CN103962117A - Preparation method of titanium dioxide with adjustable colors and efficient photocatalytic activity - Google Patents
Preparation method of titanium dioxide with adjustable colors and efficient photocatalytic activity Download PDFInfo
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Abstract
The invention discloses a preparation method of titanium dioxide with adjustable colors and efficient photocatalytic activity, belongs to the technical field of chemistry and material science, and solves the technical problems that in the prior art, the preparation method of visible-light response titanium dioxide is high in cost, complicated in steps, and poor in stability, and furthermore the prepared titanium dioxide is not adjustable in color, and low in catalytic activity. The preparation method disclosed by the invention comprises the following steps: uniformly mixing a metal hydride with titanium dioxide to obtain a mixture; under the protection of an inert gas, performing a solid-phase reaction on the mixture at 200-400 DEG C, and obtaining the titanium dioxide with adjustable colors from light gray to blue and black finally. The preparation method is simple, controllable, low in cost, and convenient for mass production; in the meantime, the prepared titanium dioxide is adjustable in colors, stable in physicochemical property and high in photocatalytic activity, and can be widely applied to the fields of self-cleaning coatings, paints, coatings, photocatalysis, solar cells and the like.
Description
Technical field
The present invention relates to the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of a kind of color, belong to chemistry and material science.
Background technology
Titanium dioxide is as a kind of semi-conducting material being most widely used, there is cheapness, nontoxic, physics, stable chemical nature and relatively high photocatalytic activity, be a kind of desirable photochemical catalyst, gas sensor, solar cell and paint material, have a wide range of applications at the chemical industry such as coating, plastics, papermaking, paint, cosmetics, photocatalyst, medicine and field of Environment Protection.
Titanium dioxide presents white conventionally, is a kind of wide bandgap semiconductor (its Rutile Type energy gap is 3.0eV, and Anatase energy gap is 3.2eV), only can utilize the ultraviolet light part of solar spectrum, and electricity conversion is less than 2.2% conventionally.Therefore, how to expand titanium dioxide as seen, even near infrared light absorption, on the one hand make it have colourful color, further expand its application in the field such as coating, paint; Improve on the other hand its photocatalytic activity and photoelectric conversion performance, expand its application in fields such as energy environments, become the key that current titanium dioxide industry is expanded.
In prior art, mainly adopt metal ion mixing, nonmetal doping and Ti
3+the method of auto-dope realizes the visible light-responded of titanium dioxide.(Science2011 as synthetic in a kind of black poriferous titanium dioxide based on surface hydriding, 331,746), the method be by poriferous titanium dioxide at 20 atmospheric hydrogen and 200 DEG C, hydrogenation 5 days, having prepared energy gap is the black titanium dioxide of 1.54eV highlight catalytic active.Since then, the research of black titanium dioxide arouses widespread concern.A series ofly relate to high pressure, high temperature hydrogenation, plasma assists hydrogenation, and the methods such as aluminothermy are developed successively.But said method not only needs high temperature, expensive equipment, and complicated operation, consuming time, to ingredient requirement harshness, therefore seriously hinder its large-scale industrial production.In addition, above method is difficult to titanium dioxide to realize controlledly synthesis, and its color and high catalytic activity are difficult to be guaranteed.
Summary of the invention
Preparation method's cost of the object of the invention is to solve visible light-responsible titanium dioxide in prior art is high, complex steps, poor stability, the technical problem that titanium dioxide color is non-adjustable and catalytic activity is low of preparing, provides the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of a kind of color.
The preparation method of what color of the present invention was adjustable the have titanium dioxide of high efficiency photocatalysis activity, comprises following step:
(1) metal hydride and titanium dioxide are mixed, obtain mixture;
(2) under inert atmosphere, mixture is added after thermal response at 200-400 DEG C, cooling, obtain crude product;
(3) by crude product washing, vacuum drying, obtain the adjustable titanium dioxide with high efficiency photocatalysis activity of color.
Preferably, described metal hydride is (0.2-2) with the amount of substance ratio of titanium dioxide: 1, and more preferably 1:1.
Preferably, the time that adds thermal response described in is 5min-10h.
Preferably, described metal hydride is sodium borohydride, lithium aluminium hydride, sodium hydride, calcium hydride or titantium hydride.
Preferably, described titanium dioxide is any one or a few the mixing in anatase phase titanium dioxide, red schorl phase titanium dioxide, brookite titanium dioxide, amorphous titania; More preferably, described titanium dioxide is photochemical catalyst P25.
Preferably, in described step (3), adopt water and ethanol washing.
Preferably, in described step (3), 30-100 DEG C of vacuum drying.
Preferably, in described step (2), inert atmosphere is argon gas, helium or nitrogen.
Beneficial effect of the present invention:
(1) preparation method of the present invention is simple, and cost is low, is applicable to all titanium dioxide raw materials, is convenient to large-scale production;
(2) preparation method of the present invention can prepare the titanium dioxide of different colours, and color is controlled, can realize from white-pale yellow-light gray-light blue-blueness-dark blue a series of colors to black and the preparation of Neutral colour titanium dioxide, solve the single difficult problem of titanium dioxide color for a long time, be expected to further expand the application of titanic oxide material in fields such as paint, coating, there is very large commercial application prospect;
(3) titanium dioxide that prepared by preparation method of the present invention can keep the original pattern of raw material and size constancy substantially, does not produce reunion, is conducive to realize the regulation and control to product size, pattern by the selection to raw material and regulation and control;
(4) titanium dioxide that prepared by preparation method of the present invention has good visible light-responded property, high photocatalytic activity (under ultraviolet-visible irradiation, the Photocatalyzed Hydrogen Production speed of titanium dioxide prepared by the present invention reaches as high as 7.2 times of commercially available titanium dioxide optical catalyst P25 under the same terms); At Photocatalyzed Hydrogen Production, photocatalysis sewage processing, air cleaning, ultraviolet-visible light sterilization, antiviral, the photocatalysis field such as self-cleaning surface coating have huge potential using value;
(5) titanium dioxide that prepared by the present invention to the Photocatalytic activity of dye molecule methyl orange also higher than commercialization photochemical catalyst P25.
Brief description of the drawings
In Fig. 1, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of (a) preparing for the embodiment of the present invention 1, the optical photograph of the different titania powders of (b) preparing for the embodiment of the present invention 1;
In Fig. 2, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of (a) preparing for the embodiment of the present invention 4, the optical photograph of the different titania powders of (b) preparing for the embodiment of the present invention 4;
In Fig. 3, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of (a) preparing for the embodiment of the present invention 5, the optical photograph of the different titania powders of (b) preparing for the embodiment of the present invention 5;
In Fig. 4, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of (a) preparing for the embodiment of the present invention 7, the optical photograph of the different titania powders of (b) preparing for the embodiment of the present invention 7;
In Fig. 5, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of (a) preparing for the embodiment of the present invention 8, the optical photograph of the different titania powders of (b) preparing for the embodiment of the present invention 8;
In Fig. 6, (a) for storing the ultraviolet-visible solid diffuse reflection spectrum of the CIOMP-8 after 1 year under the freshly prepd CIOMP-8 of embodiment 1 and normal temperature condition; (b) for storing the optical photograph of the CIOMP-8 after 1 year under the freshly prepd CIOMP-8 of embodiment 1 and normal temperature condition;
In Fig. 7, (a) being the transmission electron microscope picture of the photochemical catalyst P25 of embodiment 1, is (b) transmission electron microscope picture of the CIOMP-8 of embodiment 1; (c) be the high resolution transmission electron microscopy figure of the photochemical catalyst P25 of embodiment 1; (d) be the high resolution transmission electron microscopy figure of the CIOMP-2 of embodiment 1; (e) be the high resolution transmission electron microscopy figure of the CIOMP-6 of embodiment 1; (f) be the high resolution transmission electron microscopy figure of the CIOMP-8 of embodiment 1;
Fig. 8 be the embodiment of the present invention 1 in differential responses temperature, the X-ray powder diffraction pattern of prepared shades of colour titania powder of differential responses time;
In Fig. 9, (a) be the embodiment of the present invention 1 in differential responses temperature, the Raman spectrogram of prepared shades of colour titania powder of differential responses time; (b) be that the photochemical catalyst P25 of the embodiment of the present invention 1 and CIOMP-8 are at 144cm
-1raman spectrogram is amplified in main peak displacement;
In Figure 10, the TiX-X-ray photoelectron spectroscopy X photoelectron spectroscopy (XPS) of the different titania powders of (a) preparing for the embodiment of the present invention 1; (b) the valence band photoemission figure (VBXPS) of the different titania powders of preparing for the embodiment of the present invention 1;
Figure 11 be the embodiment of the present invention 1 in differential responses temperature, the photochemical catalyzing hydrogen output of prepared shades of colour titania powder of differential responses time under ultraviolet-visible irradiation schemed over time.
Detailed description of the invention
Color is adjustable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, taking various crystalline state or amorphous titanium dioxide as raw material, using metal hydride as reducing agent, by the get everything ready titanium dioxide of adjustable color and high efficiency photocatalysis activity of low-temperature solid phase reaction legal system, specifically comprise the following steps:
(1) by even to metal hydride and titanium dioxide mixed grinding, obtain mixture;
(2) under inert atmosphere, mixture is added to thermal response 5min-10h at 200-400 DEG C, and along with the increase of reaction temperature or the prolongation in reaction time, titanium dioxide color changes into light yellow by white gradually, light grey, light blue, blueness, navy blue is to black, the color of preparation as required, stop reaction in good time, cooling in inert atmosphere, obtain crude product;
Reaction temperature in step (2) is lower than 200 DEG C, and reaction speed is not even carried out slowly; Higher than 400 DEG C, reaction speed is too fast, reacts uncontrollable, and when production, energy cost increases;
(3) by crude product water and ethanol washing several, remove unreacted metal hydride, then at 30-100 DEG C, preferably 70 DEG C, vacuum drying, obtains the adjustable titanium dioxide with high efficiency photocatalysis activity of color.
In the present invention, metal hydride is preferably (0.2-2) with the amount of substance ratio of titanium dioxide: 1, the ratio of metal hydride and titanium dioxide is less, it is poorer that both react uniformity, under same reaction temperature, will make titanium dioxide reach identical degree for the treatment of, the required reaction time is longer; And metal hydride and titanium dioxide ratio are larger, it is better that both react uniformity, under same reaction temperature, to make titanium dioxide reach identical degree for the treatment of, the required reaction time is shorter, but reducing agent cost increases, so metal hydride compares more preferably 1:1 with the amount of substance of titanium dioxide; Metal hydride can be selected sodium borohydride, lithium aluminium hydride, sodium hydride, calcium hydride or titantium hydride, titanium dioxide can be any one or a few the mixing in anatase phase titanium dioxide, red schorl phase titanium dioxide, brookite titanium dioxide and amorphous titania, as the mixing of anatase phase titanium dioxide and red schorl phase titanium dioxide, photochemical catalyst P25 (the photochemical catalyst P25 that the embodiment of the present invention adopts goldschmidt chemical corporation to produce); Inert atmosphere is the gas that argon gas, helium or nitrogen etc. do not react with metal hydride.
Preparation method of the present invention, the color of the titanium dioxide of preparation and photocatalysis characteristic, depend on the kind of metal hydride in step (1), titanium dioxide raw material there is form and both mixed proportions.Also depend in step (2) regulation and control in reaction temperature and reaction time simultaneously.But on the whole,, by regulation and control reaction temperature and reaction time, the color that preparation method of the present invention can realize titanium dioxide changes into light yellow from white, light grey, light blue, blueness, navy blue is to a series of colors of black and the controlled modulation of intermediate state secondary colour.
Principle of the present invention: under suitable reaction temperature, metal hydride is subject to thermal activation or decomposition, produces reactive hydrogen atom or metal, and reactive hydrogen atom or metal react with titanium dioxide, capture titanium dioxide surface oxygen atom, causes titanium dioxide to produce oxygen vacancies.Along with the intensification of the extent of reaction, oxygen vacancies concentration increases, thereby causes titanium dioxide color and photocatalytic activity that corresponding variation occurs.
Further illustrate the present invention below in conjunction with drawings and Examples.
Embodiment 1
In conjunction with Fig. 1,6-11 explanation embodiment 1
(1) 1.9g sodium borohydride and 4.0g photochemical catalyst P25 (metal hydride: P25=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 300 DEG C or 350 DEG C, keep 5-120min, naturally cool to room temperature, obtain crude product;
(3) by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains titania powder respectively, and mark is as table 1.
In Fig. 1, (a) the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of preparing for the embodiment of the present invention 1, in Fig. 1 (a), curve is followed successively by the ultraviolet-visible solid diffuse reflection spectrum of CIOMP-8, CIOMP-7, CIOMP-6, CIOMP-5, CIOMP-4, CIOMP-3, CIOMP-2, CIOMP-1 and P25 from top to bottom; (b) optical photograph of the different titania powders of preparing for the embodiment of the present invention 1; The change color of titania powder is as shown in table 1.As can be seen from Figure 1, prepared titanium dioxide presents wide absorption to the visible and near infrared light between 400-900nm, and along with the rising of reaction time and reaction temperature, absorb and strengthen, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of variations to black.
Table 1 is the change color of the titania powder prepared different temperatures, differential responses time
In Fig. 6, (a) for storing the ultraviolet-visible solid diffuse reflection spectrum of the CIOMP-8 after 1 year under the freshly prepd CIOMP-8 of embodiment 1 and normal temperature condition; (b) for storing the optical photograph of the CIOMP-8 after 1 year under the freshly prepd CIOMP-8 of embodiment 1 and normal temperature condition; As can be seen from Figure 6, after long-term placement of titanium dioxide prepared by the present invention, outward appearance and ultraviolet-visible solid diffuse reflection spectrum are not all observed significant change, and titanium dioxide good stability prepared by the present invention is described.
In Fig. 7, (a) being the transmission electron microscope picture of the P25 of embodiment 1, is (b) transmission electron microscope picture of the CIOMP-8 of embodiment 1; (c) be the high resolution transmission electron microscopy figure of the P25 of embodiment 1; (d) be the high resolution transmission electron microscopy figure of the CIOMP-2 of embodiment 1; (e) be the high resolution transmission electron microscopy figure of the CIOMP-6 of embodiment 1; (f) be the high resolution transmission electron microscopy figure of the CIOMP-8 of embodiment 1; Can find out from Fig. 7 (a) and 7 (b), titanium dioxide prepared by P25 and the present invention all presents the irregular nano particle that diameter is about 25nm left and right; From Fig. 7 (c)-(f) can find out, P25, CIOMP-2, CIOMP-6 and CIOMP-8 kernel portion lattice separation of diffraction stripe are 0.35nm, are Anatase (101) crystal face; Fig. 7 illustrates that titanium dioxide prepared by preparation method of the present invention can keep the original pattern of raw material and size constancy substantially.
Fig. 8 be the embodiment of the present invention 1 in differential responses temperature, the X-ray powder diffraction pattern of prepared shades of colour titania powder of differential responses time; As can be seen from Figure 8, along with reaction temperature raises and reaction time prolongation, in the X-ray powder diffraction spectrogram of the titanium dioxide of preparation, occur three new diffraction maximums, laying respectively at 2 θ is 31.3,42.3,46.3 places;
In Fig. 9, (a) be the embodiment of the present invention 1 in differential responses temperature, the Raman spectrogram of prepared shades of colour titania powder of differential responses time; (b) be that the P25 of the embodiment of the present invention 1 and CIOMP-8 are at 144cm
-1raman spectrogram is amplified in main peak displacement; As can be seen from Figure 9, along with reaction temperature raises and reaction time prolongation, the main peak of the Raman spectrum of the titanium dioxide of preparation is subjected to displacement;
In Figure 10, the Ti XPS of the different titania powders of (a) preparing for the embodiment of the present invention 1; (b) the VB XPS of the different titania powders of preparing for the embodiment of the present invention 1; Can find out from Figure 10 (a), along with reaction temperature raises and reaction time prolongation, Ti XPS first moves to low energy direction, then moves to high energy direction gradually; Can find out from Figure 10 (b), titanium dioxide valence band prepared by the present invention changes little in initial reaction stage, but long when too high with reaction temperature when the reaction time, there will be about 0.5eV on move.
In conjunction with Fig. 7-10 explanation principle of the present invention, from Fig. 7 (c)-(f) can find out, along with the increase in reaction temperature and reaction time, metal hydride is subject to thermal activation or decomposition, produce reactive hydrogen atom or metal, reactive hydrogen atom or metal react with titanium dioxide, cause titanium dioxide to produce oxygen vacancies.Along with the increase of oxygen vacancies concentration, the long-range order of titanium dioxide surface crystal is destroyed, thereby surface engenders one deck disordered layer, presents and has TiO
2@TiO
2-xnucleocapsid structure.The appearance of disordered layer also causes occurring three new diffraction maximums in the X-ray powder diffraction spectrogram (Fig. 8) of higher reaction temperatures and longer reaction time titanium dioxide after treatment, they can belong to a series of reduction-state titanium dioxide, for example: Ti
9o
17, Ti
8o
15, Ti
3o
5mixture.Meanwhile, also cause the Raman spectrum (Fig. 9) of titanium dioxide at 144cm
-1the main peak at place is subjected to displacement.Figure 10 (a) can show, along with the increase in reaction temperature and reaction time, titanium dioxide nano-particle Surface Oxygen hole concentration increases gradually, and in initial reaction stage, oxygen vacancies concentration is lower, shows as Ti
3+form, along with reaction carrying out, oxygen vacancies concentration further increases, Ti
3+further be reduced, change the more titanium of lower valency into, therefore cause Ti XPS in titanium dioxide first to move to low energy direction, more gradually to representing that the high energy direction that oxygen vacancies concentration is larger moves.Figure 10 (b) can show, the valence band of titanium dioxide changes little in initial reaction stage, but long when too high with reaction temperature when the reaction time, there will be about 0.5eV on move.In addition, the generation meeting of oxygen vacancies about 0.5-1.0eV place under titanium dioxide conduction band introduces a series of cavity energy bands, thereby the energy gap of the titanium dioxide that narrows makes it have visible absorption, and presents different colours.
Figure 11 be the embodiment of the present invention 1 in differential responses temperature, the photochemical catalyzing hydrogen output of prepared shades of colour titania powder of differential responses time under ultraviolet-visible irradiation schemed over time.Wherein, (a) be 0.05gCIOMP-2, CIOMP-4, CIOMP-6, CIOMP-7 or CIOMP-8, 120mL25% methanol/water mixed solution, the Pt of load 1%, photochemical catalyzing hydrogen output under ultraviolet-visible irradiation is schemed over time, can find out from 11 (a), the photocatalytic activity of CIOMP-1-8 of the present invention is all apparently higher than P25, wherein the highest with CIOMP-6 photocatalytic activity, its product hydrogen activity under ultraviolet-visible irradiation is up to 6.5mmol/gh, be about under the same terms 7.2 times of commercialization titanium dioxide nano photocatalysis agent P25 at present, (b) be the highest CIOMP-6 the recycling under ultraviolet-visible irradiation of Photocatalyzed Hydrogen Production speed, its hydrogen output is schemed over time, can find out from 11 (b), CIOMP-6 is recycling after 8 times, its catalytic activity remains unchanged substantially, illustrates that titanium dioxide prepared by the present invention has good stability, (c) be 0.05g CIOMP-6,120mL25% methanol/water mixed solution, the Pt of load 1%, under visible ray (λ >400nm) irradiates, hydrogen output is schemed over time, can find out from 11 (c), CIOMP-6 also has good visible light catalysis activity, and the hydrogen-producing speed under visible ray (λ >400nm) irradiates is about 180 μ mol/gh, (d) be under simulated solar irradiation, the methyl orange solution of 0.05g CIOMP-6 and P25 photocatalytic degradation 50mL20ppm, methyl orange concentration changes with time figure, methyl orange initial concentration is: 20ppm, can find out from 11 (d), titanium dioxide prepared by the present invention to the Photocatalytic activity of dye molecule methyl orange also higher than commercialized catalyst P25.
Embodiment 2
(1) 0.38g sodium borohydride and 4.0g photochemical catalyst P25 (metal hydride: P25=0.2:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 400 DEG C, keep 120min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains black titanium dioxide powder respectively.
Embodiment 3
(1) 3.8g sodium borohydride and 4.0g photochemical catalyst P25 (metal hydride: P25=2:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 350 DEG C, keep 10min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains black titanium dioxide powder respectively.
Embodiment 4
In conjunction with Fig. 2, embodiment 4 is described
(1) titanium dioxide (Anatase) (metal hydride: titanium dioxide=1:1) of 1.9g sodium borohydride and 4.0g Anatase is ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 300 DEG C-400 DEG C, keep 10-600min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains anatase phase titanium dioxide powder respectively.
In Fig. 2, (a) the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of preparing for the embodiment of the present invention 4, in Fig. 2 (a), curve is followed successively by 400 DEG C of reaction 10h from top to bottom, 350 DEG C of reaction 60min, the ultraviolet-visible solid diffuse reflection spectrum of 300 DEG C of reaction 60min, 300 DEG C of reaction 30min, 300 DEG C of reaction 20min, 300 DEG C of reactions 10min and Anatase; (b) optical photograph of the different titania powders of preparing for the embodiment of the present invention 4; In Fig. 2 (b), Anatase is white, it is light yellow that 300 DEG C of reaction 10min obtain titanium dioxide, 300 DEG C of reaction 20min obtain titanium dioxide for light grey, it is grey that 300 DEG C of reaction 30min obtain titanium dioxide, 300 DEG C of reaction 60min obtain titanium dioxide for blue, and it is black-and-blue that 350 DEG C of reaction 60min obtain titanium dioxide, and it is black that 400 DEG C of reaction 60min obtain titanium dioxide.As can be seen from Figure 2, prepared titanium dioxide presents wide absorption to the visible and near infrared light between 400-900nm, and along with the rising of reaction time and reaction temperature, absorb and strengthen, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of variations to black.
Embodiment 5
In conjunction with Fig. 3, embodiment 5 is described
(1) titanium dioxide (Rutile) (metal hydride: titanium dioxide=1:1) of 1.9g sodium borohydride and 4.0g Rutile Type is ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 300 DEG C-400 DEG C, keep 20-60min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains red schorl phase titanium dioxide powder respectively.
In Fig. 3, (a) the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of preparing for the embodiment of the present invention 5, in 3 (a), curve is followed successively by 400 DEG C of reaction 60min from top to bottom, 375 DEG C of reaction 60min, 350 DEG C of reaction 60min, 300 DEG C of reaction 60min, 300 DEG C of reaction titanium dioxide of obtaining of 20min and the ultraviolet-visible solid diffuse reflection spectrum of Rutile; (b) optical photograph of the different titania powders of preparing for the embodiment of the present invention 5; Wherein, Rutile is white, 300 DEG C of titanium dioxide of obtaining of reaction 20min are light yellow, 300 DEG C of titanium dioxide of obtaining of reaction 60min are grey, 350 DEG C of titanium dioxide of obtaining of reaction 60min are pewter, 375 DEG C of titanium dioxide of obtaining of reaction 60min are for blue, and the titanium dioxide that 400 DEG C of reaction 60min obtain is black.As can be seen from Figure 3, prepared titanium dioxide presents wide absorption to the visible and near infrared light between 400-900nm, and along with the rising of reaction time and reaction temperature, absorb and strengthen, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of variations to black.
Embodiment 6
(1) titanium dioxide (Brookite) (metal hydride: titanium dioxide=1:1) of 1.9g sodium borohydride and 4.0g brookite is ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 400 DEG C, keep 2h, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains black brookite titania powder respectively.
Embodiment 7
In conjunction with Fig. 4, embodiment 7 is described
(1) 1.9g sodium borohydride and 4.0g amorphous titania (metal hydride: titanium dioxide=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 300 DEG C-325 DEG C, keep 30-60min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains titania powder respectively.
In Fig. 4, (a) the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of preparing for the embodiment of the present invention 7, in Fig. 4 (a), curve is followed successively by 325 DEG C of reaction 60min from top to bottom, and (amorphous titania is in the drawings with TiO for 300 DEG C of reaction 60min, 300 DEG C of reaction titanium dioxide of obtaining of 30min and amorphous titania
2represent) ultraviolet-visible solid diffuse reflection spectrum; (b) optical photograph of the different titania powders of preparing for the embodiment of the present invention 7; Wherein, amorphous titania is white, and 300 DEG C of titanium dioxide of obtaining of reaction 30min are light blue, and the titanium dioxide that 300 DEG C of reaction 60min obtain is Dark grey, and the titanium dioxide that 325 DEG C of reaction 60min obtain is black.As can be seen from Figure 4, prepared titanium dioxide presents wide absorption to the visible and near infrared light between 400-900nm, and along with the rising of reaction time and reaction temperature, absorb and strengthen, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of variations to black.
Embodiment 8
In conjunction with Fig. 5, embodiment 8 is described
(1) 1.9g lithium aluminium hydride and 4.0g photochemical catalyst P25 (metal hydride: P25=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 200 DEG C-300 DEG C, keep 30-60min, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains titania powder respectively.
In Fig. 5, (a) the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders of preparing for the embodiment of the present invention 8, in Fig. 5 (a), curve is followed successively by 300 DEG C of reaction 60min from top to bottom, 200 DEG C of reaction 60min, 200 DEG C of reaction titanium dioxide of obtaining of 30min and the ultraviolet-visible solid diffuse reflection spectrum of P25; (b) optical photograph of the different titania powders of preparing for the embodiment of the present invention 8; Wherein, P25 is white, and 200 DEG C of titanium dioxide of obtaining of reaction 30min are for light grey, and the titanium dioxide that 200 DEG C of reaction 60min obtain is grey, and the titanium dioxide that 300 DEG C of reaction 60min obtain is Dark grey.As can be seen from Figure 5, prepared titanium dioxide presents wide absorption to the visible and near infrared light between 400-900nm, and along with the rising of reaction time and reaction temperature, absorb and strengthen, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of variations to black.
Embodiment 9
(1) sodium hydride of 2.0g60% and 4.0g photochemical catalyst P25 (metal hydride: P25=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 400 DEG C, keep 5h, naturally cool to room temperature, obtain crude product;
(3), by the crude product of gained after reaction, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtains navy blue titania powder respectively.
Embodiment 10
(1) 2.1g calcium hydride and 4.0g photochemical catalyst P25 (metal hydride: P25=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 400 DEG C, keep 10h, naturally cool to room temperature, obtain crude product;
(3) by the crude product of gained after reaction, use respectively watery hydrochloric acid, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtain blue titania powder.
Embodiment 11
(1) 2.5g titantium hydride and 4.0g photochemical catalyst P25 (metal hydride: P25=1:1) are ground evenly in mortar, obtain mixture;
(2) mixture is put into porcelain boat, in the atmosphere furnace that is filled with argon gas, with the heating rate of 10 DEG C/min, be heated to 400 DEG C, keep 10h, naturally cool to room temperature, obtain crude product;
(3) by the crude product of gained after reaction, use respectively hydrochloric acid, water and ethanol washing 3 times, 70 DEG C of vacuum drying, obtain blue titania powder.
Obviously, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color, is characterized in that, comprises following step:
(1) metal hydride and titanium dioxide are mixed, obtain mixture;
(2) under inert atmosphere, mixture is added after thermal response at 200-400 DEG C, cooling, obtain crude product;
(3) by crude product washing, vacuum drying, obtain the adjustable titanium dioxide with high efficiency photocatalysis activity of color.
2. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, described metal hydride is (0.2-2) with the amount of substance ratio of titanium dioxide: 1.
3. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 2, is characterized in that, described amount of substance is than being 1:1.
4. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, described in add thermal response time be 5min-10h.
5. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, described metal hydride is sodium borohydride, lithium aluminium hydride, sodium hydride, calcium hydride or titantium hydride.
6. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, it is characterized in that, described titanium dioxide is any one or a few the mixing in anatase phase titanium dioxide, red schorl phase titanium dioxide, brookite titanium dioxide, amorphous titania.
7. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 6, is characterized in that, described titanium dioxide is photochemical catalyst P25.
8. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, in described step (3), adopts water and ethanol washing.
9. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, in described step (3), adopts 30-100 DEG C of vacuum drying.
10. the preparation method of the adjustable titanium dioxide with high efficiency photocatalysis activity of color according to claim 1, is characterized in that, in described step (2), inert atmosphere is argon gas, helium or nitrogen.
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