682A CN 201110063868 A CN201110063868 A CN 201110063868A CN 102367180 A CN102367180 A CN 102367180A
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titanium source
order
preparing
nano tio
tio
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CN102367180B (en
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赵伟
齐涛
秦鸣
王丽娜
初景龙
曲景奎
黎少华
薛天艳
余志辉
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Institute of Process Engineering of CAS
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Abstract

The invention discloses a method for preparing a high-pore order degree nano mesoporous TiO2 material with a uniform spherical structure by using titanium liquid/metatitanic acid on an industrial titanium white production line as a titanium source and a common and low-priced mixed surfactant as a structure guide agent in a warm hydrothermal system, wherein the high-pore order degree nano mesoporous TiO2 material is formed by secondary accumulation of primary nano particles. The high-pore order degree nano mesoporous TiO2 material and derivatives thereof doped/loaded with other active components have better application property on the aspects of absorption separation, catalysis and the like. Meanwhile, the high-pore order degree nano mesoporous TiO2 material has a wide application prospect in the fields of solar cells, nano reactors and the like. The method has the advantages of simpleness in operation, low cost and high activity.

Description

A kind of mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source 2Method
One, technical field
The present invention is the titanium source with the titanium liquid/metatitanic acid on the commercial titanium white powder production line; With conventional, cheap tensio-active agent (comprising anionic, cationic, non-ionic type etc.) is structure directing agent; In gentle hydrothermal system, prepared by elementary nanoparticle secondary and piled up the mesoporous TiO that forms with homogeneous globosity 2Material.Other active ingredient verivate of this material and doping/load thereof has shown the good applicability ability at aspects such as polycomponent ion purifying, removal of impurities, photochemical catalysis.Simultaneously, also have broad application prospects in fields such as solar cell, nano-reactors.
Two, background technology
Since the early seventies in last century, Japanese scientist Fujishima finds TiO 2But monocrystalline electrode brine electrolysis has produced since the hydrogen, TiO 2Material obtains broad research at aspects such as photochemical catalysis, environmental purification, hydrogen production by water decomposition.The wherein successful commercialization of P25.Because conventional TiO 2The material specific surface area is low, reaction interface and active sites are less, and therefore, people actively utilize and compound (as: the perovskite typed CeCo of other oxide compound xTi 1-xO 3+ δ, In 12NiCr 2Ti 10O 42Deng), methods such as ion doping (as: N-F mixes, Ce-N mixes etc.), dye photoactivation improve its catalytic activity.In recent years, along with TiO 2Material is constantly used in fields such as fractionation by adsorption, support of the catalyst, to percent crystallinity height, good stability, TiO that specific surface area is big 2Materials demand is increasing, thereby some synthesising mesoporous TiO have been arranged 2The research report of material, as: Antonelli, Rossmanith etc. are precursor with chemical pure organic titanium source, utilize some unconventional phosphoric acid salt/segmented copolymer class tensio-active agent to synthesize the TiO with meso-hole structure for structure directing agent 2, but the mesoporous TiO of gained 2Thermally-stabilised relatively poor (instability in the time of 500 ℃) and chemically reactive are lower, and preparation cost is also higher; The landlocked little magnificent seminar of state sets out with the two steady potassium titanates that are situated between, and utilizes the method for IX successfully to obtain all TiO preferably of stability and chemically reactive 2(B) mesoporous titania meterial, but this material does not have the characteristic diffraction peak of ordered meso-porous structure at the little angular zone of powder X-ray diffraction (XRD), shows that its meso-hole structure is the chaotic distribution state, or the like.And, make mesoporous TiO 2Material really obtains large-scale application in fields such as separation, support of the catalyst, and precondition must be the mesoporous TiO that can prepare high stability, the high duct degree of order with cheap, easy, repeatable method 2Material.
Three, summary of the invention
The present invention is directed to existing mesoporous TiO 2The deficiency that material exists when practical application has been researched and developed a kind of cheapness, the repeatable high high duct of preparation degree of order mesoporous nano TiO 2The method of the material and the dirt product that spreads out thereof.
The synthesis step of material is following: under the room temperature, tensio-active agent is dissolved in deionized water for stirring mixes, under agitation slowly add commercial titanium source solution again; Continue to stir into uniform mixture (if the verivate of preparation hole wall doping active ingredient at this moment, can add the active specy precursor together); This mixed solution is moved in reaction kettle, under 80-150 ℃ of temperature crystallization 1-4 days, take out the back suction filtration; Washing, drying obtains the former powder of synthesis type; With the direct roasting 1-4h between 350-600 ℃ in air of the former powder of synthesis type, obtain piling up the mesoporous TiO of the high duct degree of order that forms with homogeneous globosity by elementary nanoparticle secondary 2Sample.Through pickling process active specy precursor (as: ammonium meta-vanadate/iron nitrate/Xiao Suangu etc.) is loaded on this sample, roasting 2-3h carries out activation treatment between 400-600 ℃.
Material ratio and reaction conditions in above-mentioned synthesizing are:
(1) concentration of titanium precursor thing is 1-5wt%;
(2) mol ratio of tensio-active agent and titanium precursor material is: 0.25～0.8
(3) mol ratio between the mixed surfactant is 12～2
(4) the direct roasting 1-4h between 350-600 ℃ in air of the former powder of synthesis type
Titanium precursor thing and active ingredient precursor mol ratio are when (5) preparing hole wall doping active ingredient verivate: 200～20
(6) load the mesoporous nano TiO of active specy precursor 2Roasting 1-4h carries out activation treatment between 400-600 ℃
Synthesis condition of the present invention is better in following ranges:
(1) concentration of titanium precursor thing is 2-4wt%
(2) mol ratio of tensio-active agent and titanium precursor material is: 0.3～0.5; Mol ratio between the mixed surfactant is 7～2
(3) the direct roasting 2-3h between 400-550 ℃ in air of the former powder of synthesis type
Titanium precursor thing and active ingredient precursor mol ratio are when (4) preparing hole wall doping active ingredient verivate: 100～50
(5) load the mesoporous nano TiO of active specy precursor 2Roasting 2-3h carries out activation treatment between 450-550 ℃
The characterization result of sample shows: no matter be as the titanium source with the titanium liquid on the industrial production line or metatitanic acid; At the little angular zone of sample X-ray diffractogram (XRD); The characteristic diffraction peak of order mesoporous structure has all appearred in sample before and after roasting, show that sample is the mesoporous TiO of the high duct degree of order 2Material, but not the TiO in unordered accumulation hole 2Material.The nitrogen absorption result of sample has further confirmed this point, and the most probable pore distribution curve of two samples is all very narrow, is much better than existing mesoporous TiO 2The characterization result of material.The sem photograph of sample (SEM) shows that when being the titanium source with the metatitanic acid, the gained sample is the spheroidal particle of tens nanometers, and the reunion that has together.And when being the titanium source with titanium liquid, the gained sample is for being piled up the particle with homogeneous globosity that forms by elementary nanoparticle secondary.
Four, description of drawings
Fig. 1 is the mesoporous TiO of gained when being the titanium source with the industrial metatitanic acid 2The characteristic X-ray diffractogram (XRD) of material.
Fig. 2 is the mesoporous TiO of gained when being the titanium source with the industrial metatitanic acid 2The nitrogen absorption result of material.
Fig. 3 is the mesoporous TiO of gained when being the titanium source with the industrial metatitanic acid 2The sem photograph of material (SEM).
Fig. 4 is the mesoporous TiO of gained when being the titanium source with commercial titanium liquid 2The characteristic X-ray diffractogram (XRD) of material.
Fig. 5 is the mesoporous TiO of gained when being the titanium source with commercial titanium liquid 2The nitrogen absorption result of material.
Fig. 6 is the mesoporous TiO of gained when being the titanium source with commercial titanium liquid 2The sem photograph of material (SEM).
Five, embodiment
Further describe characteristic of the present invention through instance below.
Instance 1:
With obtaining the metatitanic acid acid solution in a certain amount of metatitanic acid vitriolization solution.Under the room temperature, CTAB and dodecyl carboxylic acid sodium are dissolved in deionized water for stirring mix, under agitation add the metatitanic acid acid solution again; Continue to stir into uniform mixture, this mixed solution is moved in the reaction kettle, crystallization is 2 days in 120 ℃ of baking ovens; Take out the back suction filtration, deionized water wash, 70 ℃ of dryings; Obtain the former powder of synthesis type, the former powder of synthesis type directly behind 500 ℃ of roasting 2h, is promptly obtained the mesoporous TiO of spheroidal particle in air 2Sample.Typical X RD spectrogram, nitrogen absorption result, SEM picture are seen Fig. 1～Fig. 3 respectively.
Instance 2:
With instance 1, the metatitanic acid acid solution is changed to titanium liquid on the production line as the titanium source, also can obtain piling up the mesoporous TiO that forms with homogeneous globosity by elementary nanoparticle secondary 2Sample.Typical X RD spectrogram, nitrogen absorption result, SEM picture are seen Fig. 4～Fig. 6 respectively.
Instance 3:
With instance 1, when being the titanium source, when the blending surface reactive systems is changed to dodecyl carboxylic acid sodium and polyoxyethylene octyl phenyl ether, also can obtain having the mesoporous TiO of the high duct degree of order with the metatitanic acid acid solution 2Material.
Instance 4:
With instance 2; With the titanium liquid on the production line during as the titanium source; When titanium liquid is added CTAB and dodecyl carboxylic acid sodium mixing solutions, add ammonium meta-vanadate or cerous nitrate, the vanadium or the adulterated mesoporous TiO of cerium that can obtain having the high duct degree of order respectively 2Sample.

Claims (8)

1. mesoporous nano TiO who prepares the high duct degree of order with cheap commercial titanium source 2Method, it is characterized in that with the titanium liquid/metatitanic acid on the commercial titanium white powder production line be the titanium source, the mesoporous TiO under gentle hydrothermal condition 2The preparation of other active ingredient verivate of molecular sieve and doping/load thereof is with conventional, cheap single cats product (as: CTAB is called for short CTAB etc.), AS (as: dodecyl carboxylic acid sodium; Be called for short SL etc.) and nonionogenic tenside (as: polyoxyethylene octyl phenyl ether is called for short OP-10 etc.) or to mix the multivariate table surface-active agent be structure directing agent, at room temperature; Tensio-active agent is dissolved in deionized water for stirring mixes, under agitation add commercial titanium source solution again, continue to stir into uniform mixture; This mixed solution is moved in the reaction kettle; Under 80-150 ℃ of temperature crystallization 1-4 days, take out the back suction filtration, washing; Dry; Obtain the former powder of synthesis type,, obtain piling up the mesoporous TiO of the high duct degree of order that forms with homogeneous globosity by elementary nanoparticle secondary with the direct roasting 1-4h between 350-600 ℃ in air of the former powder of synthesis type 2Sample.Through one-step synthesis or pickling process, other active ingredient to be mixed/loaded on this sample, activated processing promptly obtains the derived product of its difference in functionality,
Various materials when reaction conditions are following:
(1) concentration of titanium precursor thing is 1-5wt%;
(2) the reaction mass mol ratio is:
1.0TiO 2: x (CTAB/SL): y (SL/CTAB/OP-10): zH 2SO 4: 220H 2O, wherein 0.24＜x＜0.8,0＜y＜0.12,2＜z＜12;
(3) mol ratio of x and y is ∞～2.
2. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, the mol ratio that it is characterized in that x and y is 8/1～3/1.
3. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, it is characterized in that the value of x and z is respectively 0.3～0.6 and 5～10.
4. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, the concentration that it is characterized in that the titanium precursor thing is 2-4wt%.
5. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, it is characterized in that mixed solution crystallization temperature in reaction kettle is 100-130 ℃.
6. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, it is characterized in that directly roasting 2-3h between 400-550 ℃ in air of the former powder of synthesis type.
7. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, when it is characterized in that the titanium source added surfactant soln, add ammonium meta-vanadate/cerous nitrate/sodium wolframate isoreactivity species precursor, through the verivate of its hole wall doping active ingredient of single stage method preparation.
8. according to the said mesoporous nano TiO for preparing the high duct degree of order with cheap commercial titanium source of claim 1 2Method, it is characterized in that ammonium meta-vanadate/iron nitrate/Xiao Suangu isoreactivity species precursor is loaded on mesoporous nano TiO through pickling process 2Sample on, and roasting 2-3h carries out activation treatment between 400-600 ℃.
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CN102872854A (en) * 2012-09-29 2013-01-16 南京工业大学 Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof
CN103771509A (en) * 2014-01-23 2014-05-07 齐鲁工业大学 Method for preparing uniform spherical mesoporous titanium dioxide
CN106955728A (en) * 2017-03-27 2017-07-18 浙江巨能环境工程设备有限公司 A kind of preparation method of high efficiency load type ozone oxidation catalyst and application
CN114011393A (en) * 2021-10-27 2022-02-08 安徽元琛环保科技股份有限公司 Mesoporous TiO2Preparation method of supported efficient denitration catalyst and prepared denitration catalyst

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CN101433835A (en) * 2008-12-05 2009-05-20 浙江师范大学 Mesoporous TiO2 supported V2O5 catalyst with high specific surface area as well as preparation method and use thereof
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CN101070184A (en) * 2006-05-12 2007-11-14 中国科学院理化技术研究所 Preparation method of monodisperse spherical mesoporous titanium dioxide colloid particles with controllable size and morphology
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102872854A (en) * 2012-09-29 2013-01-16 南京工业大学 Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof
CN103771509A (en) * 2014-01-23 2014-05-07 齐鲁工业大学 Method for preparing uniform spherical mesoporous titanium dioxide
CN103771509B (en) * 2014-01-23 2015-01-14 齐鲁工业大学 Method for preparing uniform spherical mesoporous titanium dioxide
CN106955728A (en) * 2017-03-27 2017-07-18 浙江巨能环境工程设备有限公司 A kind of preparation method of high efficiency load type ozone oxidation catalyst and application
CN106955728B (en) * 2017-03-27 2020-05-12 浙江巨能环境工程有限公司 Preparation method and application of efficient supported ozone oxidation catalyst
CN114011393A (en) * 2021-10-27 2022-02-08 安徽元琛环保科技股份有限公司 Mesoporous TiO2Preparation method of supported efficient denitration catalyst and prepared denitration catalyst

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