CN106915769B - A kind of ultra-thin mixed crystal titanium dioxide nanoplate and its preparation method and application - Google Patents
A kind of ultra-thin mixed crystal titanium dioxide nanoplate and its preparation method and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 239000002055 nanoplate Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910003087 TiOx Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 44
- 239000003054 catalyst Substances 0.000 description 18
- 229960004424 carbon dioxide Drugs 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
The invention discloses a kind of ultra-thin mixed crystal titanium dioxide nanoplates and its preparation method and application, belong to the preparation field of catalysis material.The mixed crystal nanometer sheet is by two phase composition of anatase and rutile, and the ratio of two-phase is 7:3.The size of this nanometer sheet are as follows: be length, the width of 60 ~ 100nm and the thickness of 0.6 ~ 1.5nm of 200 ~ 250 nm.The average specific surface area that the nanometer sheet of the mixing crystal form has is about 193.3m2 g‑1.One of light-catalyzed reaction of the ultra-thin mixed crystal titanium dioxide nanoplate application is the reaction of photocatalytic reduction of carbon oxide under normal temperature and pressure, and shows the yield of preferable carbon dioxide photocatalytic conversion efficiency and higher methane.Present invention process is simple, environment-friendly and green, nontoxic, and reactivity is high, and stability is good, and wide application field, reusable, low energy consumption, and cost is small, meets needs of production, has biggish application potential.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of ultra-thin mixed crystal titanium dioxide nanoplate and its
Preparation method and application.
Background technique
In recent years, semiconductor light-catalyst has attracted the extensive concern of people, since it is administered in environmental contaminants, cleaning
The wide application prospect of the production of the energy and solar energy utilized etc..In numerous photochemical catalysts, titanium dioxide conduct
One of photochemical catalyst the most noticeable has many excellent properties, such as high activity, nontoxic, prolonged stability,
It is inexpensive and environmental-friendly etc..There are three types of crystal forms for titanium dioxide, are respectively: anatase, rutile and brockite.At these three
Anatase has highest reactivity in crystal form, and rutile has best thermodynamic stability, but this is not exhausted
Pair.Some researches show that the photocatalytic activity of rutile is better than the activity of anatase in some cases, the pattern of this and they
There is very big relationship with state.However the mixing material of anatase and Rutile Type is had been found that in many research groups so far
Material all has higher reactivity than their any one phase pure materials, and reason is that in mixed phase, there is a rutile titanias
The synergistic effect of mine phase and Rutile Type, this effect is in two alternate transfers using electronics as approach, therefore can effectively be pressed down
System reduces the compound of electrons and holes, to promote light induced electron and efficiently separating for hole and substantially proposing for photocatalysis efficiency
It is high.Such as P25, a kind of mixed crystal material containing about 80% anatase and 20% rutile, have very high photocatalysis living
Property, and have been applied to many aspect such as solar batteries, photochemical catalyst etc..But people are to mixed other than P25
The research of brilliant material is not that very sufficiently, reason is that synthesis mixed crystal material complex process and the control modulation ratio to its pattern
It is more difficult etc..Up to the present, the level that three dimensional particles are also only resided within to the research of mixed crystal titanium dioxide, to its shape
There is also clearly disadvantageous for the control synthesis of looks and associated catalytic activity research.Why the mixed crystal two of other patterns is studied
Titanium oxide, correlative study show by taking anatase titania as an example, two-dimentional sheet-like morphology compared with three dimensional particles pattern,
With faster reaction rate, the advantages that high reaction efficiency, dosage is few, easily separated regeneration.For mixed crystal titanium dioxide,
Appearance structure is to catalytic activity and application power or has a very big impact even decisive role.Therefore, other shapes are studied
The mixed crystal titanium dioxide of looks structure provides directive significance to the development and application of new material.
Why the thickness of catalysis material to be reduced, the mixed crystal titanium dioxide of study two-dimensional (2D), according to relevant report,
Reducing the thickness of semiconductor and increasing its size can be improved the percentage in effective active site.Many two-dimensional materials by
Various fields are applied to, they generally all have biggish specific surface area, special electronics and optical characteristics.And only have several
The ultra-thin monolayer two-dimensional material of a atomic layer level thickness can fully expose active site, and show to be different from it
Three-dimensional structure peculiar property.In addition to this, this ultra-thin two-dimension material can provide a platform for us and go at one
Molecular level profoundly understands catalysis and light-catalysed essence up.Up to the present, people have been synthesized dioxy
Change the zero dimension of titanium, one-dimensional, the material of two and three dimensions.Wherein the titanium dioxide under two-dimensional state is most potential material catalysis
Superior performance and tempting prospect are shown in reaction.Accordingly, it is considered to the pattern and performance of the titanium dioxide of mixed crystal type
Shortage is also compared in research, especially even more rare to the preparation and performance study of the mixed crystal titanium dioxide of Two-dimensional morphology, let alone
Development and utilization to it.We develop a kind of preparation method of the two-dimentional mixed crystal carbon dioxide nanometer sheet of simple process, choosing
A kind of suitable presoma nanometer sheet, the titanium dioxide of one-step synthesis mixed crystal, and the monolayer for keeping its ultra-thin are selected
Structure is constant.The ultra-thin mixed crystal titanium dioxide has both Anatase and Rutile Type, while having the advantages of two-dimensional material again.
It is in performance or more more advantageous than ordinary titanium dioxide mixed crystal material, such as property optically and electrically.It is ultra-thin mixed with this
Crystal titanium dioxide is as photochemical catalyst, and photocatalytic reduction of carbon oxide produces other carbon compounds at normal temperatures and pressures, by luminous energy
It is converted into photocatalytic applications potentiality and prospect that chemical energy is used to illustrate the material.It is in conjunction with the advantages of two-dimension nano materials and mixed
The electronic structure feature of brilliant material develops the performance of material and expands its application range.By the mixed crystal material of such unique texture
Clean energy resource is produced applied to potential light-catalyzed reaction, photocatalysis organic synthesis and photocatalysis environmental improvement etc., this will
New hope is brought for the exploitation of clean energy resource and the exploitation of solar energy.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, provide a kind of ultra-thin mixed crystal titanium dioxide nanoplate and its
Preparation method and application.It is anti-for photocatalysis that ultra-thin mixed crystal titanium dioxide nano material produced by the present invention can be used as photochemical catalyst
It answers, photocatalytic reduction of carbon oxide and generates methane under normal temperature and pressure, the selectivity for obtaining methane reaches 90% or more.The catalysis
Agent is efficient, nontoxic, and preparation process is simple, and stability is high, easy to operate, at low cost, has broad application prospects and potentially
Industrial value, and can extend in other a variety of light-catalyzed reactions.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of ultra-thin mixed crystal titanium dioxide nanoplate, the mixed phase containing anatase and rutile, and anatase and golden red
The ratio of stone is 7:3；The size of the ultra-thin mixed crystal titanium dioxide nanoplate are as follows: the length of 200 ~ 250 nm, 60 ~
The width of 100nm, the thickness of 0.6 ~ 1.5nm；The specific surface area average out to 193.3m of the nanometer sheet2 g-1。
The preparation method of ultra-thin mixed crystal titanium dioxide nanoplate as described above, with metatitanic acid nanometer sheet H1.07Ti1.73O4·
H2O is predecessor, and by HCl treatment, the mixed crystal nano material is prepared in the method for one-step synthesis, the specific steps are as follows:
(1) under conditions of ultrasonic agitation, toward H1.07Ti1.73O4·H2It is added dropwise in the colloid aqueous solution of O nanometer sheet
The hydrochloric acid of 1mol/L, until the precipitating of generation is re-dissolved in hydrochloric acid solution；
(2) after the mixed liquor stirring for 24 hours obtained step (1), centrifuge separation, and sufficiently washed with deionized water to ion
Concentration is lower than 0.1ppm；
(3) it is placed in baking oven and dries to get the titanium dioxide nanoplate of ultra-thin mixed crystal is arrived for 60 DEG C.
The present invention also protects the application of ultra-thin mixed crystal titanium dioxide nanoplate, the ultra-thin mixed crystal nano titania
Piece is as heterogeneous photocatalyst in light-catalyzed reaction.
The ultra-thin mixed crystal titanium dioxide nanoplate is used for photocatalytic reduction of carbon oxide under normal temperature and pressure and generates first
Alkane, the selectivity for obtaining methane reach 90% or more.
The beneficial effects of the present invention are:
(1) ultra-thin mixed crystal titanium dioxide nano material produced by the present invention can be used as catalyst and be used for light-catalyzed reaction,
Catalyst is efficient, nontoxic, and preparation process is simple, and stability is high, easy to operate, at low cost, has broad application prospects and dives
Industrial value, and can extend in other a variety of light-catalyzed reactions；
(2) catalyst of ultrathin nanometer mixed crystal material of the invention as photocatalytic reduction of carbon oxide has efficient
Photocatalytic activity and reaction stability can restore carbon dioxide and generate methane, and the selectivity for obtaining methane reaches 90% or more；
(3) when ultrathin nanometer mixed crystal material of the invention is as photochemical catalyst, to other light-catalyzed reactions such as photocatalysis
Clean energy resource preparation, photocatalysis environmental contaminants are administered, and photocatalysis organic synthesis etc. all has potential application prospect；
(4) when ultrathin nanometer mixed crystal material of the invention is as catalyst, Examination on experimental operation is simple, easily operated, has
It is promoted the use of conducive to large-scale.
Detailed description of the invention
Fig. 1 is the ultra-thin mixed crystal titanium dioxide nanoplate of catalyst of the invention, predecessor H1.07Ti1.73O4·H2O and P25
The X-ray diffraction (XRD) figure of nanometer sheet；
Fig. 2 be ultra-thin mixed crystal titanium dioxide nanoplate of the invention transmission electron microscope (TEM) figure and high-resolution it is saturating
Penetrate electron microscope (HRTEM) figure；
Fig. 3 is that the atomic force microscope test chart of ultra-thin mixed crystal titanium dioxide nanoplate of the invention and ultraviolet-visible are overflow
Reflectogram；
Fig. 4 is the nitrogen (N of ultra-thin mixed crystal titanium dioxide nanoplate of the invention2) adsorption desorption isothermal curve figure and its ratio
Surface area；
Fig. 5 is of the invention to be catalyzed two under normal temperature and pressure illumination condition using ultra-thin mixed crystal titanium dioxide nanoplate as catalyst
The product figure of carbonoxide reduction.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
Ultra-thin H1.07Ti1.73O4·H2The preparation of O nanometer sheet predecessor
By K2CO3, Li2CO3And TiO2After the mass ratio grinding uniformly of 1:13:3, it is placed in corundum crucible, 800 DEG C
2 h are calcined, are cooled to room temperature, are regrind, 1000 DEG C of 20 h of calcining are repeated once；Obtain stratiform K0.80Ti1.73Li0.67O4
Compound, by gained K0.80Ti1.73Li0.67O4Sample is added stirring, every 24 h in the hydrochloric acid solution (1 mol/L) of 1000 ml and changes
One hypo acid is recycled by four times, then centrifuge separation is washed products therefrom to neutrality with deionized water, 60 DEG C of dryings, i.e.,
For stratiform H1.07Ti1.73O4·H2O；By above-mentioned stratiform H1.07Ti1.73O4•H2O and TBAOH(tetrabutylammonium hydroxide) (40 wt%)
Solution is mixed according to molar ratio 1:1, and magnetic agitation 15 days, 3000 rpm centrifugation removed unstripped nonwoven fabric from filaments, can be obtained
H1.07Ti1.73O4•H2The colloid aqueous solution of O nanometer sheet.
The preparation of ultra-thin mixed crystal titanium dioxide nanoplate
Take H1.07Ti1.73O4·H225 ~ 30ml of colloid aqueous solution of O nanometer sheet is placed in vial, in the item of ultrasonic agitation
The hydrochloric acid of 1mol/L is added dropwise under part, has flocculent deposit to be gradually precipitated, continuing dropwise addition hydrochloric acid, dissolution is dispersed in again to precipitating
In solution, this suspension is placed on blender and is stirred for 24 hours, centrifuge separation, deionized water, which is washed to ion concentration, to be lower than
0.1ppm, 60 DEG C of dryings are to get the powder for arriving ultra-thin mixed crystal titanium dioxide nanoplate in baking oven.
Fig. 1 illustrates ultra-thin mixed crystal titanium dioxide nanoplate and ultra-thin predecessor H of the invention1.07Ti1.73O4·H2O receives
The X-ray diffraction (XRD) figure of the titanium dioxide of rice piece and object of reference P25, it can be found that the predecessor of preparation from figure
H1.07Ti1.73O4·H2O nanometer sheet in two phase compositions for becoming rutile and anatase after peracid treatment, constituent with
The titanium dioxide of P25 is similar, is equal to 25 ° and 27 ° or so (101) that can distinguish anatase and rutile at 2 angles θ
(111) crystal face；Fig. 2 illustrates transmission electron microscope (TEM) figure and height of ultra-thin mixed crystal titanium dioxide nanoplate of the invention
Resolution Transmission Electron microscope (HRTEM) figure, as can be seen from the figure its pattern is flaky material, and length is about 200 ~ 250nm,
Width is about 60 ~ 100nm, it can be seen that the spacing of lattice for being parallel to upper and lower facet is 0.235nm from HRTEM figure, belongs to two
(001) crystal face of titanium oxide.Fig. 3 illustrate the ultra-thin mixed crystal titanium dioxide nanoplate of synthesis atomic force microscope and it is ultraviolet can
See the spectrogram that diffuses, as can be seen from the figure the thickness average out to 1.3nm or so of the material, it is believed that be monolayer
Thickness, furthermore material ratio P25 has better absorbing properties.The N that Fig. 4 shows2De contamination isothermal curve figure, the material
The average specific surface area of material is about 193.3m2 g-1, specific surface area is P25 more than 3 times.
Performance test
Ultra-thin mixed crystal titanium dioxide nanoplate is catalyzed reduction carbon dioxide under illumination condition.
The ultra-thin mixed crystal titanium dioxide nanoplate of preparation is used as catalyst and is catalyzed reduction carbon dioxide under illumination condition.
It weighs 10 mg nanometer sheets to be placed in quartz ampoule, catalyst is evenly spread on test tube wall, vacuumizes to drain air, is full of
Simultaneously 10 μ L water are added in carbon dioxide, stir at normal temperature, are then turned on light source and carry out light-catalyzed reaction, product uses Agilent
7890 gas chromatographic detections；Testing the light source used is 300 W xenon lamps；Fig. 5 shows with ultra-thin mixed crystal nano titania
Piece is the product figure that catalyst is catalyzed carbon dioxide reduction under normal temperature and pressure illumination condition.As can be seen from the figure this is ultra-thin mixed
Crystal titanium dioxide nanometer sheet is significantly larger than the activity of the P25 under equal conditions to the activity of photocatalytic reduction of carbon oxide.Simultaneously
The ultra-thin two-dimension titanium dioxide nanoplate reaches 90% or more to the selectivity for generating methane.Therefore, synthesized ultra-thin two-dimension two
The selectivity of TiOx nano piece carbon dioxide reduction activity and higher synthesizing methane with higher is a kind of with extensive
The photochemical catalyst of application prospect.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (1)
1. a kind of preparation method of ultra-thin mixed crystal titanium dioxide nanoplate, it is characterised in that: the ultra-thin mixed crystal titanium dioxide
Nanometer sheet contains the mixed phase of anatase and rutile, and the ratio of anatase and rutile is 7:3；The ultra-thin mixed crystal two
The size of TiOx nano piece are as follows: the length of 200 ~ 250 nm, the width of 60 ~ 100nm, the thickness of 0.6 ~ 1.5nm；It is described to receive
The specific surface area average out to 193.3m of rice piece2 g-1；The ultra-thin mixed crystal titanium dioxide nanoplate the preparation method comprises the following steps: with titanium
Sour nanometer sheet H1.07Ti1.73O4·H2O is predecessor, and by HCl treatment, the method for one-step synthesis is prepared described ultra-thin mixed
Crystal titanium dioxide nanometer sheet, the specific steps are as follows:
(1) under conditions of ultrasonic agitation, toward H1.07Ti1.73O4·H21mol/L is added dropwise in the colloid aqueous solution of O nanometer sheet
Hydrochloric acid, until the precipitating of generation is dispersed in hydrochloric acid solution again；
(2) after the suspension stirring for 24 hours obtained step (1), centrifuge separation, and sufficiently washed with deionized water to ion concentration
Lower than 0.1ppm；
(3) it is placed in baking oven and dries to get the titanium dioxide nanoplate of ultra-thin mixed crystal is arrived for 60 DEG C.
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| Single Nanocrystals of Anatase-Type TiO 2 Prepared from Layered Titanate Nanosheets: Formation Mechanism;Qi Feng;《Langmuir》;20071231;第1页-第29页 |
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