CN103962117B - Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity - Google Patents
Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity Download PDFInfo
- Publication number
- CN103962117B CN103962117B CN201410187184.7A CN201410187184A CN103962117B CN 103962117 B CN103962117 B CN 103962117B CN 201410187184 A CN201410187184 A CN 201410187184A CN 103962117 B CN103962117 B CN 103962117B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- high efficiency
- color tunable
- efficiency photocatalysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses the preparation method that a kind of Color tunable has the titanium dioxide of high efficiency photocatalysis activity, belong to chemistry and materials science field.The preparation method's cost solving visible light-responsible titanium dioxide in prior art is high, complex steps, poor stability, the non-adjustable and technical problem that catalytic activity is low of the titanium dioxide color prepared.Metal hydride and titanium dioxide first mix by preparation method of the present invention, obtain mixture; Under inert gas shielding, make mixture, at 200-400 DEG C, solid phase reaction occur again, color can be prepared from light gray through the adjustable titanium dioxide of the most Zhongdao black of blueness.Preparation method of the present invention is simple, controlled, cost is low, be convenient to large-scale production, the titanium dioxide Color tunable simultaneously, physicochemical properties are stablized, photocatalytic activity is high, there is extensive use in fields such as automatic cleaning coating, paint, coating, photocatalysis, solar cells.
Description
Technical field
The present invention relates to the preparation method that a kind of Color tunable has the titanium dioxide of high efficiency photocatalysis activity, belong to chemistry and material science.
Background technology
Titanium dioxide is as a kind of semi-conducting material be 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 usually, and be 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 portion of solar spectrum, electricity conversion is less than 2.2% usually.Therefore, how to expand titanium dioxide as seen, even near infrared light absorption, on the one hand make it have colourful color, expand its application in the field such as coating, paint further; On the other hand improve 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.As a kind of synthesis of the black poriferous titanium dioxide based on surface hydriding (Science2011,331,746), the method be by poriferous titanium dioxide at 20 atmospheric hydrogen and 200 DEG C, hydrogenation 5 days, has prepared the black titanium dioxide that energy gap is 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, the methods such as plasma assists hydrogenation, aluminothermy are developed successively.But said method not only needs high temperature, expensive equipment, and complicated operation, consuming time, harsh to ingredient requirement, therefore seriously hinder its large-scale industrial production.In addition, above method is difficult to realize controlledly synthesis to titanium dioxide, and its color and high catalytic activity are difficult to be guaranteed.
Summary of the invention
The object of the invention is to solve that preparation method's cost of visible light-responsible titanium dioxide in prior art is high, complex steps, poor stability, non-adjustable and the technical problem that catalytic activity is low of the titanium dioxide color prepared, provides a kind of Color tunable to have the preparation method of the titanium dioxide of high efficiency photocatalysis activity.
The preparation method with the titanium dioxide of high efficiency photocatalysis activity of Color tunable of the present invention, comprises following step:
(1) metal hydride and titanium dioxide are mixed, obtain mixture;
(2), under an inert atmosphere, after mixture is added thermal response at 200-400 DEG C, cooling, obtains crude product;
(3) by crude product washing, vacuum drying, the titanium dioxide that Color tunable has high efficiency photocatalysis activity is obtained.
Preferably, described metal hydride and the amount of substance of titanium dioxide are than being (0.2-2): 1, more preferably 1:1.
Preferably, the time adding 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; It is further preferred that 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 material, is convenient to large-scale production;
(2) preparation method of the present invention can prepare the titanium dioxide of different colours, and color controllable, can realize from white-pale yellow-light gray-light blue-blueness-dark blue a series of color to black and the preparation of Neutral colour titanium dioxide, solve the difficult problem that titanium dioxide color is single for a long time, be expected to expand the application of titanic oxide material in fields such as paint, coating further, 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 the regulation and control by realizing the selection of raw material and regulation and control product size, pattern;
(4) titanium dioxide that prepared by preparation method of the present invention has good visible light-responded property, high photocatalytic activity (under ultraviolet-visible light irradiates, 7.2 times of commercially available titanium dioxide optical catalyst P25 under the Photocatalyzed Hydrogen Production speed of titanium dioxide prepared by the present invention reaches as high as the same terms); At Photocatalyzed Hydrogen Production, photocatalysis sewage process, purification of air, ultraviolet-visible light sterilization, antiviral, the photocatalysis field such as self-cleaning surface coating have huge potential using value;
(5) titanium dioxide prepared of the present invention to the Photocatalytic activity of dye molecule methyl orange also higher than commercial photocatalytic agent P25.
Accompanying drawing explanation
In Fig. 1, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders that (a) is prepared for the embodiment of the present invention 1, the optical photograph of the different titania powders that (b) is prepared for the embodiment of the present invention 1;
In Fig. 2, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders that (a) is prepared for the embodiment of the present invention 4, the optical photograph of the different titania powders that (b) is prepared for the embodiment of the present invention 4;
In Fig. 3, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders that (a) is prepared for the embodiment of the present invention 5, the optical photograph of the different titania powders that (b) is prepared for the embodiment of the present invention 5;
In Fig. 4, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders that (a) is prepared for the embodiment of the present invention 7, the optical photograph of the different titania powders that (b) is prepared for the embodiment of the present invention 7;
In Fig. 5, the ultraviolet-visible solid diffuse reflection spectrum of the different titania powders that (a) is prepared for the embodiment of the present invention 8, the optical photograph of the different titania powders that (b) is prepared for the embodiment of the present invention 8;
In Fig. 6, (a) is 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 () is 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, the transmission electron microscope picture of the photochemical catalyst P25 that (a) is embodiment 1, (b) is the transmission electron microscope picture of the CIOMP-8 of embodiment 1; The high resolution transmission electron microscopy figure of c photochemical catalyst P25 that () is embodiment 1; D high resolution transmission electron microscopy figure that () is the CIOMP-2 of embodiment 1; E high resolution transmission electron microscopy figure that () is the CIOMP-6 of embodiment 1; F high resolution transmission electron microscopy figure that () is 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 the shades of colour titania powder prepared by the differential responses time;
In Fig. 9, (a) for the embodiment of the present invention 1 is in differential responses temperature, the Raman spectrogram of the shades of colour titania powder prepared by the differential responses time; B photochemical catalyst P25 and CIOMP-8 that () is the embodiment of the present invention 1 is at 144cm
-1main peak shifts amplifies Raman spectrogram;
In Figure 10, TiX-X-ray photoelectron spectroscopy X photoelectron spectroscopy (XPS) of the different titania powders that (a) is prepared for the embodiment of the present invention 1; The valence band photoemission figure (VBXPS) of b different titania powders that () prepares for the embodiment of the present invention 1;
Figure 11 be the embodiment of the present invention 1 in differential responses temperature, the shades of colour titania powder prepared by the differential responses time ultraviolet-visible light irradiate under photochemical catalyzing hydrogen output scheme over time.
Detailed description of the invention
Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, with various crystalline state or amorphous titanium dioxide for raw material, using metal hydride as reducing agent, be there is by low heat temperature solid state reaction preparation the titanium dioxide of adjustable color and high efficiency photocatalysis activity, specifically comprise the following steps:
(1) metal hydride and titanium dioxide mixed grinding is even, obtain mixture;
(2) under an inert atmosphere, mixture is added 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, blue, navy blue is to black, the color prepared as required, in good time stopping reaction, cools in inert atmosphere, obtains 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 during production, energy cost increases;
(3) by crude product with water and ethanol washing several, remove unreacted metal hydride, then at 30-100 DEG C, preferably 70 DEG C, vacuum drying, obtains the titanium dioxide that Color tunable has high efficiency photocatalysis activity.
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, both reaction uniformities are poorer, will make the degree for the treatment of that titanium dioxide reaches identical under same reaction temperature, the required reaction time is longer; And metal hydride and titanium dioxide ratio larger, both reaction uniformities are better, the degree for the treatment of that titanium dioxide reaches identical will be made under same reaction temperature, 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 select 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), the existing forms of titanium dioxide raw material, and both mixed proportions.Also depend in step (2), the 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 is light yellow from white transition, light grey, light blue, blue, a series of color of navy blue to black and the controlled modulation of intermediate state secondary colour.
Principle of the present invention: at an appropriate reaction temperature, metal hydride activated by heat or decomposition, produce reactive hydrogen atom or metal, and reactive hydrogen atom or metal react with titanium dioxide, capture titanium dioxide surface oxygen atom, causes titanium dioxide generation oxygen vacancies.Along with the intensification of the extent of reaction, oxygen vacancies concentration increases, and thus causes titanium dioxide color and photocatalytic activity that corresponding change occurs.
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1
Composition graphs 1,6-11 illustrate 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 being 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, wash 3 times respectively, 70 DEG C of vacuum drying, obtain titania powder with water and ethanol, mark is as table 1.
In Fig. 1, the ultraviolet-visible solid diffuse reflection spectrum of a different titania powders that () prepares 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; The optical photograph of b different titania powders that () prepares for the embodiment of the present invention 1; The color change 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, influx and translocation, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of changes to black.
The color change of the titania powder that table 1 is different temperatures, prepared by the differential responses time
In Fig. 6, (a) is 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 () is 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 titanium dioxide prepared by the present invention is placed for a long time, outward appearance and ultraviolet-visible solid diffuse reflection spectrum all do not observe significant change, and titanium dioxide good stability prepared by the present invention is described.
In Fig. 7, (a) is the transmission electron microscope picture of the P25 of embodiment 1, and (b) is the transmission electron microscope picture of the CIOMP-8 of embodiment 1; C high resolution transmission electron microscopy figure that () is the P25 of embodiment 1; D high resolution transmission electron microscopy figure that () is the CIOMP-2 of embodiment 1; E high resolution transmission electron microscopy figure that () is the CIOMP-6 of embodiment 1; F high resolution transmission electron microscopy figure that () is the CIOMP-8 of embodiment 1; As can be seen 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 about 25nm; Being 0.35nm as can be seen from Fig. 7 (c)-(f), P25, CIOMP-2, CIOMP-6 and CIOMP-8 kernel portion lattice separation of diffraction stripe, is 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 the shades of colour titania powder prepared by the differential responses time; As can be seen from Figure 8, along with reaction temperature raises and reaction time prolongation, the diffraction maximum that in the X-ray powder diffractogram of the titanium dioxide of preparation, appearance three is new, laying respectively at 2 θ is 31.3,42.3,46.3 places;
In Fig. 9, (a) for the embodiment of the present invention 1 is in differential responses temperature, the Raman spectrogram of the shades of colour titania powder prepared by the differential responses time; B () is for P25 and CIOMP-8 of the embodiment of the present invention 1 is at 144cm
-1main peak shifts amplifies Raman spectrogram; 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 TiXPS of the different titania powders that (a) is prepared for the embodiment of the present invention 1; The VBXPS of b different titania powders that () prepares for the embodiment of the present invention 1; As can be seen from Figure 10 (a), along with reaction temperature raises and reaction time prolongation, TiXPS first moves to low energy direction, then moves to high energy direction gradually; As can be seen from Figure 10 (b), titanium dioxide valence band prepared by the present invention is little in initial reaction stage change, but when reacted between long and reaction temperature is too high time, there will be about 0.5eV on move.
Composition graphs 7-10 illustrates principle of the present invention, as can be seen from Fig. 7 (c)-(f), along with reaction temperature and the increase in reaction time, metal hydride activated by heat or decomposition, produce reactive hydrogen atom or metal, reactive hydrogen atom or metal and titanium dioxide react, and 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, thus surface engenders one deck disordered layer, presents and has TiO
2tiO
2-xnucleocapsid structure.The appearance of disordered layer also causes the diffraction maximum that in the X-ray powder diffractogram (Fig. 8) of the titanium dioxide after higher reaction temperatures and the process of longer reaction time, appearance three is new, they can belong to a series of reduction-state titanium dioxide, such as: 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 reaction temperature and the increase in 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 increases further, Ti
3+be reduced further, change the titanium of more lower valency into, therefore cause TiXPS in titanium dioxide first to move to low energy direction, then move to the high energy direction representing oxygen vacancies concentration larger gradually.Figure 10 (b) can show, the valence band of titanium dioxide is little in initial reaction stage change, but when reacted between long and reaction temperature is too high time, there will be about 0.5eV on move.In addition, the generation of oxygen vacancies can introduce a series of hole bands in about 0.5-1.0eV place under titanium dioxide conduction band, thus the energy gap of the titanium dioxide that narrows, make it have visible absorption, and present different colours.
Figure 11 be the embodiment of the present invention 1 in differential responses temperature, the shades of colour titania powder prepared by the differential responses time ultraviolet-visible light irradiate under photochemical catalyzing hydrogen output scheme over time.Wherein, a () is 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 light irradiates is schemed over time, as can be seen 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 ultraviolet-visible light irradiate under product hydrogen activity up to 6.5mmol/gh, to be about under the same terms 7.2 times of commercialization titanium dioxide nano photocatalysis agent P25 at present, b () is the highest CIOMP-6 of Photocatalyzed Hydrogen Production speed recycling under ultraviolet-visible light irradiates, its hydrogen output is schemed over time, as can be seen from 11 (b), CIOMP-6 is after recycling 8 times, its catalytic activity remains unchanged substantially, illustrates that titanium dioxide prepared by the present invention has good stability, c () is 0.05gCIOMP-6,120mL25% methanol/water mixed solution, the Pt of load 1%, under visible ray (λ >400nm) irradiates, hydrogen output is schemed over time, as can be seen 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 μm of ol/gh, d () is under simulated solar irradiation irradiates, the methyl orange solution of 0.05gCIOMP-6 and P25 photocatalytic degradation 50mL20ppm, methyl orange concentration changes with time figure, methyl orange initial concentration is: 20ppm, as can be seen 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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain black titanium dioxide powder.
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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain black titanium dioxide powder.
Embodiment 4
Composition graphs 2 illustrates embodiment 4
(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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain anatase phase titanium dioxide powder.
In Fig. 2, the ultraviolet-visible solid diffuse reflection spectrum of a different titania powders that () prepares 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 reaction 10min and Anatase; The optical photograph of b different titania powders that () prepares 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, influx and translocation, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of changes to black.
Embodiment 5
Composition graphs 3 illustrates embodiment 5
(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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain red schorl phase titanium dioxide powder.
In Fig. 3, the ultraviolet-visible solid diffuse reflection spectrum of a different titania powders that () prepares 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, the ultraviolet-visible solid diffuse reflection spectrum of 300 DEG C of reaction 60min, 300 DEG C of reaction titanium dioxide of obtaining of 20min and Rutile; The optical photograph of b different titania powders that () prepares 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, influx and translocation, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of changes 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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain black brookite titania powder.
Embodiment 7
Composition graphs 4 illustrates embodiment 7
(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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain titania powder.
In Fig. 4, the ultraviolet-visible solid diffuse reflection spectrum of a different titania powders that () prepares 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; The optical photograph of b different titania powders that () prepares 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, influx and translocation, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of changes to black.
Embodiment 8
Composition graphs 5 illustrates embodiment 8
(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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain titania powder.
In Fig. 5, the ultraviolet-visible solid diffuse reflection spectrum of a different titania powders that () prepares 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, the ultraviolet-visible solid diffuse reflection spectrum of 200 DEG C of reaction 60min, 200 DEG C of reaction titanium dioxide of obtaining of 30min and P25; The optical photograph of b different titania powders that () prepares 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, influx and translocation, titanium dioxide color is deepened gradually, presents from white-pale yellow-light gray-light blue-blueness-dark blue a series of changes 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 being 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, wash 3 times with water and ethanol respectively, 70 DEG C of vacuum drying, obtain navy blue titania powder.
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 being 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 watery hydrochloric acid respectively, water and ethanol wash 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 being 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 hydrochloric acid respectively, water and ethanol wash 3 times, 70 DEG C of vacuum drying, obtain blue titania powder.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.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 improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, comprises following step:
(1) metal hydride and titanium dioxide are mixed, obtain mixture;
(2), under an inert atmosphere, after mixture is added thermal response at 200-400 DEG C, cooling, obtains crude product;
(3) by crude product washing, vacuum drying, the titanium dioxide that Color tunable has high efficiency photocatalysis activity is obtained.
2. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, described metal hydride is (0.2-2) with the amount of substance ratio of titanium dioxide: 1.
3. Color tunable according to claim 2 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, described amount of substance is than being 1:1.
4. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, described in add thermal response time be 5min-10h.
5. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, described metal hydride is sodium borohydride, lithium aluminium hydride, sodium hydride, calcium hydride or titantium hydride.
6. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, 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. Color tunable according to claim 6 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, described titanium dioxide is photochemical catalyst P25.
8. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, in described step (3), adopts water and ethanol washing.
9. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, in described step (3), adopts 30-100 DEG C of vacuum drying.
10. Color tunable according to claim 1 has the preparation method of the titanium dioxide of high efficiency photocatalysis activity, it is characterized in that, in described step (2), inert atmosphere is argon gas, helium or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410187184.7A CN103962117B (en) | 2014-05-05 | 2014-05-05 | Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410187184.7A CN103962117B (en) | 2014-05-05 | 2014-05-05 | Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103962117A CN103962117A (en) | 2014-08-06 |
| CN103962117B true CN103962117B (en) | 2016-04-27 |
Family
ID=51232405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410187184.7A Expired - Fee Related CN103962117B (en) | 2014-05-05 | 2014-05-05 | Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103962117B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828865B (en) * | 2015-03-26 | 2016-06-29 | 中国科学院新疆理化技术研究所 | A kind of preparation method of the single brookite titanium dioxide of black |
| CN106179292A (en) * | 2016-07-07 | 2016-12-07 | 石家庄铁道大学 | The ashing nano-TiO of energy responding to visible light2the preparation method of photocatalyst |
| CN106379933B (en) * | 2016-08-26 | 2017-12-29 | 浙江工业大学 | A kind of preparation method of lithium titanate powdery |
| CN106582595B (en) * | 2016-12-28 | 2019-07-23 | 上海应用技术大学 | A kind of blue TiO2The preparation method of catalyst |
| CN107296972A (en) * | 2017-05-31 | 2017-10-27 | 四川建源节能科技有限公司 | It is a kind of to be used for the photochemical catalyst of dispelling abnormal flavor in VMC |
| KR101936043B1 (en) * | 2017-12-29 | 2019-01-08 | 한국세라믹기술원 | Titanium oxide inorganic pigment particle and manufacturing method of the same |
| CN108490738B (en) * | 2018-03-22 | 2020-09-29 | 深圳市华星光电技术有限公司 | Black matrix material composition and manufacturing method of black matrix |
| CN108816211B (en) * | 2018-06-22 | 2021-07-16 | 安徽大学 | Preparation method of blue rutile titanium dioxide ceramic material with high catalytic activity |
| KR102074136B1 (en) * | 2018-09-28 | 2020-02-06 | 한국세라믹기술원 | Functional titanium oxide nanoparticle customized by skin color and capable of preventing whitening and manufacturing method of the same |
| CN109772380B (en) * | 2019-02-25 | 2022-07-05 | 江苏大学 | Hydrogenated titanium dioxide composite three-dimensional flower ball bismuth oxychloride photocatalyst and preparation method thereof |
| CN110526289B (en) * | 2019-07-16 | 2021-10-08 | 南京碧盾环保科技股份有限公司 | Blue anatase phase TiO2Nanocrystals and methods of making the same |
| CN110550655B (en) * | 2019-10-18 | 2022-03-22 | 吉林大学 | Method for preparing titanium dioxide nano particles in gray anatase phase |
| CN110790305A (en) * | 2019-11-27 | 2020-02-14 | 湖南科莱新材料有限公司 | Preparation method of black titanium dioxide powder |
| CN112892515A (en) * | 2021-01-29 | 2021-06-04 | 浙江大学 | All-optical-response titanium dioxide nanotube photocatalyst rich in surface oxygen vacancies and low-temperature preparation method and application thereof |
| CN113262812A (en) * | 2021-05-11 | 2021-08-17 | 赵海涛 | Color-controllable zeolite modification method |
| CN113499762B (en) * | 2021-05-18 | 2022-05-10 | 浙江大学 | Simple preparation method of blue/black titanium dioxide photocatalytic material |
| CN114031112B (en) * | 2021-09-15 | 2023-06-16 | 中国科学技术大学 | Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window |
| CN113896237B (en) * | 2021-10-15 | 2023-08-08 | 广东工业大学 | Preparation method of blue titanium dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623635A (en) * | 2009-08-13 | 2010-01-13 | 湖南理工学院 | Visible light response composite photocatalyst and preparation method thereof |
| CN101884914A (en) * | 2009-05-11 | 2010-11-17 | 中国科学院大连化学物理研究所 | TiO2 photocatalyst for photocatalytic reforming biomass hydrogen preparation and preparation and application |
| CN102247828A (en) * | 2011-05-13 | 2011-11-23 | 西北有色金属研究院 | Hydrotreated TiO2 nanotube array and preparation method thereof |
-
2014
- 2014-05-05 CN CN201410187184.7A patent/CN103962117B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884914A (en) * | 2009-05-11 | 2010-11-17 | 中国科学院大连化学物理研究所 | TiO2 photocatalyst for photocatalytic reforming biomass hydrogen preparation and preparation and application |
| CN101623635A (en) * | 2009-08-13 | 2010-01-13 | 湖南理工学院 | Visible light response composite photocatalyst and preparation method thereof |
| CN102247828A (en) * | 2011-05-13 | 2011-11-23 | 西北有色金属研究院 | Hydrotreated TiO2 nanotube array and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Hydrogen-Treated TiO2 Nanowire Arrays for Photoelectrochemical Water Splitting";Gongming Wang;《nano letters》;20110628;第11卷(第7期);第3027页右栏16-25行，图1c * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103962117A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103962117B (en) | Color tunable has the preparation method of the titanium dioxide of high efficiency photocatalysis activity | |
| Chen et al. | In-situ synthesis of AgNbO3/g-C3N4 photocatalyst via microwave heating method for efficiently photocatalytic H2 generation | |
| Hu et al. | Preparation of flower-like CuS by solvothermal method for photocatalytic, UV protection and EMI shielding applications | |
| Cui et al. | Preparation of ZnIn2S4/K2La2Ti3O10 composites and their photocatalytic H2 evolution from aqueous Na2S/Na2SO3 under visible light irradiation | |
| Shrestha et al. | Self-organized TiO2 nanotubes: Visible light activation by Ni oxide nanoparticle decoration | |
| Lu et al. | Photocatalytic hydrogen production over solid solutions between BiFeO3 and SrTiO3 | |
| CN103736476B (en) | A kind of calcium titanate/calcium oxide composite photo-catalyst and method for making thereof and purposes | |
| Zhao et al. | Unique bar-like sulfur-doped C3N4/TiO2 nanocomposite: excellent visible light driven photocatalytic activity and mechanism study | |
| Chen et al. | Hydrilla derived ZnIn2S4 photocatalyst with hexagonal-cubic phase junctions: A bio-inspired approach for H2 evolution | |
| CN101254467A (en) | Precipitating-hydrothermal preparation with high visible light catalytic activity nano CdxZn1-xS photocatalyst | |
| CN106563485A (en) | Carbon nitride/potassium calcium niobate composite material and preparing method and application thereof | |
| CN102895964A (en) | Preparation method for blue sheet-like titanium dioxide nanomaterial | |
| CN105170173A (en) | Perovskite material/organic polymer compound photocatalyst, preparation and application | |
| CN106000384B (en) | A kind of preparation method and its photocatalytic applications for forming controllable tin-based oxide | |
| CN107162057A (en) | A kind of non-stoichiometry molybdenum oxide material with excellent visible absorption performance and its preparation method and application | |
| Xie et al. | Functions of boric acid in fabricating TiO2 for photocatalytic degradation of organic contaminants and hydrogen evolution | |
| CN103613130B (en) | Preparation method of titanium dioxide nanowire-lead sulfide quantum dot composite material | |
| Wang et al. | Novel Bi4Ti3O12 hollow-spheres with highly-efficient CO2 photoreduction activity | |
| CN104028292A (en) | N-TiO2/C and N-TiO2 and preparation method thereof | |
| CN106975497A (en) | Titanium dioxide nanoplate and copper-zinc-tin-sulfur nano particle hetero-junctions preparation method and application | |
| KR101548296B1 (en) | Manufacturing method of bimetallic transition metal doped titanium dioxide | |
| Asjad et al. | An intriguing case of morphology control and phase transitions in TiO2 nanostructures with enhanced photocatalytic activity | |
| CN103055839A (en) | Composite oxide photocatalyst (Li2TiO3) with lithium halite structure and preparation method thereof | |
| CN102500350A (en) | High-efficiency titanium dioxide composite photocatalyst and preparation method thereof | |
| CN109876814A (en) | A kind of oxygen defect TiO2@ZnFe2O4The preparation method of heterojunction photocatalysis material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160427 Termination date: 20180505 |