CN102179260B - Multi-component doped photocatalytic material and preparation method thereof - Google Patents
Multi-component doped photocatalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multi-component doped photocatalytic material and a preparation method thereof and relates to a photocatalytic material. The a multi-component doped photocatalytic material comprises titanium dioxide and a doping component, wherein the doping component, based on the molar percentage of the doping component and the titanium dioxide, comprises less than or equal to 1 percent of metal and less than or equal to 50 percent of non-metal substance. The metal may be iron, cobalt, nickel, copper, aluminum or the like; and the non-metal substance may be nitrogen, sulfur, carbon or the like. Through the strong complexing action of citric acid, the citric acid form a stable quinary ring or a hexatomic ring with metal atoms; and the carboxyls in the citric acid and the hydroxys of glycol undergo esterification. The citric acid is a polycarboxylic acid, so by repeatedly performing the complexing reaction and esterification like this, the molecular chain is prolonged to form a polymer with a spatial netty structure. After subsequent treatment such as preburning, deep burning and the like of the polymer, the multi-component doped photocatalytic material can be obtained.
Description
Technical field
The present invention relates to catalysis material, particularly multi-component doped photocatalytic material and preparation method thereof.
Background technology
Photocatalysis mainly is divided into surround lighting catalysis and energy photocatalysis two large classes.Surround lighting catalysis relates generally to the aspects such as sterilization, sterilization, light degradation, self-cleaning, and wherein existing a considerable amount of technology have realized commercialization.The photocatalytic hydrogen production by water decomposition energy is mainly studied in energy photocatalysis, and the hydrogen manufacturing of photocatalysis Decomposition renewable resource can wait.Along with the greenhouse effects in modern age, fossil fuel is exhausted, the becoming increasingly conspicuous of the variety of issues such as energy crisis, and photolysis water hydrogen can become the study hotspot of this area gradually.
Known catalysis material has oxide, sulfide, nitride, titanate, tantalates, tungstates and niobates etc. at present.Wherein, titanium dioxide semiconductor is considered to have most the catalysis material of application potential because of its cheap and easy to get, nontoxic numerous advantages such as stable.But titanium dioxide semiconductor has caused its photoresponse value lower because of its special valence band structure, can only utilize the less problems such as ultraviolet light of ratio in the sunshine.Present research emphasis, be exactly by all means with means, improve the absorbing properties of Titania Photocatalytic System, improve photocatalysis efficiency.The approach and the means that improve optically catalytic TiO 2 efficient roughly have following several: ion doping, nonmetal doping, noble metal loading, implanted ions etc.Wherein, doping method is easy to operate because of it, cost is lower and effect is remarkable etc., and advantage is widely used.
Doping type titanium dioxide has multiple preparation method, infusion process for example, coprecipitation etc.Chinese patent application 200910106481.3 discloses a kind of composite nanometer titanium dioxide photocatalysis material and preparation method, the method modified silicon dioxide sol that from TiO 2 sol, mixed, replaced original Ti-O-Ti key by the Ti-O-Si key, reduced the oxidation-reduction potential of titanium, make the titanium dioxide light absorption wavelength produce red shift, improve the visible light utilization rate of titanium, improved simultaneously adhesive force and the hardness of coating.Can't reach the problem and blemish that molecule and atomic level etc. are unfavorable for improving photocatalytic activity but that the synthetic method that these are comparatively traditional, each component of ubiquity are disperseed is inhomogeneous, be difficult to avoid metal surface hydroxylating and each component to be mixed.
Summary of the invention
The object of the invention is to for each component in the prior art disperse inhomogeneous, be difficult to avoid metal surface hydroxylating and each component to be mixed can't to reach the problems such as molecule and atomic level, a kind of multi-component doped photocatalytic material and preparation method thereof is provided.
Described multi-component doped photocatalytic material comprises titanium dioxide and doping component, and described doping component comprises metal and nonmetal, with the molar percentage calculating of doping component and titanium dioxide, the content of described metal≤1%, described nonmetallic content≤50%.
Described metal can be at least a in iron, cobalt, nickel, copper, the aluminium etc., described nonmetal at least a in nitrogen, sulphur, the carbon etc. of can be.
The preparation method of described multi-component doped photocatalytic material may further comprise the steps:
1) with metatitanic acid fourth fat, absolute ethyl alcohol, alloy, citric acid and ethylene glycol with mol ratio 1000: (40000～60000): (0.1～2000): (5000～20000): (30000～50000) are mixed to get mixture, and described alloy is metallic compound and nonmetallic compound;
2) with step 1) the gained mixture is warming up to 50～70 ℃ and carries out complexing;
3) mixture after the complexing is warming up to 100～170 ℃ and carries out esterification;
4) with step 3) mixture after the esterification is warming up to 200～400 ℃ and carries out calcination, obtains the spongy product of black;
5) carry out calcination with again being warming up to 450～850 ℃ after the spongy product grinding of gained black, the product after the calcination is ground sieve, gained 100～300 purpose products are multi-component doped photocatalytic material.
In step 1) in, described metallic compound can be metal nitrate or metal halide; Described metal nitrate can be the nitrate of iron, copper, aluminium etc.; Described metal halide can be iron chloride, frerrous chloride etc.; Described nonmetallic compound can be compound that contains nitrogen, sulphur, carbon etc. etc., such as urea etc.
In step 2) in, the time of described complexing can be 0.5～2h.
In step 3) in, the time of described esterification can be 2～10h.
In step 4) in, the speed of described intensification can be 1～10 ℃/min, is preferably 4 ℃/min, and the time of described calcination can be 1～5h.
In step 5) in, the speed of described intensification can be 1～10 ℃/min, is preferably 4 ℃/min, and the time of described calcination can be 1～5h.
The present invention forms stable five-membered ring, six-membered ring structure by strong complexing and the metallic atom of citric acid, again by the hydroxyl generation esterification of carboxyl and the ethylene glycol of citric acid.Because citric acid is polybasic carboxylic acid, complexing and esterification occur so repeatedly, can make strand elongated so that form the cancellated polymer in space.This polymer can obtain multi-component doped photocatalytic material through subsequent treatment such as pre-calcination, degree of depth calcinations.
The present invention has following advantage:
1) the multi-component doped photocatalytic material better heat stability of the present invention's preparation, and organic principle all can be removed fully through high temperature sintering, and it is comparatively pure therefore to prepare products therefrom.
2) the preparation system among the present invention is non-aqueous media, establishment the hydrolysis of metal ion among traditional preparation method, and surface hydroxylation effect.
3) metal complex and ethylene glycol mix by polymerisation and form relatively-stationary space network structure among the present invention, so that various material can mix at atom or molecular level.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of the multi-component doped photocatalytic material of embodiment of the invention preparation.In Fig. 1, abscissa be the angle of diffraction 2 θ (°), ordinate is diffracted intensity (a.u.); Curve a is the multi-component doped photocatalytic material of embodiment 1 preparation, and curve b is the multi-component doped photocatalytic material of embodiment 2 preparations, and curve c is the multi-component doped photocatalytic material of embodiment 3 preparations.
Fig. 2 is the UV-Vis DRS collection of illustrative plates of the multi-component doped photocatalytic material of embodiment of the invention preparation.In Fig. 2, abscissa is wavelength (nm), and ordinate is absorbance (a.u.); Curve a is the multi-component doped photocatalytic material of embodiment 1 preparation, and curve b is the multi-component doped photocatalytic material of embodiment 2 preparations, and curve c is the multi-component doped photocatalytic material of embodiment 3 preparations.
Fig. 3 is the multi-component doped photocatalytic material photocatalytic hydrogen production by water decomposition reactivity figure of embodiment of the invention preparation.In Fig. 3, abscissa is time (h), and ordinate is hydrogen output (μ L); Curve a is the multi-component doped photocatalytic material of embodiment 1 preparation, and curve b is the multi-component doped photocatalytic material of embodiment 2 preparations, and curve c is the multi-component doped photocatalytic material of embodiment 3 preparations.
The specific embodiment
1) get 1mol ethanol, 0.02mol metatitanic acid fourth fat, the 0.02mmol cobalt nitrate, 0.02mol urea, the 0.2mol citric acid, 0.8mol ethylene glycol, cobalt titanium mol ratio is 1: 1000, nitrogen titanium mol ratio is 1: 1, and with each reactant successively injecting reactor;
2) be warming up to 60 ℃ under the electric stirring each reactant is mixed, the retention time is 1h; Then be warming up to 140 ℃, sustained response 5h under the vigorous stirring, solvent evaporated also makes citric acid and the reaction of ethylene glycol generation polymerization esterification, along with the carrying out of reaction, the system very thickness that becomes;
3) change the thickness product after the esterification fully over to cleaning container and be built in the Muffle furnace, with the heating rate of 4 ℃/min, begin to rise to 350 ℃ of lower constant temperature 3h from room temperature, obtain the pre-firing product of the spongiform porous of black;
4) pre-firing product is changed in the mortar and again to place Muffle furnace after carefully grinding, with the heating rate of 4 ℃/min, begin to rise to 650 ℃ of lower constant temperature 2h from room temperature, obtain whole firing product;
5) with final firing product porphyrize and sieve, gained 100～300 purpose products are multi-component doped photocatalytic material.
Embodiment 2
1) get 1mol ethanol, 0.02mol metatitanic acid fourth fat, the 0.02mmol cobalt nitrate, the 0.2mol citric acid, 0.8mol ethylene glycol, cobalt titanium mol ratio is 1: 1000, and with each reactant successively injecting reactor;
2) be warming up to 60 ℃ under the electric stirring each reactant is mixed, the retention time is 1h; Then be warming up to 140 ℃, sustained response 5h under the vigorous stirring, solvent evaporated also makes citric acid and the reaction of ethylene glycol generation polymerization esterification, along with the carrying out of reaction, the system very thickness that becomes;
3) change the thickness product after the esterification fully over to cleaning container and be built in the Muffle furnace, with the heating rate of 4 ℃/min, begin to rise to 350 ℃ of lower constant temperature 3h from room temperature, obtain the pre-firing product of the spongiform porous of black;
4) pre-firing product is changed in the mortar and again to place Muffle furnace after carefully grinding, with the heating rate of 4 ℃/min, begin to rise to 650 ℃ of lower constant temperature 2h from room temperature, obtain whole firing product;
5) with final firing product porphyrize and sieve, gained 100～300 purpose products are multi-component doped photocatalytic material.
Embodiment 3
1) get 1mol ethanol, 0.02mol metatitanic acid fourth fat, 0.02mol urea, the 0.2mol citric acid, 0.8mol ethylene glycol, titanium nitrogen mol ratio is 1: 1, and with each reactant successively injecting reactor;
2) be warming up to 60 ℃ under the electric stirring each reactant is mixed, the retention time is 1h; Then be warming up to 140 ℃, sustained response 5h under the vigorous stirring, solvent evaporated also makes citric acid and the reaction of ethylene glycol generation polymerization esterification, along with the carrying out of reaction, the system very thickness that becomes;
3) change the thickness product after the esterification fully over to cleaning container and be built in the Muffle furnace, with the heating rate of 4 ℃/min, begin to rise to 350 ℃ of lower constant temperature 3h from room temperature, obtain the pre-firing product of the spongiform porous of black;
4) pre-firing product is changed in the mortar and again to place Muffle furnace after carefully grinding, with the heating rate of 4 ℃/min, begin to rise to 650 ℃ of lower constant temperature 2h from room temperature, obtain whole firing product;
5) with final firing product porphyrize and sieve, gained 100～300 purpose products are multi-component doped photocatalytic material.
Products obtained therefrom is carried out the XRD diffraction detect (referring to Fig. 1), the multi-component doped photocatalytic material among the present invention is the titanium dioxide of anatase crystal, and perfect crystalline, product are pure.Doping component does not have signal in collection of illustrative plates, this shows that doping component is uniformly dispersed in material.
UV-vis DRS (UV-Vis DRS) shows: the multi-component doped photocatalytic material among the present invention is all comparatively superior at full wave photo absorption performance, especially at the royal purple visible region of 400～500nm, and photo absorption performance more remarkable (referring to Fig. 2).
Above embodiment sample is placed homemade photocatalyst reaction vessel, test photodissociation water hydrogen production reaction is active under identical condition, and experimental result (referring to Fig. 3) shows: the multi-component doped photocatalytic material among the present invention has higher photocatalytic hydrogen production by water decomposition reactivity.
Claims (5)
1. multi-component doped photocatalytic material, it is characterized in that described multi-component doped photocatalytic material comprises titanium dioxide and doping component, described doping component comprises metal and nonmetal, molar percentage with doping component and titanium dioxide calculates, the content of described metal≤1%, described nonmetallic content≤50%; Described metal is iron, cobalt, nickel, copper, aluminium; Described nonmetal be nitrogen, sulphur, carbon;
Described multi-component doped photocatalytic material is prepared by following methods:
1) with butyl titanate, absolute ethyl alcohol, alloy, citric acid and ethylene glycol with mol ratio 1000: (40000～60000): (0.1～2000): (5000～20000): (30000～50000) are mixed to get mixture, and described alloy is metallic compound and nonmetallic compound;
2) step 1) gained mixture is warming up to 50～70 ℃ and carries out complexing; The time of described complexing is 0.5～2h;
3) mixture after the abundant complexing is warming up to 100～170 ℃ and carries out esterification; The time of described esterification is 2～10h;
4) mixture after the step 3) esterification is warming up to 200～400 ℃ and carries out calcination, obtain the spongy product of black;
5) carry out calcination with again being warming up to 450～850 ℃ after the spongy product grinding of gained black, the product after the calcination is ground sieve, gained 100～300 purpose products are multi-component doped photocatalytic material.
2. multi-component doped photocatalytic material as claimed in claim 1 is characterized in that in step 1), and described metallic compound is metal nitrate or metal halide.
3. multi-component doped photocatalytic material as claimed in claim 2 is characterized in that described metal nitrate is iron nitrate, copper nitrate or aluminium nitrate; Described metal halide is iron chloride or frerrous chloride.
4. multi-component doped photocatalytic material as claimed in claim 1 is characterized in that in step 4), and the speed of described intensification is 1～10 ℃/min, and the time of described calcination is 1～5h.
5. multi-component doped photocatalytic material as claimed in claim 1 is characterized in that in step 5), and the speed of described intensification is 1～10 ℃/min, and the time of described calcination is 1～5h.
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| CN107552079B (en) * | 2017-08-16 | 2019-12-27 | 同济大学 | Titanium dioxide photocatalyst with spongy porous structure and preparation and application thereof |
| CN111530485B (en) * | 2019-11-25 | 2023-05-26 | 中国石油大学(华东) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof |
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| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101596457A (en) * | 2009-07-06 | 2009-12-09 | 宁波山泉建材有限公司 | The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope |
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| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101596457A (en) * | 2009-07-06 | 2009-12-09 | 宁波山泉建材有限公司 | The nano titanium dioxide photocatalyst and the preparation method of boron and other element codope |
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