CN106915769A - 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 143
- 239000013078 crystal Substances 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 52
- 239000002055 nanoplate Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 7
- 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
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 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
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 17
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002356 single layer Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000010410 layer Substances 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
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910003087 TiOx Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method 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
- 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
- 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
- 235000009566 rice Nutrition 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
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 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
-
- 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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- C01—INORGANIC CHEMISTRY
- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- C01—INORGANIC CHEMISTRY
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of ultra-thin mixed crystal titanium dioxide nanoplate and its preparation method and application, belong to the preparation field of catalysis material.The mixed crystal nanometer sheet be by anatase and the phase composition of rutile two, and two-phase ratio be 7:3.The size of this nanometer sheet is：It is the thickness of the length of 200 ~ 250 nm, the width of 60 ~ 100nm and 0.6 ~ 1.5nm.The average specific surface area that the nanometer sheet of the mixing crystal formation has 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 methane higher.Present invention process is simple, and environment-friendly and green is nontoxic, and reactivity is high, good stability, application field wide, and reusable, energy consumption is low, and cost is small, meets needs of production, with larger application potential.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of ultra-thin mixed crystal titanium dioxide nanoplate and its
Preparation method and application.
Background technology
In recent years, semiconductor light-catalyst has attracted the extensive concern of people, because it is administered in environmental contaminants, cleaning
The wide application prospect for the aspect such as utilizing of the production of the energy and solar energy.In numerous photochemical catalysts, titanium dioxide conduct
, with many excellent property, such as high activity is nontoxic, prolonged stability for one of photochemical catalyst the most noticeable,
It is inexpensive and environment-friendly etc..Titanium dioxide has three kinds of crystal formations, is respectively：Anatase, rutile and brockite.At these three
Anatase has highest reactivity in crystal formation, and rutile has best thermodynamic stability, but this is not exhausted
To.There are some researches show being better than the activity of anatase in the photocatalytic activity of rutile in some cases, this pattern with them
There is very big relation with state.But have been found that the mixing material of anatase and Rutile Type in many research groups so far
Material all has reactivity higher than their any one phase pure materials, and reason is that a sharp titanium is there is in mixed phase
The synergy of ore deposit phase and Rutile Type, this effect be with electronics in two alternate transfers as approach, therefore can effectively press down
System reduces the compound of electronics and hole, so as to promote light induced electron and efficiently separating for hole and significantly proposing for photocatalysis efficiency
It is high.A kind of such as P25, mixed crystal material containing about 80% anatase and 20% rutile is lived with photocatalysis very high
Property, and many aspect such as solar cells are had been applied to, photochemical catalyst etc..But, people are to mixed in addition to P25
The research of brilliant material is not that very fully, reason is that synthesis mixed crystal material complex process and the control modulation ratio to its pattern
The aspect such as more difficult.Up to the present, the research to mixed crystal titanium dioxide also only resides within the aspect of three dimensional particles, to its shape
The control synthesis of looks and associated catalytic activity research also exist clearly disadvantageous.Why the mixed crystal two of other patterns is studied
Titanium oxide, correlative study shows, by taking anatase titania as an example, its two-dimentional sheet-like morphology compared with three dimensional particles pattern,
With faster reaction rate, reaction efficiency high, consumption is few, the advantages of easily separated regeneration.For mixed crystal titanium dioxide, its
Appearance structure is to catalysis activity and application power or has a very big impact even decisive role.Therefore, other shapes are studied
Development and application of the mixed crystal titanium dioxide of looks structure to new material provide directive significance.
Why the thickness of catalysis material, study two-dimensional are reduced（2D）Mixed crystal titanium dioxide, according to relevant report,
Reducing the thickness of semiconductor and increase its size can improve the percentage in effective active site.Many two-dimensional materials by
Various fields are applied to, they typically all have larger specific surface area, special electronics and optical characteristics.And only have several
The ultra-thin monolayer two-dimensional material of individual atomic layer level thickness can fully expose avtive spot, and show to be different from it
Three-dimensional structure peculiar property.In addition, this ultra-thin two-dimension material can be gone at one for we provide a platform
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.Titanium dioxide wherein under two-dimensional state is most potential material catalysis
Superior performance and tempting prospect is shown in reaction.Accordingly, it is considered to arrive the pattern and performance of the titanium dioxide of mixed crystal type
Shortage is also compared in research, and the especially preparation and performance study to the mixed crystal titanium dioxide of Two-dimensional morphology is even more rare, let alone
Exploitation to it.We develop a kind of preparation method of the two-dimentional mixed crystal carbon dioxide nanometer sheet of process is simple, choosing
A kind of suitable presoma nanometer sheet, the titanium dioxide of one-step synthesis mixed crystal are selected, and has kept its ultra-thin monolayer
Structure is constant.The ultra-thin mixed crystal titanium dioxide has Anatase and Rutile Type concurrently, while there is two-dimensional material again.
It is in performance or more more advantageous than ordinary titanium dioxide mixed crystal material, property for example optically and electrically.It is ultra-thin mixed with this
Crystal titanium dioxide produces other carbon compounds as photochemical catalyst, at normal temperatures and pressures photocatalytic reduction of carbon oxide, by luminous energy
Chemical energy is converted into for illustrating the photocatalytic applications potentiality and prospect of the material.With reference to the advantage of two-dimension nano materials and mixed
The electronic structure feature of brilliant material, develops the performance of material and expands its range of application.By the mixed crystal material of this kind of unique texture
It is applied to potential light-catalyzed reaction production clean energy resource, the aspect such as photocatalysis organic synthesis and photocatalysis environmental improvement, this general
It is that the exploitation of clean energy resource and the exploitation of solar energy bring new hope.
The content 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-that obtained ultra-thin mixed crystal titanium dioxide nano material of the invention can be used for photocatalysis as photochemical catalyst
Should, photocatalytic reduction of carbon oxide and methane being produced under normal temperature and pressure, the selectivity for obtaining methane reaches more than 90%.The catalysis
Efficiently, nontoxic, preparation process is simple, stability is high for agent, and easily operation, low cost, have broad application prospects and potentially
Industrial value, and can expand to other various light-catalyzed reactions.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of ultra-thin mixed crystal titanium dioxide nanoplate, the mixed phase containing anatase and rutile, and anatase and rutile
Ratio is 7:3；The size of described ultra-thin mixed crystal titanium dioxide nanoplate is：The length of 200 ~ 250 nm, 60 ~ 100nm's
Width, 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 method for one-step synthesis prepares the mixed crystal nano material, comprises the following steps that：
（1）Under conditions of ultrasonic agitation, toward H1.07Ti1.73O4·H21mol/L is added dropwise in the colloid aqueous solution of O nanometer sheets
Hydrochloric acid, until the precipitation for producing is re-dissolved in hydrochloric acid solution；
（2）By step（1）After the mixed liquor stirring 24h for obtaining, centrifugation, and fully washed to ion concentration with deionized water
Less than 0.1ppm；
（3）60 DEG C of drying in baking oven are placed in, that is, obtain the titanium dioxide nanoplate of ultra-thin mixed crystal.
The present invention also protects the application of ultra-thin mixed crystal titanium dioxide nanoplate, described ultra-thin mixed crystal nano titania
Piece is used in light-catalyzed reaction as heterogeneous photocatalyst.
Described ultra-thin mixed crystal titanium dioxide nanoplate is for photocatalytic reduction of carbon oxide under normal temperature and pressure and produces first
Alkane, the selectivity for obtaining methane reaches more than 90%.
The beneficial effects of the present invention are：
（1）Obtained ultra-thin mixed crystal titanium dioxide nano material of the invention can be used for light-catalyzed reaction, catalysis as catalyst
Efficiently, nontoxic, preparation process is simple, stability is high for agent, and easily operation, low cost, have broad application prospects and potentially
Industrial value, and can expand to other various light-catalyzed reactions；
（2）Ultrathin nanometer mixed crystal material of the invention is urged as the catalyst of photocatalytic reduction of carbon oxide with efficient light
Change activity and reaction stability, carbon dioxide can be reduced and methane is produced, the selectivity for obtaining methane reaches more than 90%；
（3）When ultrathin nanometer mixed crystal material of the invention is as photochemical catalyst, to other light-catalyzed reactions such as photocatalysis cleaning
Prepared by the energy, 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, it is easy to operate, and is conducive to
Promote the use of on a large scale.
Brief description of the drawings
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 of nanometer sheet（XRD）Figure；
Fig. 2 is the transmission electron microscope of ultra-thin mixed crystal titanium dioxide nanoplate of the invention（TEM）Figure and high-resolution transmit electricity
Sub- microscope（HRTEM）Figure；
Fig. 3 is the AFM test chart and UV-Vis DRS of ultra-thin mixed crystal titanium dioxide nanoplate of the invention
Figure；
Fig. 4 is the nitrogen of ultra-thin mixed crystal titanium dioxide nanoplate of the invention（N2）Adsorption desorption isothermal curve figure and its specific surface
Product；
Fig. 5 is of the invention to be catalyzed titanium dioxide as catalyst with ultra-thin mixed crystal titanium dioxide nanoplate under normal temperature and pressure illumination condition
The product figure of carbon 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 predecessors
By K2CO3, Li2CO3And TiO2According to 1：13：After 3 mass ratio grinding is uniform, it is placed in corundum crucible, 800 DEG C of calcinings
2 h, are cooled to room temperature, regrinding, 1000 DEG C of 20 h of calcining, are repeated once；Obtain stratiform K0.80Ti1.73Li0.67O4Chemical combination
Thing, by gained K0.80Ti1.73Li0.67O4Sample adds the hydrochloric acid solution of 1000 ml（1 mol/L）Middle stirring, every 24 h is changed once
Acid, by four circulations, then centrifugation is washed to neutrality products therefrom with deionized water, 60 DEG C of dryings, as layer
Shape H1.07Ti1.73O4·H2O；By above-mentioned stratiform H1.07Ti1.73O4•H2O and TBAOH（TBAH）（40 wt%）Solution
According to mol ratio 1:1 mixing, magnetic agitation 15 days, 3000 rpm centrifugations remove unstripped nonwoven fabric from filaments, you can obtain
H1.07Ti1.73O4•H2The colloid aqueous solution of O nanometer sheets.
The preparation of ultra-thin mixed crystal titanium dioxide nanoplate
Take H1.07Ti1.73O4·H225 ~ the 30ml of colloid aqueous solution of O nanometer sheets is placed in vial, under conditions of ultrasonic agitation
The hydrochloric acid of 1mol/L is added dropwise over, there is flocculent deposit gradually to separate out, continued dropwise addition hydrochloric acid to dissolving again is precipitated and be dispersed in solution
In, this suspension being placed in 24h is stirred on agitator, centrifugation, deionized water is washed to ion concentration less than 0.1ppm, is dried
60 DEG C of dryings in case, that is, obtain the powder of ultra-thin mixed crystal titanium dioxide nanoplate.
Fig. 1 illustrates ultra-thin mixed crystal titanium dioxide nanoplate of the invention and ultra-thin predecessor H1.07Ti1.73O4·H2O receives
The X-ray diffraction of the titanium dioxide of rice piece and object of reference P25（XRD）Figure, it can be found that the predecessor for preparing from figure
H1.07Ti1.73O4·H2O nanometer sheets are changed into two phase compositions of rutile and anatase after through peracid treatment, its constituent with
The titanium dioxide of P25 is similar, and 25 ° and 27 ° or so (101) that can distinguish anatase and rutile are equal at 2 θ angles
(111) crystal face；Fig. 2 illustrates the transmission electron microscope of ultra-thin mixed crystal titanium dioxide nanoplate of the invention（TEM）Figure and height
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 being 0.235nm parallel to the spacing of lattice of upper and lower facet from HRTEM figures, belongs to two
Titanium oxide（001）Crystal face.Fig. 3 illustrate the ultra-thin mixed crystal titanium dioxide nanoplate of synthesis AFM and it is ultraviolet can
See the spectrogram that diffuses, as can be seen from the figure thickness average out to 1.3nm of the material or so, it is believed that be monolayer
Thickness, in addition the material there are more preferable absorbing properties than P25.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, its 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 for preparing is catalyzed reduction carbon dioxide as catalyst under illumination condition.
Weigh 10 mg nanometer sheets to be placed in quartz ampoule, catalyst is evenly spread on test tube wall, vacuumize to drain air, be full of
Carbon dioxide simultaneously adds 10 μ L water, stirs at normal temperatures, and being then turned on light source carries out light-catalyzed reaction, and product uses Agilent
7890 gas chromatographic detections；The light source that experiment is 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 more than 90% to the selectivity for producing methane.Therefore, synthesized ultra-thin two-dimension two
TiOx nano piece has the selectivity of the active and higher synthesizing methane of carbon dioxide reduction higher, is that one kind has extensively
The photochemical catalyst of application prospect.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (6)
1. a kind of ultra-thin mixed crystal titanium dioxide nanoplate, it is characterised in that：Described ultra-thin mixed crystal titanium dioxide nanoplate contains
The mixed phase of anatase and rutile, and the ratio of anatase and rutile is 7:3；Described ultra-thin mixed crystal nano titania
The size of piece is：The length of 200 ~ 250 nm, the width of 60 ~ 100nm, the thickness of 0.6 ~ 1.5nm.
2. ultra-thin mixed crystal titanium dioxide nanoplate according to claim 1, it is characterised in that：The ratio table of the nanometer sheet
Area average out to 193.3m2 g-1。
3. a kind of method for preparing ultra-thin mixed crystal titanium dioxide nanoplate as claimed in claim 1 or 2, it is characterised in that：
With metatitanic acid nanometer sheet H1.07Ti1.73O4·H2O is predecessor, and by HCl treatment, the method for one-step synthesis prepares institute
State mixed crystal nano material.
4. preparation method according to claim 3, it is characterised in that：Comprise the following steps that：
（1）Under conditions of ultrasonic agitation, toward H1.07Ti1.73O4·H21mol/L is added dropwise in the colloid aqueous solution of O nanometer sheets
Hydrochloric acid, until the precipitation for producing is re-dissolved in hydrochloric acid solution；
（2）By step（1）After the mixed liquor stirring 24h for obtaining, centrifugation, and fully washed to ion concentration with deionized water
Less than 0.1ppm；
（3）60 DEG C of drying in baking oven are placed in, that is, obtain the titanium dioxide nanoplate of ultra-thin mixed crystal.
5. a kind of application of ultra-thin mixed crystal titanium dioxide nanoplate as claimed in claim 1, it is characterised in that：Described is ultra-thin
Mixed crystal titanium dioxide nanoplate is used in light-catalyzed reaction as heterogeneous photocatalyst.
6. application according to claim 5, it is characterised in that：Described ultra-thin mixed crystal titanium dioxide nanoplate is used for normal temperature
Photocatalytic reduction of carbon oxide and methane is produced under normal pressure, the selectivity for obtaining methane reaches more than 90%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111097403A (en) * | 2018-10-26 | 2020-05-05 | 中国科学院金属研究所 | High-valence metal ion doped titanium-based nano material and preparation method and application thereof |
| CN116081583A (en) * | 2023-02-15 | 2023-05-09 | 浙江大学 | Preparation method of ultrathin titanium nitride nanosheets and ultrathin titanium nitride nanosheets |
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| CN103771508A (en) * | 2014-01-20 | 2014-05-07 | 国家纳米科学中心 | Fractionated mixed-crystalline TiO2 micro/nano material as well as preparation method and use thereof |
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| CN103771508A (en) * | 2014-01-20 | 2014-05-07 | 国家纳米科学中心 | Fractionated mixed-crystalline TiO2 micro/nano material as well as preparation method and use thereof |
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| QI FENG: "Single Nanocrystals of Anatase-Type TiO 2 Prepared from Layered Titanate Nanosheets: Formation Mechanism", 《LANGMUIR》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097403A (en) * | 2018-10-26 | 2020-05-05 | 中国科学院金属研究所 | High-valence metal ion doped titanium-based nano material and preparation method and application thereof |
| CN111097403B (en) * | 2018-10-26 | 2022-12-13 | 中国科学院金属研究所 | High-valence metal ion doped titanium-based nano material and preparation method and application thereof |
| CN116081583A (en) * | 2023-02-15 | 2023-05-09 | 浙江大学 | Preparation method of ultrathin titanium nitride nanosheets and ultrathin titanium nitride nanosheets |
| CN116081583B (en) * | 2023-02-15 | 2023-09-19 | 浙江大学 | Preparation method of ultrathin titanium nitride nanosheets and ultrathin titanium nitride nanosheets |
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