CN103203253A - Method for synthesizing polyoxometalates/titanium dioxide catalyst - Google Patents
Method for synthesizing polyoxometalates/titanium dioxide catalyst Download PDFInfo
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- CN103203253A CN103203253A CN2013101193098A CN201310119309A CN103203253A CN 103203253 A CN103203253 A CN 103203253A CN 2013101193098 A CN2013101193098 A CN 2013101193098A CN 201310119309 A CN201310119309 A CN 201310119309A CN 103203253 A CN103203253 A CN 103203253A
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- titanium dioxide
- heteropolyacid salt
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- polyoxometalates
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Abstract
The invention belongs to the technical field of catalysts, and in particular designs a method for synthesizing a covalent bonding polyoxometalates/mesoporous titanium dioxide catalyst in one step. The method is characterized in that polyoxometalates is directly introduced in a titanium dioxide photocatalyst synthesizing process through a sol-gel method so as to prepare a polyoxometalates/titanium dioxide photocatalyst. By utilizing the method, a pore blockage problem caused by synthesizing polyoxometalates/titanium dioxide through a double-grafting method is avoided, and a problem that polyoxometalates has falling off and losing in a photocatalysis process is solved; and moreover, the method is simple in operation step and short in reaction period, and the prepared photocatalyst has a high photocatalysis effect and can be recycled for a plurality of times.
Description
Technical field
The present invention relates to chemical technology field, be specifically related to the preparation of photochemical catalyst, more specifically relate to a kind of synthetic method of heteropolyacid salt/titanium dioxide optical catalyst.
Background technology
At present, China's water pollution situation especially severe, one of approach is exactly to carry out photocatalytic oxidation degradation.Titanium dioxide and heteropolyacid salt are the green light catalyst of two kinds of extensive uses.But because heteropolyacid salt is very easily soluble in water, brought difficulty for the separation recovery of catalyst, and the recombination rate height of titanium dioxide photoproduction carrier.Therefore the two is combined and not only can avoid both defectives, can also obtain higher photocatalysis efficiency.Bibliographical information is arranged, and mesoporous TiO 2 ratio nano titanium dioxide has higher photocatalytic activity, so mesoporous TiO 2 will be the carrier of a good carried heteropoly acid salt.
The researchers of the overwhelming majority adopt the secondary grafting method to synthesize heteropolyacid salt/titanium dioxide optical catalyst, i.e. synthesis of titanium dioxide at first, then the reaction by heteropolyacid salt and titanium dioxide surface with its grafting to titanium dioxide.But this method causes the titanium dioxide duct to stop up easily, is unfavorable for introducing dye molecule in photocatalytic process, thereby influences its photocatalytic applications.
People such as Guo Yi Xing adopt one-step method to synthesize heteropolyacid salt/titanium dioxide optical catalyst, heteropolyacid salt is wrapped up in the titanium dioxide network, do not have the duct blocking problem, but be to be connected by acid-base function between the two, loss easily comes off in catalytic action.If can will well address this problem with the heteropolyacid salt covalent bond in titanium dioxide.
So far heteropolyacid salt/titanium dioxide optical catalyst the mesoporous material of the synthetic covalent bond of one-step method does not appear in the newspapers yet.
Summary of the invention
The present invention is directed to the synthetic weak point that exists of existing middle heteropolyacid salt/titanium dioxide optical catalyst, the method of the heteropolyacid salt/mesopore titania photocatalyst of the synthetic covalent bond of a kind of one-step method is provided, the present invention directly introduces heteropolyacid salt in the process of sol-gel process synthesis of titanium dioxide photochemical catalyst, preparation heteropolyacid salt/titanium dioxide optical catalyst; The plug-hole problem that this invention has avoided the synthetic heteropolyacid salt/titanium dioxide of secondary grafting method to cause, solved the problem that heteropolyacid salt comes off easily and runs off in photocatalytic process, and simple operating steps, reaction time is short, the photochemical catalyst photocatalysis effect height of preparation can repeatedly be recycled.
Concrete technical scheme of the present invention is: its concrete steps are as follows:
(1) template agent P123 is dissolved in the nitrile solvent stirred overnight at room temperature;
(2) add titanium source and heteropolyacid salt TBAPW in the nitrile solvent in the step (1)
11, stirring reaction 1-3h obtains titanium colloidal sol:
(3) with step (2) gained titanium colloidal sol solvent flashing in 30-50 ℃ of baking oven, the volatilization time is 8-16h, and baking oven is warming up to 100 ℃ of aging 4-6h and obtains xerogel then;
(4) collect xerogel, the not heteropolyacid salt of binding is removed in supersound washing, then at 300-500 ℃ of following roasting 4h removed template method, and the titanium dioxide optical catalyst of heteropolyacid salt that namely obtained binding;
Wherein said template agent: the mass ratio of solvent is 1:10-1:16; The titanium source: the mass ratio of heteropolyacid salt is 1:0.01-1:0.03; The template agent: the mass ratio in titanium source is 1:4.
Described nitrile solvent is acetonitrile or butyronitrile; One or both in titanium tetrachloride, titanyl sulfate or the isopropyl titanate are selected in described titanium source for use.
Related heteropolyacid salt TBAPW among the present invention
11Full name is (Bu
4N)
7PW
11O
39Preparation process can list of references " A dimeric titanium-containing polyoxometalate synthesis, characterization, and catalysis of H2O2-based thioether oxidation " and " Tungsten-183NMR:A Complete and Unequivocal Assignment of the Tungsten-Tungsten Connectivities in Heteropolytungstates via Two-Dimensional 183W NMR Techniques ".
The general alcohol that adopts is as solvent in the building-up process of titanium dioxide in the routine techniques, and still because heteropolyacid salt is insoluble to alcohol, this has just limited in a synthetic method and has introduced heteropolyacid salt.Therefore the nitrile of using instead of the invention is made solvent, makes reaction solution form homogeneous system.
The use of alcoholic solvent in the prior art, some are insoluble to the introducing of the modification species of alcohol in synthetic to have limited titanium dioxide, and the present invention is in order directly to introduce heteropolyacid salt in the building-up process of mesoporous TiO 2, directly synthesize heteropolyacid salt/titanium dioxide mesoporous material, the inventor has selected the Na that dissolves in acetonitrile solvent for use
7PW
11O
394-butyl ammonium (Bu
4N)
7PW
11O
39, as presoma, obtain heteropolyacid salt, and be introduced in the titanium dioxide.
The present invention selects for use has very strong coordination and reactivity, and is dissolved in the TBAPW of nitrile
11As the presoma of heteropolyacid salt, with the reaction of the presoma titanium source of titanium dioxide, its principle be exactly vacant Keggin structure heteropolyacid salt can with contain titanium species reaction, the room of titanium atom being inserted the heteropolyacid salt of omission type.Adopt the presoma titanium reaction of heteropolyacid salt presoma of the present invention and titanium dioxide, thereby with the room that titanium atom inserts heteropolyacid salt, make heteropolyacid salt and titanium dioxide directly pass through covalent bond phase binding.In order to guarantee that titanium source and heteropolyacid salt fully mix, the stirring reaction time is 1-3h.
In the step (3), in the solvent evaporates process, temperature is too high, and the volatilization of solvent and the polycondensation of titanium species all can be very fast, can influence the binding between heteropolyacid salt and the titanium species.Temperature is low excessively, the volatilization difficulty of solvent, and time lengthening.Therefore the temperature of solvent evaporates is 30-50 ℃.100 ℃ aging is in order to make the polycondensation of titanium dioxide skeleton more complete, and structure is firmer.
Because adopt P123 as the structure agent of titanium dioxide skeleton among the present invention, therefore reaction finally must removal just can obtain meso-hole structure.During the high-temperature roasting demoulding, temperature is too high, can make the crystallite dimension of titanium dioxide become big, and intergranule interacts and weakens, and causes caving in of hole wall then.If temperature is low excessively, can not remove P123 fully.Therefore the control of roasting calcining temperature is at 300-500 ℃, and preferred control is at 300-450 ℃.
In sum, the invention provides the method for the heteropolyacid salt/titanium dioxide optical catalyst of the synthetic covalent bond of a kind of one-step method, the plug-hole problem of having avoided the synthetic heteropolyacid salt/titanium dioxide of secondary grafting method to cause, solved the problem that heteropolyacid salt comes off easily and runs off in photocatalytic process, and simple operating steps, reaction time is short, and the photochemical catalyst photocatalysis effect height of preparation can repeatedly be recycled.
The specific embodiment
Further specify the present invention below in conjunction with embodiment, can make those skilled in the art more fully understand the present invention, but not limit the present invention in any way.
Embodiment 1
(1) mixing is dissolved in 1g template agent P123 in the 12g nonaqueous solvents nitrile stirred overnight at room temperature;
(2) reaction adds 4g titanium tetrachloride and 0.1g heteropolyacid salt TBAPW
11, stirring reaction 1.5h obtains titanium colloidal sol:
(3) solvent evaporates and aging with step (2) gained titanium colloidal sol in 35 ℃ of following solvent flashing 12h, obtain xerogel in 100 ℃ of aging reaction 4h then;
(4) xerogel is collected in post processing, and the not heteropolyacid salt of binding is removed in supersound washing, puts into 350 ℃ of roasting 4h of Muffle furnace removed template method then, namely obtains heteropolyacid salt/titanium dioxide optical catalyst.
Embodiment 2
(1) mixing is dissolved in the 16g butyronitrile stirred overnight at room temperature with 1g template agent P123;
(2) reaction adds 1g titanium tetrachloride and 3g isopropyl titanate and 0.12g heteropolyacid salt TBAPW
11, stirring reaction 3h obtains titanium colloidal sol;
(3) solvent evaporates and aging with step (2) gained titanium colloidal sol in 45 ℃ of following solvent flashing 8h, obtain xerogel in 100 ℃ of aging reaction 5h then;
(4) xerogel is collected in post processing, and the not heteropolyacid salt of binding is removed in supersound washing, puts into 400 ℃ of roasting 4h of Muffle furnace removed template method then, namely obtains heteropolyacid salt/titanium dioxide optical catalyst.
Embodiment 3
(1) mixing is dissolved in the 10g acetonitrile stirred overnight at room temperature with 1g template agent P123;
(2) reaction adds 4g titanyl sulfate and 0.04g heteropolyacid salt TBAPW
11, stirring reaction 2.5h obtains titanium colloidal sol;
(3) solvent evaporates and aging with step (2) gained titanium colloidal sol in 30 ℃ of following solvent flashing 14h, obtain xerogel in 100 ℃ of aging reaction 4h then;
(4) xerogel is collected in post processing, and the not heteropolyacid salt of binding is removed in supersound washing, puts into 380 ℃ of roasting 4h of Muffle furnace removed template method then, namely obtains heteropolyacid salt/titanium dioxide optical catalyst.
Embodiment 4
(1) mixing is dissolved in the 14g acetonitrile stirred overnight at room temperature with 1g template agent P123;
(2) reaction adds 1g titanyl sulfate and 3g isopropyl titanate, 0.06g heteropolyacid salt TBAPW
11, stirring reaction 2h obtains titanium colloidal sol;
(3) solvent evaporates and aging with step (2) gained titanium colloidal sol in 40 ℃ of following solvent flashing 8h, obtain xerogel in 100 ℃ of aging reaction 6h then;
(4) xerogel is collected in post processing, and the not heteropolyacid salt of binding is removed in supersound washing, puts into 350 ℃ of roasting 4h of Muffle furnace removed template method then, namely obtains heteropolyacid salt/titanium dioxide optical catalyst.
Comparative example
The photocatalysis experiment selects for use azo class organic dyestuff methyl orange solution to investigate the photocatalytic activity of catalyst as the degraded object.Light source is the uviol lamp of 32W.Methyl orange solution concentration is 50mg/L, and volume is 35mL.Catalyst amount is 0.1g.It is saturated to make catalyst reach absorption before reaction earlier.Once test its absorbance every sampling in 5 minutes then.The degradation rate of methyl orange is 50% under ultraviolet irradiation.The degradation rate of simple use titanium dioxide is 50%, the degradation rate of simple use heteropolyacid salt is 40%, the sample that synthesizes among the example 1-4 is 92% to the degradation rate of methyl orange, as seen adopt the heteropolyacid salt/titanium dioxide optical catalyst of method preparation of the present invention to solve the problem that heteropolyacid salt comes off easily and runs off in photocatalytic process, and simple operating steps, reaction time is short, photocatalysis effect height.
Claims (3)
1. the synthetic method of a heteropolyacid salt/titanium dioxide optical catalyst, it is characterized in that: its concrete steps are as follows:
(1) template agent P123 is dissolved in the nitrile solvent stirred overnight at room temperature;
(2) add titanium source and heteropolyacid salt TBAPW in the nitrile solvent in the step (1)
11, stirring reaction 1-3h obtains titanium colloidal sol:
(3) with step (2) gained titanium colloidal sol solvent flashing in 30-50 ℃ of baking oven, the volatilization time is 8-16h, and baking oven is warming up to 100 ℃ of aging 4-6h and obtains xerogel then;
(4) collect xerogel, the not heteropolyacid salt of binding is removed in supersound washing, then at 300-500 ℃ of following roasting 4h removed template method, and the titanium dioxide optical catalyst of heteropolyacid salt that namely obtained binding;
Wherein said template agent: the mass ratio of solvent is 1:10-1:16; The titanium source: the mass ratio of heteropolyacid salt is 1:0.01-1:0.03; The template agent: the mass ratio in titanium source is 1:4.
2. synthetic method according to claim 1, it is characterized in that: described nitrile solvent is acetonitrile or butyronitrile; One or both in titanium tetrachloride, titanyl sulfate or the isopropyl titanate are selected in described titanium source for use.
3. synthetic method according to claim 1 and 2, it is characterized in that: the sintering temperature of step (4) removed template method is 300-450 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362807A (en) * | 2016-09-08 | 2017-02-01 | 河南师范大学 | Visible light driven photocatalysis hydrogen production catalyst as well as preparation method and application thereof |
| CN106410217A (en) * | 2016-10-25 | 2017-02-15 | 天津大学 | Three-dimensional structure photocatalysis anode for alkaline fuel cell and preparation method of three-dimensional structure photocatalysis anode |
| CN107185517A (en) * | 2017-04-28 | 2017-09-22 | 湖南文理学院 | A kind of preparation method of graphene catalysis net and its purposes in the processing of sponge municipal wastewater |
| CN112275280A (en) * | 2020-11-02 | 2021-01-29 | 河南大学 | Polyoxometallate-titanium dioxide nano composite material and preparation method and application thereof |
Citations (3)
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| CN101411991A (en) * | 2008-12-02 | 2009-04-22 | 上海理工大学 | Heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof |
| CN101612589A (en) * | 2009-07-22 | 2009-12-30 | 东北师范大学 | A kind of ordered mesoporous polyoxometallate salt-composite titania material and preparation method |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
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2013
- 2013-04-08 CN CN201310119309.8A patent/CN103203253B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101411991A (en) * | 2008-12-02 | 2009-04-22 | 上海理工大学 | Heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof |
| CN101612589A (en) * | 2009-07-22 | 2009-12-30 | 东北师范大学 | A kind of ordered mesoporous polyoxometallate salt-composite titania material and preparation method |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 苏志丽: "多金属氧酸盐/TiO2介孔杂化材料的合成及光催化性能研究", 《万方数据》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362807A (en) * | 2016-09-08 | 2017-02-01 | 河南师范大学 | Visible light driven photocatalysis hydrogen production catalyst as well as preparation method and application thereof |
| CN106410217A (en) * | 2016-10-25 | 2017-02-15 | 天津大学 | Three-dimensional structure photocatalysis anode for alkaline fuel cell and preparation method of three-dimensional structure photocatalysis anode |
| CN107185517A (en) * | 2017-04-28 | 2017-09-22 | 湖南文理学院 | A kind of preparation method of graphene catalysis net and its purposes in the processing of sponge municipal wastewater |
| CN107185517B (en) * | 2017-04-28 | 2019-08-02 | 湖南文理学院 | A kind of preparation method of graphene catalysis net and its purposes in the processing of sponge municipal wastewater |
| CN112275280A (en) * | 2020-11-02 | 2021-01-29 | 河南大学 | Polyoxometallate-titanium dioxide nano composite material and preparation method and application thereof |
| CN112275280B (en) * | 2020-11-02 | 2021-07-20 | 河南大学 | Polyoxometallate-titanium dioxide nano composite material and preparation method and application thereof |
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Effective date of registration: 20170424 Address after: 256500 Boxing Economic Development Zone, Binzhou, Shandong Co-patentee after: Yellow River Delta Jingbo Chemical Research Institute Co., Ltd. Patentee after: Shandong Bozhongcheng Clean Energy Co., Ltd. Address before: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee before: Yellow River Delta Jingbo Chemical Research Institute Co., Ltd. |