CN105148893A - Preparation method of double-crystal-form TiO2 photocatalytic material modified on G (graphene) - Google Patents
Preparation method of double-crystal-form TiO2 photocatalytic material modified on G (graphene) Download PDFInfo
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- CN105148893A CN105148893A CN201510523692.2A CN201510523692A CN105148893A CN 105148893 A CN105148893 A CN 105148893A CN 201510523692 A CN201510523692 A CN 201510523692A CN 105148893 A CN105148893 A CN 105148893A
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Abstract
The invention provides a preparation method of a double-crystal-form TiO2 photocatalytic material modified on G (graphene). Firstly, TALH, GO (graphene oxide) and urea are taken as raw materials, and single-crystal anatase TiO2/G, double-crystal anatase-brookite TiO2/G and single-crystal brookite TiO2/G are prepared with a hydrothermal synthesis method. During experiments, the phase composition of the double-crystal anatase-brookite TiO2/G is controlled through adjustment of the concentration of the urea in a TALH solution. The photocatalytic activity of a synthesized double-crystal anatase-brookite TiO2/G composite material is tested through degradation of a methyl orange solution. The composite material belongs to an inorganic photocatalytic material, is stable in performance, higher in photocatalytic activity and resistant to chemical corrosion and photocorrosion and has important significance in aspects of water photolysis, sterilization, preparation of solar sensitized batteries, environmental protection and the like.
Description
Technical field
The invention belongs to optic catalytic composite material preparation field, particularly a kind of twin crystal type TiO be modified on Graphene G
2the preparation method of catalysis material.
Background technology
Titanium dioxide is widely used for photocatalytic water, sterilization and prepares solar energy sensitized cells etc., and particularly in environmental protection, titanium dioxide presents wide application prospect especially as photochemical catalyst.Anatase, brockite, rutile are three kinds of titanium dioxide polymorph that nature exists, and in these three kinds of polymorph, anatase has been proved to be the most activated, but it can only absorb ultraviolet light, very low to the utilization rate of solar energy; Rutile activity is lower, and brockite is seldom studied in catalysis, because it has metastability, so synthesis pure phase brockite has very large difficulty in the past.Commercially available anatase-rutile titanium dioxide P25 is proved to be more superior than the activity of pure phase anatase and pure phase rutile in catalytic applications.
Existing twin crystal Anatase-brookite TiO recently
2correlative study, but have no the report of the anatase/brookite titanium dioxide nanocrystalline body be modified on Graphene G.Twin crystal Anatase-brookite TiO
2nontoxic, stable performance, it is a kind of important inorganic material, it has higher refraction coefficient and stable physical and chemical performance, and have chemical resistance and photoetch, photocatalytic activity high, to organic matter degradation non-selectivity, mineralising in water pollutant thoroughly, the advantage such as non-secondary pollution.
Summary of the invention
The object of this invention is to provide a kind of twin crystal type TiO be modified on Graphene G
2the preparation method of catalysis material, in order to the requirement of satisfied solution environmental problem.
The present invention is achieved like this, and concrete preparation method is as follows:
(1) take urea with after water-soluble solution, then add 10ml dihydroxy lactic acid network titanium acid ammonium, then this mixed solution is transferred in volumetric flask and is settled to 100ml with water;
(2) take 20mg graphene oxide and be placed in beaker, the 100ml mixed solution of the constant volume step (1) obtained is poured into and is equipped with in the beaker of graphene oxide, with preservative film, beaker is sealed, ultrasonic process 8-10h, ultrasonic power is 200w, guarantee that graphene oxide disperses, and fully contact with dihydroxy lactic acid network titanium acid ammonium;
(3) after ultrasonic process, the mixed solution that step (2) obtains is transferred in the teflon lined stainless steel autoclave of a 250ml, seals and be placed in electrothermal furnace, at 160 DEG C, reacting 24h;
(4) after the reaction of step (3) terminates, make teflon lined stainless steel autoclave naturally cool to room temperature, then high speed centrifugation must precipitate, and precipitate with deionized water washs 3 times, drier 24h at being deposited in 60 DEG C, grinding, finally H at 400 DEG C
2and N
2calcine 1h in mist, to obtain final product.
In dihydroxy lactic acid network titanium acid ammonium of the present invention, the mass fraction of water is 50%, is provided by Sigma-Aldrich company;
H of the present invention
2and N
2h in mist
2volume fraction is 5%, N
2volume fraction be 95%.
The present invention is by controlling the concentration synthetic single crystal anatase TiO of urea
2/ G, twin crystal Anatase-brookite TiO
2/ G, monocrystalline brockite TiO
2/ G, anatase TiO
2be almost spherical nanoparticle, brockite TiO
2in rod-like nano particle, twin crystal Anatase-brookite TiO
2for spherical and compound shape that is rod type, they combine with single-layer graphene equably, and graphene film can protect twin crystal Anatase-brookite TiO2 as carpet.Twin crystal Anatase-brookite TiO
2/ G Performance Ratio monocrystalline anatase TiO
2/ G, monocrystalline brockite TiO
2/ G is more active.Graphene is a kind of atomic structure of carbon of bi-dimensional cellular shape, is widely used in preparing semiconductor composite nano material, and Graphene, as the perfect electron transmission person of one, can suppress combining again of photo-generated carrier effectively, thus improves photocatalytic activity.In addition, Graphene has large surface area, can provide many Adsorptions, increases the adsorbance to reactant.For these reasons, Graphene being incorporated in twin crystal Anatase-brookite, for improving their photocatalytic activity, increasing the stability of material simultaneously, make this composite have excellent photocatalysis performance, thus prepare the superior catalysis material of combination property.This tests medicine used and product is all nontoxic, is environmental friendliness shaped material.
Advantage of the present invention: the present invention is from the angle of composite, graphene oxide and twin crystal Anatase-brookite titanium dioxide are combined with each other, prepare composite photocatalyst material, there is higher refraction coefficient and stable physical and chemical performance, and chemical resistance and photoetch, photocatalytic activity are higher.Therefore, this composite is in photocatalytic water, sterilization and prepare in solar energy sensitized cells etc., particularly in environmental protection, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis figure of the product that embodiment 1-6 obtains;
Fig. 2 be the product that obtains of embodiment 1-6 under simulated solar irradiation for the degradation curve figure of the methyl orange solution of the 50ml10PPm that degrades.
Detailed description of the invention
Below by embodiment, the invention will be further described, and the compound that embodiment 1-6 obtains represents with AxBy, and X, Y represent the phase fraction of anatase and brockite respectively.
Embodiment 1
(1) take the urea of 0.6g with after water-soluble solution, then add 10ml dihydroxy lactic acid network titanium acid ammonium, be then transferred in volumetric flask by this mixed solution and be settled to 100ml with water, the concentration now in the mixed solution of urea after constant volume is 0.1M;
(2) take 20mg graphene oxide and be placed in beaker, the 100ml mixed solution of the constant volume step (1) obtained is poured into and is equipped with in the beaker of graphene oxide, with preservative film, beaker is sealed, ultrasonic process 8h, ultrasonic power is 200w, guarantee that graphene oxide disperses, and fully contact with dihydroxy lactic acid network titanium acid ammonium;
(3) after ultrasonic process, the mixed solution that step (2) obtains is transferred in the teflon lined stainless steel autoclave of a 250ml, seals and be placed in electrothermal furnace, at 160 DEG C, reacting 24h;
(4) after the reaction of step (3) terminates, make teflon lined stainless steel autoclave naturally cool to room temperature, then high speed centrifugation must precipitate, and precipitate with deionized water washs 3 times, drier 24h at being deposited in 60 DEG C, grinding, finally H at 400 DEG C
2and N
2calcine 1h in mist, to obtain final product.
Products therefrom is TiO
2a100/G.Get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 63.86%.
Embodiment 2
Adding urea amount in step (1) is 1.5g, and the concentration in the mixed solution of urea after constant volume is 0.25M, and step (2), (3), (4) are with embodiment 1.
Products therefrom is TiO
2a90B10/G, get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 80.07%.
Embodiment 3
Adding urea amount in step (1) is 3.0g, and the concentration in the mixed solution of urea after constant volume is 0.5M, and step (2), (3), (4) are with embodiment 1.
Products therefrom is TiO
2a75B25/G, get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 94.82%.
Embodiment 4
Adding urea amount in step (1) is 6.0g, and the concentration in the mixed solution of urea after constant volume is 1.0M, and step (2), (3), (4) are with embodiment 1.
Products therefrom is TiO
2a50B50/G, get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 94.44%.
Embodiment 5
Adding urea amount in step (1) is 9.0g, and the concentration in the mixed solution of urea after constant volume is 1.5M, and step (2), (3), (4) are with embodiment 1.
Products therefrom is TiO
2a35B65/G, get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 100%.
Embodiment 6
Adding urea amount in step (1) is 42.0g, and the concentration in the mixed solution of urea after constant volume is 7.0M, and step (2), (3), (4) are with embodiment 1.
Products therefrom is TiO
2b100/G, get this product of 50mg for the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, after 120min, degradation rate reaches 86.70%.
In embodiment 1-6, in the X-ray diffraction analysis figure of products therefrom, the peak of brockite is formed gradually, and this illustrates that composite photocatalyst material has brockite crystalline phase to generate, and refers to accompanying drawing 1.From accompanying drawing 1, the diffraction peak of TiA100/G in 2 θ be 25.31 ° (101), ° 37.90 (103), 48.02 ° (200), 54.64 ° (105) and 62.83 ° (204) (2 θ).It can thus be appreciated that for load be Anatase on Graphene, and diffraction maximum is comparatively strong, and comparatively sharp-pointed, illustrates that its degree of crystallinity is better.Along with the increase of urea amount, there is small peak clearly at 30.81 ° of (121) places, illustrate that brookite generates gradually, brockite characteristic peak 30.81 ° (121), 42.34 ° (221), 46.07 ° (032) (2 θ).Do not observe about 11 ° and occur characteristic peak, this shows that graphene oxide GO is reduced, and the characteristic peak of redox graphene is positioned at about 25 °, may overlap with anatase 25.31 ° of (101) characteristic peaks.As can be seen here by controlling amount of urea, the anatase of load on Graphene, brockite and twin crystal shaped material successfully prepare.
In embodiment 1-6, products therefrom compares for the degradation effect of the methyl orange solution of the 50ml10PPm that degrades under simulated solar irradiation, refers to accompanying drawing 2.From accompanying drawing 2, under simulated solar irradiation irradiates, pure methyl orange solution has almost no change.Along with the increase of amount of urea, synthetic product TiO
2a100/G, TiO
2a90B10/G, TiO
2a75B25/G, TiO
2a50B50/G, TiO
2the degradation effect of A35B65/G strengthens successively, and amount of urea is increased to the TiO of 42g synthesis
2the catalytic effect of AB100/G declines on the contrary.TiO
2the final degradation effect of A35B65/G is best, just can be degradable by methyl orange less than 120min, and its reason may be TiO
2the particle size of A35B65/G photochemical catalyst is less, specific area is larger, the presoma dihydroxy lactic acid network titanium acid ammonium of titanium and the contact of graphene oxide GO better, the electric conductivity that Graphene has had, it is the acceptor of excitation electron, excitation electron is made to transfer to the surface of Graphene, thus inhibit the compound in light induced electron and hole, improve photocatalysis efficiency.TiO
2a100/G degradation effect is the poorest, because it is the brockite of load on Graphene, brockite catalytic effect is natively poor, and may be also that titanium dioxide and Graphene compound obtain bad, Graphene play the effect in separate electronic and hole.
In this experimentation, urea concentration is very important, controls twin crystal Anatase-brookite TiO mainly through regulating the concentration of urea in dihydroxy lactic acid network titanium acid ammonium solution
2the phase composition of/G, and the twin crystal Anatase-brookite TiO being tested synthesis by degraded methyl orange solution
2the photocatalytic activity of/G composite.From above-described embodiment, the twin crystal TiO be made up of 35% anatase and 65% brockite
2the photocatalytic activity of/G composite is best, and the concentration now in the mixed solution of urea after constant volume is 7.0M, and this is all owing to the interface charge rate of transform strengthened between anatase, brockite nanocrystal.TiO
2the hetero-junctions formed between different crystalline phase is for extremely important raising photooxidation is active.In addition, due to the not in pairs interaction of pi-electron and Ti atom or the TiO of Graphene
2and the chemical bond between Graphene, Graphene and TiO
2the band gap of heterocomplex to reduce this for raising photooxidation is active be also extremely important.
Claims (3)
1. one kind is modified at the twin crystal type TiO on Graphene G
2the preparation method of catalysis material, is characterized in that: comprise following steps:
(1) take urea with after water-soluble solution, then add 10ml dihydroxy lactic acid network titanium acid ammonium, then this mixed solution is transferred in volumetric flask and is settled to 100ml with water;
(2) take 20mg graphene oxide and be placed in beaker, the 100ml mixed solution of the constant volume step (1) obtained is poured into and is equipped with in the beaker of graphene oxide, with preservative film, beaker is sealed, ultrasonic process 8-10h, ultrasonic power is 200w, guarantee that graphene oxide disperses, and fully contact with dihydroxy lactic acid network titanium acid ammonium;
(3) after ultrasonic process, the mixed solution that step (2) obtains is transferred in the teflon lined stainless steel autoclave of a 250ml, seals and be placed in electrothermal furnace, at 160 DEG C, reacting 24h;
(4) after the reaction of step (3) terminates, make teflon lined stainless steel autoclave naturally cool to room temperature, then high speed centrifugation must precipitate, and precipitate with deionized water washs 3 times, drier 24h at being deposited in 60 DEG C, grinding, finally H at 400 DEG C
2and N
2calcine 1h in mist, to obtain final product.
2. a kind of twin crystal type TiO be modified on Graphene G according to claim 1
2the preparation method of catalysis material, is characterized in that: in described dihydroxy lactic acid network titanium acid ammonium, the mass fraction of water is 50%, is provided by Sigma-Aldrich company; Described H
2and N
2h in mist
2volume fraction is 5%, N
2volume fraction be 95%.
3. a kind of twin crystal type TiO be modified on Graphene G according to claim 1
2the preparation method of catalysis material, is characterized in that: the concentration in described step (1) in the mixed solution of urea after constant volume can be 0.1M, 0.25M, 0.5M, 1.0M, 1.5M or 7.0M respectively.
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Cited By (3)
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|---|---|---|---|---|
| CN105540656A (en) * | 2015-12-28 | 2016-05-04 | 南昌航空大学 | Anatase/brookite titanium dioxide heterojunction nano composite material |
| CN106206044A (en) * | 2016-09-27 | 2016-12-07 | 武汉大学 | A kind of small particle brookite titania nano-powder and its production and use |
| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
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| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
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Application publication date: 20151216 |