CN103771508B - A kind of classification mixed crystal TiO 2micro Nano material, preparation method and its usage - Google Patents
A kind of classification mixed crystal TiO 2micro Nano material, preparation method and its usage Download PDFInfo
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Abstract
The invention belongs to inorganic micro Nano material preparation field, relate to a kind of physical mixed legal system back-up level mixed crystal TiO
2micro Nano material, first described method is prepared by two-dimensional nano sheet by hydrothermal method is respectively the Detitanium-ore-type classification TiO that primitive structure forms
2with rutile TiO
2particle, makes rutile particles evenly be attached to anatase octahedrite surface by solvent afterwards, and under the prerequisite not destroying pattern, low temperature calcination makes both combine closely, final acquisition classification mixed crystal TiO
2micro Nano material.Described Detitanium-ore-type classification TiO
2the diameter of microballoon is at 0.8 ~ 2 μm, and nanometer sheet wide at 50 ~ 100nm, the diameter of rutile particles is at 5 ~ 15nm, and the mass percent of rutile particles is 1 ~ 40%.Classification mixed crystal TiO involved in the present invention
2micro Nano material can be used for photocatalysis field, the absorption property when degradation of methylene blue dyestuff and photocatalysis performance more excellent compared with Degussa P25.
Description
Technical field
The present invention relates to a kind of physical mixed legal system back-up level mixed crystal TiO
2micro Nano material and uses thereof, particularly a kind of Detitanium-ore-type classification TiO assembled by two-dimensional nano sheet
2with the classification mixed crystal TiO of rutile small-particle composition
2micro Nano material, preparation method, and it is in the purposes of photocatalysis field.
Background technology
TiO
2nano material due to its have that satisfactory stability, photocatalysis efficiency are high, environmental friendliness and the advantage such as cheap, become one of the most deep semiconductor material of photocatalysis field people research.TiO
2the physicochemical property such as photocatalytic activity, specific refractory power and its crystal formation, pattern, size, specific surface area and to expose the factors such as crystal face relevant.Therefore, how effectively TiO is regulated and controled
2crystal formation and pattern, make it play various advantage performance better, expand its Application Areas, be the focus of photocatalysis field research always.
In recent years, the research about two-dimension nano materials is increasing, and the micro Nano material being assembled into certain hierarchy by it is the development trend of two-dimensional material from now on.
The earlier application CN103073057A of the applicant discloses a kind of classification mixed crystal TiO
2micro Nano material, described micro Nano material is the flower-like structure that nano wire assembling is formed, and the diameter of described flower-like structure is 2 ~ 4 μm, and nanowire diameter is 10 ~ 30nm, and nanowire length is 0.9 ~ 2 μm, and crystal formation consists of anatase octahedrite-rutile-type mixed crystal.
The applicant formerly submit to but undocumented application CN201310601539.8 discloses a kind of rutile titanium dioxide micro Nano material, described micro Nano material is the classification flower-like structure that nano wire assembling is formed, described flower-like structure diameter is 400 ~ 600nm, nanowire diameter is 5 ~ 10nm, and nanowire length is 200 ~ 300nm.
Micro Nano material disclosed in above-mentioned prior art is the classification flower-like structure that one-dimensional nano line assembling is formed, and limits TiO
2micro Nano material is as the catalytic activity of catalyzer and structural stability.
Summary of the invention
For the problem of prior art, an object of the present invention is the classification mixed crystal TiO providing a kind of novel in shape, excellent performance
2micro Nano material, it has excellent photocatalytic activity, structural stability and uses stablizer.
In order to achieve the above object, present invention employs following technical scheme:
A kind of classification mixed crystal TiO
2micro Nano material, described micro Nano material is assembled the anatase octahedrite TiO with classification flower-like structure formed by two-dimensional nano sheet
2with rutile particles composition, the diameter of described flower-like structure is 0.8 ~ 2 μm, and nanometer sheet is wide is 50 ~ 100nm, and rutile particles diameter is 5 ~ 15nm, and the mass percent of rutile particles is 1 ~ 40%.If classification mixed crystal TiO
2in micro Nano material, rutile content is too much, then the flower-shaped surface of anatase octahedrite can be caused to be covered by rutile completely, decrease classification mixed crystal TiO
2pore structure and specific surface area, thus hinder reactant and TiO
2contact, cause activity decrease.
What the two-dimensional nano sheet in the present invention was orderly is assembled into classification TiO
2micro Nano material, makes TiO
2in use can holding structure stability and stability in use, this is that Catalystization applies the performance that must have.Meanwhile, nano level sheet primitive structure, can shorten the transition time in light induced electron and hole, effectively improve separation rate, thus improves the photocatalytic activity of material.And two-dimensional nano sheet primitive structure can be fully utilized, and compared with one-dimensional nano line, significantly increases the contact area of light-catalyzed reaction, thus further increases photocatalytic activity and the structural stability of material.
The duplex grain structure that another structural advantage of material of the present invention is made up of anatase octahedrite and rutile.The Mixed crystal effect of anatase octahedrite-rutile-type improves classification mixed crystal TiO simultaneously
2micro Nano material is as the catalytic activity of catalyzer.The heterojunction structure that two-phase is formed, due to the difference of position of energy band, light induced electron can migrate to rutile from anatase octahedrite, thus the effective separation causing photo-generate electron-hole right, finally improve photocatalytic activity.
The present invention, effectively in conjunction with sheet classification micro nano structure and anatase octahedrite-rutile-type duplex grain structure, obtains catalytic activity and all very excellent classification mixed crystal TiO of structural stability
2micro Nano material.
The diameter of described flower-like structure is 0.8 ~ 2 μm, such as 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm or 1.9 μm, preferably 1 ~ 1.5 μm.
Described nanometer sheet is wide is 50 ~ 100nm, such as 53nm, 56nm, 59nm, 62nm, 65nm, 68nm, 70nm, 71nm, 74nm, 76nm, 77nm, 80nm, 83nm, 85nm, 86nm, 89nm, 92nm, 95nm or 98nm, preferably 60 ~ 70nm.
The diameter of rutile particles is 5 ~ 15nm, such as 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm or 14nm, preferably 8 ~ 10nm.
In the multiphase of anatase octahedrite and rutile, the mass percent of rutile particles is 1 ~ 40%, such as 2%, 5%, 8%, 11%, 14%, 17%, 20%, 23%, 26%, 29%, 32%, 35%, 37% or 39%, preferably 3 ~ 30%.
Two of object of the present invention is to provide a kind of classification mixed crystal TiO as above
2the preparation method of micro Nano material, described method, by mixed solvent, will be the Detitanium-ore-type classification TiO that primitive structure is formed by two-dimensional nano sheet
2carry out physical mixed with rutile small-particle, prepare classification mixed crystal TiO
2micro Nano material.
A kind of classification mixed crystal TiO as above
2the preparation method of micro Nano material, described method comprises the steps:
(1) metal Ti powder is put into the mixing solutions of hydrogen peroxide and nitric acid, condensing reflux 1 ~ 3h under the oil bath of 80 ~ 120 DEG C, obtain orange solution, at 120 ~ 200 DEG C, carry out hydro-thermal reaction with NaOH solution, the reaction times is 1 ~ 10h, after naturally cooling to room temperature, by product centrifugation, washing to pH value is 6.5 ~ 7.5, and drying, calcines and obtain Detitanium-ore-type classification TiO for 300 ~ 500 DEG C
2;
(2) organic compound of titanium is dropwise added drop-wise in the mixing solutions of concentrated hydrochloric acid and low-carbon alcohol, stir in hydrothermal reaction kettle, water is mixed with above-mentioned solution, after stirring 10 ~ 60min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction, after naturally cooling to room temperature, product is centrifugal, washing, drying, namely obtains rutile particles;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2with rutile particles by solvent, stir, centrifugal, washing, dry, 200 ~ 300 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
Described Detitanium-ore-type classification TiO
2the i.e. anatase octahedrite TiO with classification flower-like structure of two-dimensional nano sheet assembling formation
2.
First the present invention prepares by two-dimensional nano sheet by hydrothermal method is respectively the Detitanium-ore-type classification TiO that primitive structure forms
2and rutile TiO
2particle, makes rutile particles evenly be attached to anatase octahedrite TiO by solvent afterwards
2surface, under the prerequisite not destroying pattern, low temperature calcination makes both combine closely, final acquisition classification mixed crystal TiO
2micro Nano material.
The concentration of the Ti powder after dissolving in described step (1) is 0.067 ~ 1.33mol/L, Ti powder containing 0.067 ~ 1.33mol in the mixing solutions of i.e. often liter of hydrogen peroxide and nitric acid, such as 0.067mol/L, 0.09mol/L, 0.1mol/L, 0.4mol/L, 0.63mol/L, 0.75mol/L, 0.9mol/L, 1.1mol/L, 1.33mol/L.When Ti powder is excessive, reaction not exclusively, easily causes wastage of material; And during titanium valve quantity not sufficient, reaction yield is very low, conventional efficient is low.
In described step (1), the concentration of hydrogen peroxide is at 5 ~ 10mol/L, hydrogen peroxide containing 5 ~ 10mol in the mixing solutions of i.e. often liter of hydrogen peroxide and nitric acid, such as 5mol/L, 5.5mol/L, 6mol/L, 6.2mol/L, 6.5mol/L, 6.9mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.3mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 9.6mol/L or 10mol/L, preferably 5.4 ~ 9.6mol/L.When hydrogen peroxide concentration is low, easily to be formed or the nano wire that is scattered or one-dimensional nano line are microballoon or the hexagon sheet output of primitive, stable sheet grading material can not be formed; And hydrogen peroxide concentration too high time, and NaOH mixing after, easily stagnate, stir insufficient, product heterogeneity.
In described step (1), the concentration of nitric acid is 0.1 ~ 1mol/L, nitric acid containing 0.1 ~ 1mol in the mixing solutions of i.e. often liter of hydrogen peroxide and nitric acid, preferably 0.2 ~ 0.9mol/L, such as 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.49mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, 0.65mol/L, 0.7mol/L, 0.75mol/L, 0.8mol/L, 0.83mol/L, 0.85mol/L, 0.9mol/L, 0.95mol/L or 0.96mol/L.Concentration of nitric acid, within the scope of this, fully could dissolve Ti powder.
In described step (1), the concentration of NaOH is 5 ~ 12mol/L, such as 5.5mol/L, 6mol/L, 6.5mol/L, 6.9mol/L, 7mol/L, 7.3mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 8.6mol/L, 9mol/L, 9.5mol/L, 9.8mol/L, 10mol/L, 10.5mol/L, 11mol/L or 11.5mol/L, preferably 5.8 ~ 11.2mol/L.When NaOH concentration is too low, reaction product is uneven, and output is very low.
Step (1) described oil bath temperature is 80 ~ 120 DEG C, such as 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C, 98 DEG C, 100 DEG C, 102 DEG C, 104 DEG C, 106 DEG C, 108 DEG C, 110 DEG C, 112 DEG C, 114 DEG C, 116 DEG C or 118 DEG C.
Step (1) described return time is 1 ~ 3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8h.
The temperature of step (1) described hydro-thermal reaction is 120 ~ 200 DEG C, such as 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C.Hydrothermal temperature is too low, does not reach the energy needed for reaction, can not form sheet grading material.
The time of step (1) described hydro-thermal reaction is 1 ~ 10h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h.The hydro-thermal reaction time is too short, is merely able to form granular product.
Step (1) step (1) described washing, for first to adopt pickling, after pickling 1 ~ 5 time, then is 6.5 ~ 7.5 by deionized water wash to pH value, such as 6.6,6.7,6.8,6.9,7,7.1,7.2,7.3 or 7.4.Described acid be hydrochloric acid or/and nitric acid etc., acid concentration is 0.05 ~ 0.5mol/L, such as 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L or 0.45mol/L.The object of this step is sodium ion residual in hydrogen ion substitution product, form titanate, otherwise the sodium ion in product can not be removed in calcining, finally can not form TiO
2.
Step (1) described calcining temperature is 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C or 490 DEG C.This step object is that dried product is titanate structure, could crystallization be Detitanium-ore-type TiO after calcining
2, but temperature is too high, easily causes flower-shaped hierarchy to subside, and specific surface area declines.
The organic compound of titanium is selected from the mixture of any one or at least two kinds in tetrabutyl titanate, titanium isopropylate or tetraethyl titanate in described step (2), preferred tetrabutyl titanate and/or titanium isopropylate, further preferred tetrabutyl titanate.
In described step (2), the concentration of organic compound in total solution of titanium is 0.01 ~ 1mol/L, such as 0.03mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, 0.65mol/L, 0.7mol/L, 0.75mol/L, 0.8mol/L, 0.85mol/L, 0.9mol/L or 0.95mol/L, preferably 0.1 ~ 0.3mol/L.The solution obtained after described total solution and step (2) mix with water.The organic concentration of titanium is too high, and reaction not exclusively, easily causes wastage of material.
Low-carbon alcohol is selected from the mixture of any one or at least two kinds in ethanol, propyl alcohol or butanols in described step (2), preferred alcohol, further preferred dehydrated alcohol.
Preferably, step (2) described water is deionized water, in described step (2), the volume ratio of low-carbon (LC) alcohol and water is 1:30 ~ 30:1, such as 1:25,1:20,1:15,1:10,1:5,1:4,1:1,2:1,5:1,8:1,10:1,13:1,15:1,18:1,20:1,22:1,24:1,26:1 or 28:1, preferred 15:1 ~ 1:15.
In described step (2), concentrated hydrochloric acid adds the formation promoting rutile particles, its concentration is 0.1 ~ 10mol/L, such as 0.3mol/L, 0.8mol/L, 1mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 3.9mol/L, 4mol/L, 4.5mol/L, 4.6mol/L, 5mol/L, 5.5mol/L, 5.8mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 8.9mol/L, 9mol/L or 9.5mol/L, preferably 1 ~ 2mol/L.
Described concentrated hydrochloric acid refers to the hydrochloric acid of massfraction more than 37%.
The described stirring 10 ~ 60min of step (2), such as, stir 13min, 16min, 19min, 22min, 25min, 28min, 31min, 34min, 37min, 40min, 43min, 46min, 49min, 52min, 55min or 58min.Churning time is long, and in final product, rutile particles pattern will be grown up, and cannot obtain the rutile small-particle that diameter is 5 ~ 15nm.
In described step (2), hydrothermal temperature is at 100 ~ 150 DEG C, such as 105 DEG C, 106 DEG C, 110 DEG C, 113 DEG C, 115 DEG C, 116 DEG C, 120 DEG C, 123 DEG C, 125 DEG C, 129 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 148 DEG C or 149 DEG C.
In described step (2), the hydro-thermal reaction time is at 12 ~ 48h, such as 12h, 15h, 18h, 20h, 23h, 25h, 29h, 32h, 36h, 38h, 40h, 42h, 44h, 45h or 47h.
In described step (3), solvent is that alcoholic solvent is or/and salt kind solvent, the mixture of any one or at least two kinds in preferred alcohol, Virahol, butanols, tertiary sodium phosphate or sodium hexametaphosphate solution, the mixture in further preferred alcohol, Virahol or trisodium phosphate aqueous solution.
Described in step (3), the volume of solvent is without concrete restriction, the Detitanium-ore-type classification TiO that only need obtain at mixing step (1) and step (2)
2with in the process of rutile particles, will both submergences.
In described step (3), the concentration of sodium phosphate aqueous solution is at 0.01 ~ 0.1mol/L.
In described step (3), churning time is 0.5 ~ 10h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h.Churning time is too short, and both can not full and uniformly contact, and product morphology is uneven.
In described step (3), calcining temperature is at 200 ~ 300 DEG C, such as 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C or 290 DEG C.Before calcining, anatase octahedrite TiO
2only simply be adsorbed in rutile particles, after calcining, anatase octahedrite TiO
2can better be adsorbed in rutile particles, both combine closely, anatase octahedrite TiO
2difficult drop-off, improves its stability in use.
Three of object of the present invention is to provide a kind of classification mixed crystal TiO as above
2the purposes of micro Nano material, it is for photocatalysis field.
Compared with the prior art, the present invention has following beneficial effect:
(1) classification mixed crystal TiO of the present invention
2micro Nano material combines the advantage of classification micro nano structure and duplex grain structure, possesses excellent catalytic activity, structural stability and stability in use;
(2) the classification mixed crystal TiO adopting method of the present invention to obtain
2micro Nano material preparation technology flow process is simple, and cheaper starting materials is easy to get, easy to operate, is easy to promote the use of;
(3) classification mixed crystal TiO of the present invention
2the absorption property of micro Nano material when degradation of methylene blue dyestuff and photocatalytic activity more excellent compared with Degussa P25.
Accompanying drawing explanation
The Detitanium-ore-type classification TiO of Fig. 1 obtained by embodiment 1
2the SEM figure of micro Nano material;
The rutile TiO of Fig. 2 obtained by embodiment 1
2short grained TEM figure;
The classification mixed crystal TiO of Fig. 3 obtained by embodiment 1
2the SEM figure of micro Nano material;
The classification mixed crystal TiO of Fig. 4 obtained by embodiment 1
2the XRD figure of micro Nano material;
The classification mixed crystal TiO of Fig. 5 obtained by embodiment 1
2the photocatalytic activity comparison diagram of micro Nano material and commercial P25 degradation of methylene blue solution;
The classification mixed crystal TiO of Fig. 6 obtained by embodiment 1
2micro Nano material repeatedly circulate degraded methylene blue solution photocatalytic activity figure;
The classification mixed crystal TiO of Fig. 7 obtained by embodiment 2
2the SEM figure of micro Nano material;
The classification mixed crystal TiO of Fig. 8 obtained by embodiment 2
2the XRD figure of micro Nano material.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1
(1) 0.67mol/L metal Ti powder is put into the mixing solutions (cumulative volume remains on 150mL) of the hydrogen peroxide of 9mol/L and the nitric acid of 0.8mol/L, condensing reflux 2h under the oil bath of 80 DEG C, obtain orange solution, at 150 DEG C, hydro-thermal reaction is carried out with the NaOH solution of 10mol/L, reaction times is 5h, after naturally cooling to room temperature, by product centrifugation, it is 7 that 0.1mol/L nitric acid washs 1 after washing to pH value, dry, 450 DEG C calcine and obtain Detitanium-ore-type classification TiO
2;
(2) tetrabutyl titanate of 0.2mol/L is dropwise added drop-wise in the concentrated hydrochloric acid of 1.36mol/L and the mixing solutions of 3mL dehydrated alcohol, stir in polytetrafluoroethylliner liner, 31mL deionized water is mixed with above-mentioned solution, after stirring 30min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction at 120 DEG C, the reaction times is 24h.After naturally cooling to room temperature, product is centrifugal, washing, dry, namely obtain rutile-type small-particle;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2mixed by 30mL Virahol with rutile small-particle, centrifugal after stirring 30min, washing, dry, 300 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
Figure 1 shows that the Detitanium-ore-type classification TiO that embodiment 1 is obtained
2the field emission scanning electron microscope figure of micro Nano material, as can be seen from Fig., the diameter of this flower-like microsphere is about 1 μm, and be made up of nanometer sheet primitive structure, the wide of nanometer sheet is about 90nm.
Figure 2 shows that the short grained transmission electron microscope picture of rutile titanium dioxide that embodiment 1 is obtained, as can be seen from the figure the short grained diameter of rutile is about 6nm.
Figure 3 shows that the classification mixed crystal TiO that embodiment 1 is obtained
2the field emission scanning electron microscope figure of micro Nano material, as can be seen from Fig., the classification TiO that this material is made up of two-dimensional sheet primitive structure
2micro Nano material and small-particle form jointly.
Figure 4 shows that the classification mixed crystal TiO that embodiment 1 is obtained
2the X ray diffracting spectrum of micro Nano material, can find out the mixed crystal that this material is made up of anatase octahedrite and rutile, and wherein rutile phase content is 21%.
Fig. 5 is the classification mixed crystal TiO that embodiment 1 obtains
2the Degussa P25 nano-TiO of micro Nano material and equal in quality
2add in the methylene blue solution of same concentrations same volume, stir under dark condition 1h with reach adsorption desorption balance after, under UV-irradiation, methylene blue solution concentration is schemed over time, demonstrates comparatively Degussa P25 and Detitanium-ore-type classification TiO
2higher photocatalysis performance.
Fig. 6 is the classification mixed crystal TiO that embodiment 1 obtains
2micro Nano material adds in same concentrations same volume methylene blue solution, and the methylene blue solution concentration after three times that circulates is schemed over time, demonstrates classification mixed crystal TiO
2the stability in use that micro Nano material is good.
Embodiment 2
(1) 0.67mol/L metal Ti powder is put into the mixing solutions (cumulative volume remains on 150mL) of the hydrogen peroxide of 9mol/L and the nitric acid of 0.6mol/L, condensing reflux 2h under the oil bath of 90 DEG C, obtain orange solution, at 150 DEG C, hydro-thermal reaction is carried out with the NaOH solution of 10mol/L, reaction times is 5h, after naturally cooling to room temperature, by product centrifugation, it is 7 that 0.05mol/L nitric acid washs 5 after washing to pH value, dry, 350 DEG C calcine and obtain Detitanium-ore-type classification TiO
2;
(2) tetrabutyl titanate of 0.3mol/L is dropwise added drop-wise in the concentrated hydrochloric acid of 4mol/L and the mixing solutions of 3mL ethanol, stir in polytetrafluoroethylliner liner, 31mL deionized water is mixed with above-mentioned solution, after stirring 30min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction at 120 DEG C, the reaction times is 24h.After naturally cooling to room temperature, product is centrifugal, washing, dry, namely obtain rutile-type small-particle;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2mixed by 50mL ethanol with rutile small-particle, centrifugal after stirring 10h, washing, dry, 200 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
Figure 7 shows that the classification mixed crystal TiO that embodiment 2 is obtained
2the field emission scanning electron microscope figure of micro Nano material, as can be seen from Fig., the classification TiO that this material is made up of two-dimensional sheet primitive structure
2micro Nano material and small-particle form jointly, and wherein the diameter of grading material is 864nm, the wide 70nm of sheet, and the short grained mean diameter of rutile is 10nm.Fig. 8 is the classification mixed crystal TiO that embodiment 2 obtains
2the X ray diffracting spectrum of micro Nano material, can find out the mixed crystal that this material is made up of anatase octahedrite and rutile, and wherein rutile phase content is 26%.
Embodiment 3
(1) 0.067mol/L metal Ti powder is put into the mixing solutions (cumulative volume remains on 150mL) of the hydrogen peroxide of 5mol/L and the nitric acid of 0.1mol/L, condensing reflux 1h under the oil bath of 80 DEG C, obtain orange solution, at 120 DEG C, hydro-thermal reaction is carried out with the NaOH solution of 5mol/L, reaction times is 1h, after naturally cooling to room temperature, by product centrifugation, it is 6.5 that 0.5mol/L nitric acid washs 2 after washing to pH value, dry, 450 DEG C calcine and obtain Detitanium-ore-type classification TiO
2;
(2) tetrabutyl titanate of 0.02mol/L is dropwise added drop-wise in the concentrated hydrochloric acid of 0.1mol/L and the mixing solutions of 3mL ethanol, stir in polytetrafluoroethylliner liner, 90mL deionized water is mixed with above-mentioned solution, after stirring 10min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction at 100 DEG C, the reaction times is 12h.After naturally cooling to room temperature, product is centrifugal, washing, dry, namely obtain rutile-type small-particle;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2mixed by 0.01mol/L trisodium phosphate aqueous solution with rutile small-particle, centrifugal after stirring 2h, washing, dry, 250 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
The classification mixed crystal TiO that embodiment 3 is obtained
2micro Nano material hierarchy diameter is 802nm, the wide 50nm of nanometer sheet, and the short grained mean diameter of rutile is 5nm, rutile content about 1% in material.
Embodiment 4
(1) 1.33mol/L metal Ti powder is put into the mixing solutions (cumulative volume remains on 150mL) of the hydrogen peroxide of 10mol/L and the nitric acid of 1mol/L, condensing reflux 3h under the oil bath of 120 DEG C, obtain orange solution, at 120 DEG C, hydro-thermal reaction is carried out with the NaOH solution of 12mol/L, reaction times is 10h, after naturally cooling to room temperature, by product centrifugation, 0.1mol/L salt acid elution 1 after washing is 7.5 to pH value, dry, 450 DEG C calcine and obtain Detitanium-ore-type classification TiO
2;
(2) tetrabutyl titanate of 1mol/L is dropwise added drop-wise in the concentrated hydrochloric acid of 1mol/L and the mixing solutions of 20mL ethanol, stir in polytetrafluoroethylliner liner, 15mL deionized water is mixed with above-mentioned solution, after stirring 60min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction at 150 DEG C, the reaction times is 48h.After naturally cooling to room temperature, product is centrifugal, washing, dry, namely obtain rutile-type small-particle;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2mixed by 0.1mol/L trisodium phosphate aqueous solution with rutile small-particle, centrifugal after stirring 3h, washing, dry, 300 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
The classification mixed crystal TiO that embodiment 4 is obtained
2micro Nano material hierarchy diameter is 2 μm, the wide 100nm of nanometer sheet, and the short grained mean diameter of rutile is 10nm, rutile content about 12% in material.
Embodiment 5
(1) 0.95mol/L metal Ti powder is put into the mixing solutions (cumulative volume remains on 150mL) of the hydrogen peroxide of 8mol/L and the nitric acid of 0.9mol/L, condensing reflux 2h under the oil bath of 110 DEG C, obtain orange solution, at 200 DEG C, hydro-thermal reaction is carried out with the NaOH solution of 10mol/L, reaction times is 10h, after naturally cooling to room temperature, by product centrifugation, 0.5mol/L salt acid elution 3 after washings are 7.5 to pH value, dry, 450 DEG C calcine and obtain Detitanium-ore-type classification TiO
2;
(2) tetrabutyl titanate of 0.5mol/L is dropwise added drop-wise in the concentrated hydrochloric acid of 10mol/L and the mixing solutions of 10mL ethanol, stir in polytetrafluoroethylliner liner, 29mL deionized water is mixed with above-mentioned solution, after stirring 40min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction at 120 DEG C, the reaction times is 36h.After naturally cooling to room temperature, product is centrifugal, washing, dry, namely obtain rutile-type small-particle;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2mixed by 50mL Virahol with rutile small-particle, centrifugal after stirring 8h, washing, dry, 290 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
The classification mixed crystal TiO that embodiment 5 is obtained
2micro Nano material hierarchy diameter is 1.6 μm, the wide 70nm of sheet, and the short grained mean diameter of rutile is 15nm, rutile content about 40% in material.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (31)
1. a classification mixed crystal TiO
2micro Nano material, is characterized in that, described micro Nano material is assembled the anatase octahedrite TiO with classification flower-like structure formed by two-dimensional nano sheet
2with rutile particles composition, the diameter of described flower-like structure is 0.8 ~ 2 μm, and nanometer sheet is wide is 50 ~ 100nm, and rutile particles diameter is 5 ~ 15nm, and the mass percent of rutile particles is 1 ~ 40%; Its preparation method is: first preparing by two-dimensional nano sheet respectively by hydrothermal method is the Detitanium-ore-type classification TiO that primitive structure forms
2and rutile TiO
2particle, makes rutile particles evenly be attached to anatase octahedrite TiO by solvent afterwards
2surface, under the prerequisite not destroying pattern, low temperature calcination makes both combine closely, final acquisition classification mixed crystal TiO
2micro Nano material, described low temperature calcination temperature is 200 ~ 300 DEG C.
2. micro Nano material as claimed in claim 1, it is characterized in that, the diameter of described flower-like structure is 1 ~ 1.5 μm.
3. micro Nano material as claimed in claim 1, it is characterized in that, described nanometer sheet is wide is 60 ~ 70nm.
4. micro Nano material as claimed in claim 1, it is characterized in that, the diameter of described rutile particles is 8 ~ 10nm.
5. micro Nano material as claimed in claim 1, it is characterized in that, the mass percent of described rutile particles is 3 ~ 30%.
6. the classification mixed crystal TiO as described in one of claim 1-5
2the preparation method of micro Nano material, is characterized in that, described method comprises the steps:
(1) metal Ti powder is put into the mixing solutions of hydrogen peroxide and nitric acid, condensing reflux 1 ~ 3h under the oil bath of 80 ~ 120 DEG C, obtain orange solution, at 120 ~ 200 DEG C, carry out hydro-thermal reaction with NaOH solution, the reaction times is 1 ~ 10h, after naturally cooling to room temperature, by product centrifugation, washing to pH value is 6.5 ~ 7.5, and drying, calcines and obtain Detitanium-ore-type classification TiO for 300 ~ 500 DEG C
2;
(2) organic compound of titanium is dropwise added drop-wise in the mixing solutions of concentrated hydrochloric acid and low-carbon alcohol, stir in hydrothermal reaction kettle, water is mixed with above-mentioned solution, after stirring 10 ~ 60min, stainless steel cauldron is put in inner bag sealing, carry out hydro-thermal reaction, after naturally cooling to room temperature, product is centrifugal, washing, drying, namely obtains rutile particles;
(3) by Detitanium-ore-type classification TiO that step (1) and step (2) obtain
2with rutile particles by solvent, stir, centrifugal, washing, dry, 200 ~ 300 DEG C of calcinings, finally obtain classification mixed crystal TiO
2micro Nano material.
7. method as claimed in claim 6, is characterized in that, the concentration of the Ti powder after dissolving in described step (1) is 0.067 ~ 1.33mol/L.
8. method as claimed in claim 6, is characterized in that, in described step (1), the concentration of hydrogen peroxide is at 5 ~ 10mol/L.
9. method as claimed in claim 8, is characterized in that, in described step (1), the concentration of hydrogen peroxide is at 5.4 ~ 9.6mol/L.
10. method as claimed in claim 6, is characterized in that, in described step (1), the concentration of nitric acid is 0.1 ~ 1mol/L.
11. methods as claimed in claim 10, is characterized in that, in described step (1), the concentration of nitric acid is 0.2 ~ 0.9mol/L.
12. methods as claimed in claim 6, is characterized in that, in described step (1), the concentration of NaOH is 5 ~ 12mol/L.
13. methods as claimed in claim 12, is characterized in that, in described step (1), the concentration of NaOH is 5.8 ~ 11.2mol/L.
14. methods as claimed in claim 6, is characterized in that, step (1) described washing, for first to adopt pickling, after pickling 1 ~ 5 time, then is 6.5 ~ 7.5 by deionized water wash to pH value.
15. methods as claimed in claim 14, is characterized in that, described acid be hydrochloric acid or/and nitric acid, the concentration of described acid is 0.05 ~ 0.5mol/L.
16. methods as claimed in claim 6, is characterized in that, the organic compound of titanium is selected from the mixture of any one or at least two kinds in tetrabutyl titanate, titanium isopropylate or tetraethyl titanate in described step (2).
17. methods as claimed in claim 16, is characterized in that, in described step (2), the organic compound of titanium is selected from tetrabutyl titanate and/or titanium isopropylate.
18. methods as claimed in claim 17, is characterized in that, in described step (2), the organic compound of titanium is selected from tetrabutyl titanate.
19. methods as claimed in claim 6, is characterized in that, in described step (2), the concentration of organic compound in total solution of titanium is 0.01 ~ 1mol/L.
20. methods as claimed in claim 19, is characterized in that, in described step (2), the concentration of organic compound in total solution of titanium is 0.1 ~ 0.3mol/L.
21. methods as claimed in claim 6, is characterized in that, low-carbon alcohol is selected from the mixture of any one or at least two kinds in ethanol, propyl alcohol or butanols in described step (2).
22. methods as claimed in claim 21, is characterized in that, in described step (2), low-carbon alcohol is selected from ethanol.
23. methods as claimed in claim 6, it is characterized in that, step (2) described water is deionized water, and in described step (2), the volume ratio of low-carbon (LC) alcohol and water is 1:30 ~ 30:1.
24. methods as claimed in claim 23, is characterized in that, in described step (2), the volume ratio of low-carbon (LC) alcohol and water is 15:1 ~ 1:15.
25. methods as claimed in claim 6, is characterized in that, in described step (2), hydrothermal temperature is at 100 ~ 150 DEG C, and the hydro-thermal reaction time is at 12 ~ 48h.
26. methods as claimed in claim 6, is characterized in that, in described step (3), solvent is that alcoholic solvent is or/and salt kind solvent.
27. methods as claimed in claim 26, is characterized in that, solvent is the mixture of any one or at least two kinds in ethanol, Virahol, butanols, tertiary sodium phosphate or sodium hexametaphosphate solution in described step (3).
28. methods as claimed in claim 27, is characterized in that, in described step (3), solvent is ethanol, Virahol or trisodium phosphate aqueous solution.
29. methods as claimed in claim 28, is characterized in that, the concentration of described trisodium phosphate aqueous solution is 0.01 ~ 0.1mol/L.
30. methods as claimed in claim 6, is characterized in that, in described step (3), churning time is 0.5 ~ 10h.
31. 1 kinds of classification mixed crystal TiO as described in one of claim 1-5
2the purposes of micro Nano material, is characterized in that, described micro Nano material is used for photocatalysis field.
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| CN106915769B (en) * | 2017-03-31 | 2019-01-22 | 福州大学 | A kind of ultra-thin mixed crystal titanium dioxide nanoplate and its preparation method and application |
| CN108686592B (en) * | 2018-05-21 | 2020-11-13 | 陕西科技大学 | Preparation method of sea urchin-shaped double-shell hollow microspheres |
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