CN103816887A - Gadolinium-ion-doped mesoporous hollow nano titanium dioxide ball - Google Patents
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- CN103816887A CN103816887A CN201410108375.XA CN201410108375A CN103816887A CN 103816887 A CN103816887 A CN 103816887A CN 201410108375 A CN201410108375 A CN 201410108375A CN 103816887 A CN103816887 A CN 103816887A
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Abstract
The invention discloses a gadolinium-ion-doped mesoporous hollow nano titanium dioxide ball and a preparation method thereof, and belongs to the photocatalysis field. The preparation method takes a nano silicon dioxide ball which is synthesized by a Stober method as a template; the preparation method comprises the following steps: coating the outer side of the nano silicon dioxide ball with gadolinium-ion-doped titanium dioxide through a sol-gel method, sintering at a high temperature to convert amorphous titanium dioxide to titanium dioxide of anatase, then corroding an inner silicon dioxide core by using a sodium hydroxide solution, washing and centrifuging to obtain a gadolinium-ion-doped mesoporous hollow nano titanium dioxide ball which is high in catalytic efficiency. The titanium dioxide is made into mesoporous hollow titanium dioxide, so that the reaction specific surface area is enlarged; the doped gadolinium ions inhibit compounding between photons and cavities, thus prolonging service lives of the photons and the cavities, improving utilization rates of the photons and the cavities and improving the catalytic efficiency.
Description
Technical field
The invention belongs to photocatalysis field, be specifically related to meso-porous hollow nano titanium dioxide ball of a kind of gadolinium ion doping and preparation method thereof.
Background technology
Since TiO has been delivered at Nature in two scholar's Hashimoto Herens (Hashimoto) He Teng island clear (Fujishima) of Tokyo Univ Japan in 1972
2electrode can brine electrolysis under visible ray after, optically catalytic TiO 2 mechanism probe into and apply the heat subject that becomes researchers.
Through the research of decades, titanium dioxide is considered to have most the conductor oxidate of using value, and its application relates to sensor, photonic crystal, energy storage device and photochemical catalyst etc.Compare with other catalyst, optically catalytic TiO 2 activity is high, and chemical stability is good, low toxicity, and based on these features, titanium dioxide becomes the first-selection of photocatalysis field.Under illumination condition, titanium dioxide can produce electronics and the hole with redox ability, electronics and hole can with the surperficial organic matter generation redox reaction that is adsorbed on titanium dioxide, but the recombination velocity in electronics and hole is fast, cause some electronics and hole also not to have enough time to react compound, catalytic efficiency is low, so that suppresses electronics and hole compoundly becomes the primary of research, suppress compound the most effectively doped metal ion in titanium dioxide lattice, nonmetallic ion or the nonmetallic ion in electronics and hole.These ions can form and catch trap in titanium dioxide lattice, and electronics or hole are temporarily caught, and have extended the life-span in electronics and hole, have improved catalytic efficiency.In order to improve photocatalysis area, titanium dioxide is generally made into spherical, has improved response area simultaneously.The present invention selects gadolinium ion as doping ion, because gadolinium ion belongs to transition metal ions, the critical nature of gadolinium is that on 7 tracks, each track has an electronics, it is the unpaired electron of maximum number in rare earth element, can farthest suppress the compound of electronics and hole, simultaneously in order to improve the area of reaction, the present invention is take nano silicon as template, titanium dioxide is done to mesoporous one-tenth hollow, specific area is larger.
Summary of the invention
The object of the present invention is to provide meso-porous hollow nano titanium dioxide ball of a kind of gadolinium ion doping and preparation method thereof, titanium dioxide is made to meso-porous hollow and improved the specific area of reaction, gadolinium-doped ion has suppressed the compound of photon and hole, extend the life-span in photon and hole, improve the utilization rate in photon and hole, catalytic efficiency is improved.
For achieving the above object, the present invention adopts following technical scheme:
Take tetraethyl orthosilicate as silicon source, obtain nano silicon by Stober legal system; Then the titanium dioxide adulterating at the coated gadolinium ion in the surface of nano silicon; High-temperature calcination makes unformed titanium dioxide be transformed into the titanium dioxide of anatase; Finally use sodium hydroxide solution corrode silicon dioxide, centrifuge washing obtains the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping.
Preparation method comprises the following steps:
(1) preparation of nano silicon bead
The mixed liquor A of preparation deionized water, absolute ethyl alcohol and ammoniacal liquor, stirs 1h～1.5h under room temperature, makes it to mix, then add the mixed liquid B of tetraethyl orthosilicate and absolute ethyl alcohol, continue to stir, reaction 2h～4h, centrifuge washing, is scattered in nano silicon bead in absolute ethyl alcohol;
(2) titanium dioxide of the coated gadolinium ion doping in silica bead surface
The mixed liquor C of the silica dispersions of step (1) and absolute ethyl alcohol, hydroxypropyl cellulose, gadolinium nitrate solution, under room temperature, stir 1h～1.5h, then dropwise drip the mixed liquor D of butyl titanate and absolute ethyl alcohol, control rate of addition, 10min～15min dropwises, and temperature is slowly raised to 70 ℃～85 ℃, constant temperature backflow 80min～120min, centrifuge washing, 100 ℃ of dry 10h～18h;
(3) the prepared composite pellets of high-temperature calcination step (2);
(4) remove silica core
Composite pellets after calcining is added in sodium hydroxide solution and corroded, and centrifuge washing, removes silica core, obtains the meso-porous hollow nano titanium dioxide ball of described gadolinium ion doping.
In step (1) mixed liquor A, the volume ratio of deionized water, absolute ethyl alcohol and ammoniacal liquor is: 15.0～25.0:71.0～83.0:2.0～4.0; In mixed liquid B, the volume ratio of tetraethyl orthosilicate and absolute ethyl alcohol is 8.0～12.0:88.0～92.0; The volume ratio of mixed liquor A and mixed liquid B is 9:3～5.
The mol ratio of tetraethyl orthosilicate and gadolinium ion is 1000:1 ~ 5.
The volume ratio of step (2) absolute ethyl alcohol and butyl titanate is 25:1～4, the volume ratio of butyl titanate and gadolinium nitrate solution is 10:1～4, the mass ratio of butyl titanate and hydroxypropyl cellulose is 10:1～3, and in mixed liquor C and mixed liquor D, the volume ratio of absolute ethyl alcohol is 4:1～3.
Step (3) calcining heat is 400 ℃～600 ℃, and calcination time is 2h～4h.
In step (4), the concentration of sodium hydroxide solution is 2.0～3.0mol/L, and etching time is 2.0～4.0h.
Remarkable advantage of the present invention is: the life-span that extends electronics and hole is combined with the specific area that improves titanium dioxide, take nano silicon as kernel, at the titanium dioxide of the coated gadolinium ion doping of silica surface, high-temperature calcination composite pellets, silica core can be corroded and be removed by sodium hydroxide solution, obtains the hollow Nano titanium dioxide ball of high catalytic efficiency.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 2.
Fig. 2 is the TEM figure of embodiment 2.
Fig. 3 is the XRD figure of embodiment 1-3.
Fig. 4 is that the design sketch of the photocatalysis methylene blue of embodiment 1-3: A is solid nano titanium dioxide ball; B is meso-porous hollow nano titanium dioxide ball; C is that gadolinium ion doping is 0.1% meso-porous hollow nano titanium dioxide ball; D is that gadolinium ion doping is 0.5% meso-porous hollow nano titanium dioxide ball; E is that gadolinium ion doping is 0.3% meso-porous hollow nano titanium dioxide ball.
The specific embodiment
With specific embodiment, the present invention will be further described below, but protection scope of the present invention is not limited to this
embodiment 1
(1) preparation of nano silicon bead
Under room temperature, in 50ml conical flask, add A liquid: 4.3ml deionized water, 15ml absolute ethyl alcohol and 0.62ml ammoniacal liquor stir 0.5h.Then add B liquid: 0.86ml tetraethyl orthosilicate and 8ml absolute ethyl alcohol continue reaction 3h, and centrifuge washing is dispersed in bead in 5ml absolute ethyl alcohol.
(2) titanium dioxide of the coated gadolinium ion doping in silica bead surface
Under room temperature, in there-necked flask, add C liquid: the gadolinium nitrate solution that silica dispersions, 15ml absolute ethyl alcohol, 0.1g hydroxypropyl cellulose and the 0.1ml concentration of 5ml step (1) is 0.00284mol/L stirs 0.5h.Then dropwise drip D liquid: the mixed liquor of 1ml butyl titanate and 5ml absolute ethyl alcohol composition, control rate of addition 12min and dropwise, then temperature is slowly raised to 85 ℃, constant temperature refluxes, reaction 100min, then centrifuge washing, 100 ℃ of dry 12h in air dry oven.
(3) calcining gained composite pellets
Gained composite pellets in (2) is calcined to 3h in the Muffle furnace of 500 ℃.
(4) remove silica core
The nanosphere that calcining is obtained adds in the sodium hydroxide solution of 2.5mol/L and reacts 3h, and centrifuge washing, removes silica core, obtains the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping.
embodiment 2
(1) preparation of nano silicon bead
Under room temperature, in 50ml conical flask, add A liquid: 4.3ml deionized water, 15ml absolute ethyl alcohol and 0.62ml ammoniacal liquor stir 0.5h.Then add B liquid: 0.86ml tetraethyl orthosilicate and 8ml absolute ethyl alcohol continue reaction 3h, and centrifuge washing is dispersed in bead in 5ml absolute ethyl alcohol.
(2) titanium dioxide of the coated gadolinium ion doping in silica bead surface
Under room temperature, in there-necked flask, add C liquid: the gadolinium nitrate solution that silica dispersions, 15ml absolute ethyl alcohol, 0.1g hydroxypropyl cellulose and the 0.1ml concentration of 5ml step (1) is 0.00852mol/L stirs 0.5h.Then dropwise drip D liquid: the mixed liquor of 1ml butyl titanate and 5ml absolute ethyl alcohol composition, control rate of addition 12min and dropwise, then temperature is slowly raised to 85 ℃, constant temperature refluxes, reaction 100min, then centrifuge washing, 100 ℃ of dry 12h in air dry oven.
(3) calcining gained composite pellets
Gained composite pellets in (2) is calcined to 3h in the Muffle furnace of 500 ℃.
(4) remove silica core
The nanosphere that calcining is obtained adds in the sodium hydroxide solution of 2.5mol/L and reacts 3h, and centrifuge washing, removes silica core, obtains the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping.
embodiment 3
(1) preparation of nano silicon bead
Under room temperature, in 50ml conical flask, add A liquid: 4.3ml deionized water, 15ml absolute ethyl alcohol and 0.62ml ammoniacal liquor stir 0.5h.Then add B liquid: 0.86ml tetraethyl orthosilicate and 8ml absolute ethyl alcohol continue reaction 3h, and centrifuge washing is dispersed in bead in 5ml absolute ethyl alcohol.
(2) titanium dioxide of the coated gadolinium ion doping in silica bead surface
Under room temperature, in there-necked flask, add C liquid: the gadolinium nitrate solution that silica dispersions, 15ml absolute ethyl alcohol, 0.1g hydroxypropyl cellulose and the 0.1ml concentration of 5ml step (1) is 0.0142mol/L stirs 0.5h.Then dropwise drip D liquid: the mixed liquor of 1ml butyl titanate and 5ml absolute ethyl alcohol composition, control rate of addition 12min and dropwise, then temperature is slowly raised to 85 ℃, constant temperature refluxes, reaction 100min, then centrifuge washing, 100 ℃ of dry 12h in air dry oven.
(3) calcining gained composite pellets
Gained composite pellets in (2) is calcined to 3h in the Muffle furnace of 500 ℃.
(4) remove silica core
The nanosphere that calcining is obtained adds in the sodium hydroxide solution of 2.5mol/L and reacts 3h, and centrifuge washing, removes silica core, obtains the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping.
From Fig. 1 and Fig. 2, the meso-porous hollow nano titanium dioxide ball of the gadolinium ion doping of gained is spheroidal, and the diameter of ball is 200nm left and right, and wall thickness is 20nm left and right.
In embodiment 1, the gadolinium ion of doping accounts for 0.1% of titanium dioxide, in embodiment 2, the gadolinium ion of doping accounts for 0.3% of titanium dioxide, in embodiment 3, the gadolinium ion of doping accounts for 0.5% of titanium dioxide, Fig. 3 is the XRD figure of embodiment 1-3, the crystal formation of embodiment 1-3 titanium dioxide is anatase as shown in Figure 3, the grain size of embodiment 1 gained titanium dioxide is 17.5nm, the size of the crystal grain of embodiment 2 gained titanium dioxide is 15.2nm, the grain size of embodiment 3 gained titanium dioxide is 16.5nm, visible, adding appropriate doping ion can suppress titania grows up, as shown in Figure 4, the suitable gadolinium ion that adulterates can improve the photocatalytic activity of titanium dioxide ball, when doping is 0.3%, photocatalytic activity is best, in the time of the too much gadolinium ion of doping, these ions become the combination center in photoelectron and hole in the lattice of titanium dioxide, catalytic efficiency reduces.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (7)
1. a meso-porous hollow nano titanium dioxide ball for gadolinium ion doping, is characterized in that: take tetraethyl orthosilicate as silicon source, obtain nano silicon by Stober legal system; Then the titanium dioxide adulterating at the coated gadolinium ion in the surface of nano silicon; High-temperature calcination makes unformed titanium dioxide be transformed into the titanium dioxide of anatase; Finally use sodium hydroxide solution corrode silicon dioxide, centrifuge washing obtains the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping.
2. a method of preparing the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping as claimed in claim 1, is characterized in that: comprise the following steps:
(1) preparation of nano silicon bead
The mixed liquor A of preparation deionized water, absolute ethyl alcohol and ammoniacal liquor, stirs 1h～1.5h under room temperature, makes it to mix, then add the mixed liquid B of tetraethyl orthosilicate and absolute ethyl alcohol, continue to stir, reaction 2h～4h, centrifuge washing, is scattered in nano silicon bead in absolute ethyl alcohol;
(2) titanium dioxide of the coated gadolinium ion doping in silica bead surface
The mixed liquor C of the silica dispersions of step (1) and absolute ethyl alcohol, hydroxypropyl cellulose, gadolinium nitrate solution, under room temperature, stir 1h～1.5h, then dropwise drip the mixed liquor D of butyl titanate and absolute ethyl alcohol, control rate of addition, 10min～15min dropwises, and temperature is slowly raised to 70 ℃～85 ℃, constant temperature backflow 80min～120min, centrifuge washing, 100 ℃ of dry 10h～18h;
(3) the prepared composite pellets of high-temperature calcination step (2);
(4) remove silica core
Composite pellets after calcining is added in sodium hydroxide solution and corroded, and centrifuge washing, removes silica core, obtains the meso-porous hollow nano titanium dioxide ball of described gadolinium ion doping.
3. the preparation method of the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping according to claim 2, is characterized in that: in step (1) mixed liquor A, the volume ratio of deionized water, absolute ethyl alcohol and ammoniacal liquor is: 15.0～25.0:71.0～83.0:2.0～4.0; In mixed liquid B, the volume ratio of tetraethyl orthosilicate and absolute ethyl alcohol is 8.0～12.0:88.0～92.0; The volume ratio of mixed liquor A and mixed liquid B is 9:3～5.
4. the preparation method of the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping according to claim 2, is characterized in that: the mol ratio of tetraethyl orthosilicate and gadolinium ion is 1000:1 ~ 5.
5. the preparation method of the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping according to claim 2, it is characterized in that: the volume ratio of step (2) absolute ethyl alcohol and butyl titanate is 25:1～4, the volume ratio of butyl titanate and gadolinium nitrate solution is 10:1～4, the mass ratio of butyl titanate and hydroxypropyl cellulose is 10:1～3, and in mixed liquor C and mixed liquor D, the volume ratio of absolute ethyl alcohol is 4:1～3.
6. the preparation method of the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping according to claim 2, is characterized in that: step (3) calcining heat is 400 ℃～600 ℃, and calcination time is 2h～4h.
7. the preparation method of the meso-porous hollow nano titanium dioxide ball of gadolinium ion doping according to claim 2, is characterized in that: in step (4), the concentration of sodium hydroxide solution is 2.0～3.0mol/L, and etching time is 2.0～4.0h.
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| CN104073084A (en) * | 2014-07-10 | 2014-10-01 | 福州大学 | PVDF (Polyvinylidene Fluoride) coating material with self-cleaning property and preparation method and application thereof |
| CN105731537A (en) * | 2014-12-12 | 2016-07-06 | 南京理工大学 | Method of preparing hollow mesoporous zirconium dioxide through sol-gel protective method |
| CN107867719A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Based on hollow-core construction blueness TiO2Michaelis resonance anti-fake product and its method for anti-counterfeit |
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| CN108996477A (en) * | 2018-07-26 | 2018-12-14 | 四川理工学院 | A method of based on St*ber method synthesis of metal oxide microballoon |
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| CN107867719B (en) * | 2017-09-30 | 2020-01-03 | 常熟理工学院 | Blue TiO based on hollow structure2Mie's resonance anti-fake product and its anti-fake method |
| CN107867718A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Monodisperse hollow structure blueness TiO2Material and preparation method |
| CN107867720A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Monodisperse hollow structure purple TiO2Material and preparation method |
| CN107867720B (en) * | 2017-09-30 | 2019-11-15 | 常熟理工学院 | Monodisperse hollow structure purple TiO2Material and preparation method |
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| CN108996477A (en) * | 2018-07-26 | 2018-12-14 | 四川理工学院 | A method of based on St*ber method synthesis of metal oxide microballoon |
| CN108996477B (en) * | 2018-07-26 | 2022-02-22 | 四川理工学院 | Method for synthesizing metal oxide microspheres based on Stober method |
| CN110078521A (en) * | 2019-05-13 | 2019-08-02 | 西北工业大学 | A kind of submicron order silicon nitride hollow microsphere and preparation method |
| CN110078521B (en) * | 2019-05-13 | 2021-06-11 | 西北工业大学 | Submicron silicon nitride hollow microsphere and preparation method thereof |
| CN113697853A (en) * | 2021-08-28 | 2021-11-26 | 上海大学 | Titanium suboxide and preparation method thereof |
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Application publication date: 20140528 |