CN107540014A - A kind of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method - Google Patents
A kind of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The present invention relates to heterogeneous seed mesoporous metal oxide preparation field, specially a kind of preparation method of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth.This method is used as presoma by wet-chemical process using titanium tetrachloride, contain the silica spheres of heterogeneous seed as template, hydrothermal growth has the rutile titanium dioxide that particular crystal plane exposes, the mesopore monocrystalline rutile titanium dioxide containing heterogeneous seed is obtained after etching template, heterogeneous seed epitaxial growth co-catalyst can be realized, solves catalyst and the problem of co-catalyst interracial contact is second-rate, and photocatalysis efficiency is relatively low.Different from prior seed template, the present invention is fitted into reactor by titanium tetrachloride presoma and containing heterogeneous seed silica template, heat-treated, and the mesopore monocrystalline rutile titanium dioxide of particular crystal plane exposure is obtained after etching.
Description
Technical field
The present invention relates to heterogeneous seed mesoporous metal oxide preparation field, specially a kind of heterogeneous seed mesopore monocrystalline gold
The preparation method of red stone titanium dioxide controllable growth, it is different with ruthenic oxide (tin ash, iridium dioxide) by wet-chemical process
Matter seed, with TiCl4For presoma hydrothermal growth particular crystal plane mesopore monocrystalline rutile TiO2。
Background technology
Because titanium dioxide has the advantages that high stability, suitable band gap, low cost, nontoxic, it is as classics
Catalysis material causes extensive concern and in-depth study.Titanium dioxide optical catalyst is except applied to photochemical catalyzing
Outside, the fields such as light degradation, solar cell, optical electro-chemistry and automatically cleaning are also widely used for.Because light-catalyzed reaction is main
Carried out on the surface of semi-conducting material, and a certain amount of co-catalyst favorably uses the separation of photo-generated carrier, so research is partly led
Body material co-catalyst deposit and find improve its photocatalysis efficiency approach be Recent study emphasis.In recent years, for
The method that the deposition of co-catalyst is mainly sunk by heat sink and light, the co-catalyst interracial contact quality of both approaches deposition
It is poor so that photo-generated carrier can not be efficiently separated and reacted.
The content of the invention
It is an object of the invention to provide a kind of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation side
Method, cause RuO using the similitude of structure2(SnO2、IrO2) it is used as TiO in preparation process2The forming core site of growth, again may be used
So that as the co-catalyst in light-catalyzed reaction, this method can obtain the mesopore monocrystalline gold of all { 111 } crystal face exposures
Red stone TiO2, change the concentration of seed, the shape of sample does not change substantially.
The technical scheme is that：
A kind of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method, with titanium tetrachloride hydrochloric acid solution
As presoma, commercial sodium fluoride is similarly ruthenic oxide, the tin ash or two of rutile-type as crystal face controlling agent, selection
Yttrium oxide is as follows as heterogeneous seed, detailed process：
(1) it is seed solution to take ruthenium chloride aqueous solution or the iridium chloride aqueous solution, or take stannous chloride ethanol solution or
Water, alcohol mixed solution are seed solution, add silica spheres, prepare the silica spheres seed pattern containing heterogeneous seed；
(2) presoma, sodium fluoride and silica spheres seed pattern are put into reactor, presoma volume be 20ml~
The mass ratio of 60ml, sodium fluoride and silica spheres seed pattern is (0.1~1)：(0.5~20), after reactor sealing, put
Enter baking oven heating, take out response sample, cleaned and dried with deionized water, after etching template, with deionized water and ethanol
It is respectively washed and dries, obtains the mesopore monocrystalline rutile titanium dioxide containing different heterogeneous seeds of { 111 } crystal face exposure, it is heterogeneous
Seed is both as the forming core site in preparation process, again as the co-catalyst in photocatalysis test process.
Described presoma is the commercial pure titanium tetrachloride solution of chemistry, and silica spheres used a diameter of 5~250 are received
Rice.
Described reactor material is one kind of stainless steel, aluminium alloy, copper and tantalum, and the inner bag of reactor is polytetrafluoroethylene (PTFE)
With one kind of high density polyethylene (HDPE).
In described titanium tetrachloride hydrochloric acid solution, the molar concentration of hydrochloric acid is 0.05M~5M, the molar concentration of titanium tetrachloride
For 0.01M~1M；In described ruthenium chloride aqueous solution or the iridium chloride aqueous solution, the molar concentration of ruthenic chloride or iridium chloride is
0.001mM~0.1M；In the ethanol solution or water of described stannous chloride, alcohol mixed solution, the molar concentration of stannous chloride
For 0.001mM~0.1M, the volume ratio of ethanol and water is between 0~1.
Described heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method, preferably：Described four
In titanium chloride hydrochloric acid solution, the molar concentration of hydrochloric acid is 1M~5M, and the molar concentration of titanium tetrachloride is 0.01M~0.1M；It is described
Ruthenium chloride aqueous solution or the iridium chloride aqueous solution in, the molar concentration of ruthenic chloride or iridium chloride is 0.02mM~10mM；Described
In the ethanol solution or water of stannous chloride, alcohol mixed solution, the molar concentration of stannous chloride is 1mM~30mM, ethanol and water
Volume ratio between 0~1.
Described when being put into baking oven and heating, heating-up temperature is 100~300 DEG C, and the heat time is 2h~48h.
It is described cleaned with deionized water after when drying, drying temperature is 60~100 DEG C.
During described etching template, the molar concentration of the NaOH aqueous solution is used as 1M~5M, in 60~90 DEG C of bath temperature
0.5~2h of lower etching.
Described heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method, the heterogeneous seed of various concentrations
The sample crystallite dimension of prepared mesopore monocrystalline rutile titanium dioxide is 300nm~900nm, aperture 2 to 50 nanometers it
Between, duct exposes through sample interior, surface for { 111 } crystal face.
Described heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method, prepares silica spheres kind
During subtemplate, seed solution and silica spheres are incubated 0.5~2h in 60~80 DEG C of water-baths, then with deionized water rinsing,
The silica spheres after seed will be finished in 70~90 DEG C of heating mantles to dry, place 450~550 DEG C of insulations 20 in Muffle furnace~
40min。
The design philosophy of the present invention is as follows：
For light-catalyzed reaction, the specific surface area of sample represents the number of reaction active site to a certain extent, because
It is critically important that this obtains porous semi-conductor material；And co-catalyst deposition is to improve an importance of photocatalysis performance, mesh
Preceding main deposition process is heat deposition and light deposition, and both approaches obtain co-catalyst and catalyst interface contact quality
It is poor, it is unfavorable for the separation of carrier.Therefore, mesopore monocrystalline rutile TiO is selected in experimentation2For synthetic object,
In preparation process, RuO is utilized2(SnO2、IrO2) it is rutile structure, and the characteristics of lattice constant is close, devise heterogeneous seed
Epitaxial growth prepares mesopore monocrystalline rutile TiO2Process.After hydro-thermal and etching processing, it can obtain containing heterogeneous seed conduct
The mesopore single crystal samples of co-catalyst, using RuO2During as seed, prepared sample shows preferable Photocatalyzed Hydrogen Production
With production oxygen performance.
Advantages of the present invention and beneficial effect are：
1st, the present invention is a kind of heterogeneous seed epitaxial growth mesopore monocrystalline rutile TiO2Preparation method, in different seeds
Mesoporous sample can be obtained under concentration.
2nd, co-catalyst needed for seed needed for mesoporous sample preparation process and light-catalyzed reaction is incorporated in by the inventive method
Together, the mesopore monocrystalline rutile TiO of co-catalyst modification in situ is obtained2。
3rd, the inventive method forms heterogeneous seed mesopore monocrystalline rutile TiO2Pattern is homogeneous, pore size distribution is uniform, particle diameter
Big I is regulated and controled by seed concentration.
In a word, the adjustable heterogeneous kind of with regular morphology, even aperture distribution, particle size is prepared using the present invention
Sub- mesopore monocrystalline rutile TiO2, for materials synthesis in itself and the research of subsequent photocatalytic activity has important meaning.
It is in the present invention the heterogeneous seed mesopore monocrystalline rutile TiO of synthesis for materials synthesis2Crystal applies various concentrations
RuCl3(IrCl3) aqueous solution and various concentrations SnCl2Water and ethanol solution.To heterogeneous seed epitaxial growth mesopore TiO2Light
For catalytic activity research, heterogeneous seed is as co-catalyst and TiO2Contact be atomic scale, in the absence of macroscopic view boundary
Face, thus during light-catalyzed reaction carrier separative efficiency it is higher, so as to cause its photochemical catalyzing hydrogen production potential to have
Difference.This also causes there is deeper understanding to the mode of growth in situ co-catalyst, so as to for hereafter with heterogeneous seed system
Other standby mesoporous oxides provide the foundation.
Brief description of the drawings
Mesopore monocrystalline rutile TiO under Fig. 1 various concentrations seeds2SEM photograph；Wherein, (a) is schemed, (b) is 0.04mMol
RuO2Make the sample being prepared during seed, figure (c), (d) are 1mMol IrO2Make the sample being prepared during seed, figure (e),
(f) it is 10mMol SnO2Make the sample being prepared during seed.
Mesopore monocrystalline rutile TiO under Fig. 2 various concentrations seeds2TEM photos；Wherein, (a) is schemed, (b) is respectively
0.04mMRuO2With 1mM IrO2Make to be prepared the transmission photo of sample during seed, figure (c) is 10mMol SnO2When making seed
The transmission photo of sample is prepared.Two illustrations schemed in (a) are respectively 0.04mM RuO2The mesopore obtained under seed concentration
Monocrystalline rutile TiO2Low power pattern phase and selected diffraction collection of illustrative plates, figure (b) in two illustrations be respectively 1mM IrO2Seed
The mesopore monocrystalline rutile TiO obtained under concentration2Low power pattern phase and selected diffraction collection of illustrative plates, figure (c) in two illustrations
Respectively 10mM SnO2The mesopore monocrystalline rutile TiO obtained under seed concentration2Low power pattern phase and selected diffraction collection of illustrative plates.
Mesopore monocrystalline rutile TiO under Fig. 3 difference seeds2XRD spectrum；Wherein, it is 0.04mMRuO to scheme (a)2Make seed
When the XRD spectrum of sample is prepared, figure (b) is 1mM IrO2Make to be prepared the XRD spectrum of sample during seed, figure (c) is
10mMol SnO2Make that sample XRD spectrum is prepared during seed；X-axis is the θ of the angle of diffraction 2 (degree), and Y-axis is intensity (a.u.).
Fig. 4 is mesopore monocrystalline rutile TiO under different seeds2N2Adsorption curve and graph of pore diameter distribution；Wherein, figure (a) is
0.04mM RuO2Make to be prepared during seed sample adsorption curve and graph of pore diameter distribution (wherein illustration represents 0.04mMRuO2It is dense
The graph of pore diameter distribution of sample is prepared under degree), figure (b) is 10mMol SnO2Make to be prepared during seed sample adsorption curve and
Graph of pore diameter distribution (wherein illustration represents to prepare the graph of pore diameter distribution of sample under 10mMol SnO2 concentration).Scheme in (a) and figure (b),
X-axis is relative pressure (P/P0), and Y-axis is adsorbance (mmol/g).Scheme (a) and scheme in the illustration of (b), X-axis is aperture (nm), Y
Axle is pore volume (cm3/g·nm)。
Embodiment
In specific implementation process, the heterogeneous seed mesopore monocrystalline rutile TiO of the present invention2The preparation method of controllable growth,
It is seed pattern preparation process first：With certain density RuCl3.xH2The O aqueous solution is seed solution, takes above-mentioned 50mL molten
Liquid, adds a certain amount of silica spheres (3g~25g), after 70 DEG C of water-bath 1h, with a large amount of deionized water rinsings, in 80 DEG C of heating
The silica spheres after seed will be finished in set to dry, placing heating in Muffle furnace, (2 DEG C/min rises to 500 DEG C, insulation
30min)。TiO2Precursor solution process for preparation：By TiCl4It is slowly dropped into hydrochloric acid, adds a certain amount of water, is made into certain dense
The TiCl of degree4Aqueous hydrochloric acid solution, with needing ice-water bath in solution processes.Followed by heterogeneous seed mesopore monocrystalline TiO2Preparation：Take
A certain amount of silica spheres seed pattern (500mg~5g) is put into the polytetrafluoroethylliner liner containing precursor solution,
Hydro-thermal certain time in the baking oven of certain temperature, after inner bag cooling, silica spheres seed pattern is collected, with a large amount of deionizations
Water rinses, and is dried in 80 DEG C of heating mantles, collects, is put into the finite concentration NaOH aqueous solution water-bath 1h under certain temperature, etches
Silica spheres seed pattern, mesopore TiO is collected by centrifugation2Sample, it is respectively washed 2~3 times, is collected simultaneously with deionized water and ethanol
Drying sample.Meanwhile heterogeneous seed is also an option that SnO2Or IrO2, preparation process is similar to the above, and simply seed solution is selected
IrCl3.xH2The O aqueous solution, or seed solution select SnCl2Ethanol solution or water, the mixed solution of ethanol.Wherein, specifically
It is characterised by：
1st, TiCl used in reaction4For the commercial pure solution of chemistry, silica spheres seed pattern is diameter 50nm or so SiO2
Bead.
2nd, reactor material is one kind of stainless steel, aluminium alloy, copper and tantalum, and inner bag is polytetrafluoroethylene (PTFE) and high-density polyethylene
One kind of alkene.
3rd, the seed solution concentration：For RuCl3.xH2The O aqueous solution or IrCl3.xH2The O aqueous solution, its concentration are
0.02mM~10mM；For SnCl2Solution, its concentration are 1mM~30mM, SnCl2Solution reclaimed water and the volume ratio of ethanol are 0~1
Between.
4th, etch in template procedure, the molar concentration of the NaOH aqueous solution used is 1M~5M, 60~90 DEG C of bath temperature.
5th, it is described be put into baking oven heat when, heating-up temperature be 100~300 DEG C, the heat time is 2h~48h.
6th, it is described cleaned with deionized water after when drying, drying temperature is 60~100 DEG C.
7th, with RuO2Mesopore monocrystalline rutile TiO can be obtained when making seed, under various concentrations2, the size of sample exists
Between 500nm~900nm, the seed co-catalyst list carrying capacity difference of various concentrations causes test photocatalysis performance to have difference；
Equally, using SnO2Or IrO2When making seed, the similar mesopore monocrystalline rutile TiO of pattern can obtain2。
The present invention is described in detail with reference to embodiment.
Embodiment
In the present embodiment, with RuO2Mesopore monocrystalline rutile TiO is prepared as heterogeneous seed2Exemplified by：
Seed pattern preparation process：Take the closely packed SiO of 3g2Ball template is put into 50mL molar concentrations 0.04mM RuCl3Water
In solution, 70 DEG C of 1h of water-bath, a large amount of deionized water rinsings of silica spheres seed pattern are then taken out, are put into 80 DEG C of heating mantles
Middle drying；Afterwards, 500 DEG C of insulation 30min in Muffle furnace are placed, obtain the silica spheres seed pattern containing heterogeneous seed.
Prepare TiCl4Presoma：1.64mL TiCl4It is slowly dropped into (frozen water in the concentrated hydrochloric acid that 292mL concentration is 37wt%
Bath), deionized water is then added to 1L, is well mixed.
Prepare mesoporous sample：Above-mentioned precursor solution 40mL is taken, is put into polytetrafluoroethylliner liner, adds 80mg NaF
As pattern controlling agent, 500mg silica spheres seed patterns are added, above-mentioned polytetrafluoroethyllining lining is encapsulated into outside stainless steel
In set, baking oven is heated to 200 DEG C of insulation 12h.Room temperature is cooled to, takes the template particles deionization in polytetrafluoroethyllining lining
Water is rinsed, after 80 DEG C of dryings, is put into 100mL molar concentrations 2M NaOH solution, and 80 DEG C of water-baths are incubated 1h, to template
Perform etching.After the completion of etching, distinguish eccentric cleaning 2~3 times with deionized water and ethanol, dry and collect sample.
With IrO2Or SnO2Mesopore monocrystalline rutile TiO is prepared as seed2Process it is similar therewith.
Fig. 1 illustrates RuO2、IrO2、SnO2Make the mesopore monocrystalline rutile TiO of seed preparation2SEM photograph, show sample
Product are loose structure, monocrystalline rutile TiO2The crystallite dimension of sample is between 400nm~900nm.
Fig. 2 illustrates RuO2、IrO2、SnO2Make the mesopore monocrystalline rutile TiO of seed preparation2TEM photos, diffraction spot
Point shows that sample is mono-crystalline structures, and shape appearance figure can be seen that pore structure exposes through sample interior, surface for { 111 } crystal face.
Fig. 3 illustrates RuO2、IrO2、SnO2Make the mesopore monocrystalline rutile TiO of seed preparation2XRD spectrum, show sample
Product are Rutile Type.
Fig. 4 illustrates RuO2And SnO2Make the mesopore monocrystalline rutile TiO of seed preparation2N2Adsorption isothermal curve and hole
Footpath distribution curve, show that sample contains abundant pore structure, pore-size distribution shows that the aperture of sample is about 50nm and titanium dioxide
Silicon ball seed pattern size is consistent.
Embodiment result shows that the present invention, using titanium tetrachloride as presoma, contains heterogeneous seed by wet-chemical process
Silica spheres as template, hydrothermal growth have particular crystal plane expose rutile titanium dioxide, etch template after obtain
Mesopore monocrystalline rutile titanium dioxide containing heterogeneous seed, can realize heterogeneous seed epitaxial growth co-catalyst, solve and urge
The problem of agent and co-catalyst interracial contact are second-rate, and photocatalysis efficiency is relatively low.It is different from prior seed template, this hair
It is bright to be fitted into by titanium tetrachloride presoma and containing heterogeneous seed silica template in reactor, it is heat-treated, obtained after etching
The mesopore monocrystalline rutile titanium dioxide of particular crystal plane exposure.
Claims (10)
1. a kind of heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method, it is characterised in that with four chlorinations
Titanium salt acid solution is similarly the ruthenic oxide of rutile-type, two as presoma, commercial sodium fluoride as crystal face controlling agent, selection
Tin oxide or iridium dioxide are as follows as heterogeneous seed, detailed process：
(1) it is seed solution to take ruthenium chloride aqueous solution or the iridium chloride aqueous solution, or takes the ethanol solution or water, second of stannous chloride
Mixed alkoxide solution is seed solution, adds silica spheres, prepares the silica spheres seed pattern containing heterogeneous seed；
(2) presoma, sodium fluoride and silica spheres seed pattern are put into reactor, presoma volume be 20ml~
The mass ratio of 60ml, sodium fluoride and silica spheres seed pattern is (0.1~1)：(0.5~20), after reactor sealing, put
Enter baking oven heating, take out response sample, cleaned and dried with deionized water, after etching template, with deionized water and ethanol
It is respectively washed and dries, obtains the mesopore monocrystalline rutile titanium dioxide containing different heterogeneous seeds of { 111 } crystal face exposure, it is heterogeneous
Seed is both as the forming core site in preparation process, again as the co-catalyst in photocatalysis test process.
2. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, described presoma is the commercial pure titanium tetrachloride solution of chemistry, a diameter of 5~250 nanometers of silica spheres used.
3. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is that described reactor material is one kind of stainless steel, aluminium alloy, copper and tantalum, and the inner bag of reactor is polytetrafluoroethylene (PTFE)
With one kind of high density polyethylene (HDPE).
4. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, in described titanium tetrachloride hydrochloric acid solution, the molar concentration of hydrochloric acid is 0.05M~5M, the molar concentration of titanium tetrachloride
For 0.01M~1M；In described ruthenium chloride aqueous solution or the iridium chloride aqueous solution, the molar concentration of ruthenic chloride or iridium chloride is
0.001mM~0.1M；In the ethanol solution or water of described stannous chloride, alcohol mixed solution, the molar concentration of stannous chloride
For 0.001mM~0.1M, the volume ratio of ethanol and water is between 0~1.
5. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, preferably：In described titanium tetrachloride hydrochloric acid solution, the molar concentration of hydrochloric acid is 1M~5M, mole of titanium tetrachloride
Concentration is 0.01M~0.1M；In described ruthenium chloride aqueous solution or the iridium chloride aqueous solution, the molar concentration of ruthenic chloride or iridium chloride
For 0.02mM~10mM；In the ethanol solution or water of described stannous chloride, alcohol mixed solution, the molar concentration of stannous chloride
For 1mM~30mM, the volume ratio of ethanol and water is between 0~1.
6. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, described when being put into baking oven and heating, and heating-up temperature is 100~300 DEG C, and the heat time is 2h~48h.
7. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, it is described cleaned with deionized water after when drying, drying temperature is 60~100 DEG C.
8. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, during described etching template, the molar concentration of the NaOH aqueous solution is used as 1M~5M, at 60~90 DEG C of bath temperature
Etch 0.5~2h.
9. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, the sample crystallite dimension of the mesopore monocrystalline rutile titanium dioxide prepared by the heterogeneous seed of various concentrations for 300nm~
900nm, between 2 to 50 nanometers, duct exposes through sample interior, surface for { 111 } crystal face in aperture.
10. according to the heterogeneous seed mesopore monocrystalline rutile titanium dioxide controllable growth preparation method described in claim 1, it is special
Sign is, when preparing silica spheres seed pattern, seed solution and silica spheres 60~80 DEG C of water-baths insulations 0.5~
2h, then with deionized water rinsing, in 70~90 DEG C of heating mantles will finish the silica spheres after seed dries, and places Muffle
450~550 DEG C of 20~40min of insulation in stove.
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| CN111013580A (en) * | 2019-11-06 | 2020-04-17 | 浙江师范大学 | Catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method and application thereof |
| CN111013580B (en) * | 2019-11-06 | 2023-04-07 | 浙江师范大学 | Catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method and application thereof |
| CN112121781A (en) * | 2020-08-26 | 2020-12-25 | 太原科技大学 | Visible light response titanium-silicon composite oxide photocatalyst with chiral stacking structure and preparation and application thereof |
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| CN107540014B (en) | 2019-08-16 |
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