CN111268725A - Preparation method and application of {001} crystal face exposed porous titanium dioxide nanosheet - Google Patents
Preparation method and application of {001} crystal face exposed porous titanium dioxide nanosheet 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 158
- 239000002135 nanosheet Substances 0.000 title claims abstract description 65
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 60
- 239000013078 crystal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000011941 photocatalyst Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
-
- B01J35/40—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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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- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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
- C01P2006/16—Pore diameter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A preparation method and application of a {001} crystal face exposed porous titanium dioxide nanosheet belong to a preparation method and application of a semiconductor photocatalytic material. In particular to a method for preparing a {001} crystal face exposed porous titanium dioxide nanosheet in a cyclohexanol-hexafluorotitanic acid-tetrabutyltitanate reaction system, and application of the nanosheet as a semiconductor material in photocatalytic decomposition and hydrolysis hydrogen evolution reaction. In the method, hexafluorotitanic acid and tetrabutyl titanate are dissolved in cyclohexanol; putting the obtained solution into a closed homogeneous reaction container for reaction; and after the reaction is finished, quickly cooling, separating, washing and drying to obtain the target product. The method has the advantages of simple process, good repeatability, high purity of the obtained product, good dispersibility, uniform and controllable size distribution, nano porous structure and high {001} crystal face exposure ratio, and is expected to be produced in large scale. The titanium dioxide nanosheet is used as a photocatalytic material, and the hydrolysis hydrogen evolution performance of the titanium dioxide nanosheet is excellent, so that the titanium dioxide nanosheet has good economic benefit and wide market prospect.
Description
Technical Field
The invention relates to a preparation method and application of a semiconductor photocatalytic material, in particular to a preparation method and application of a {001} crystal face exposed porous titanium dioxide nanosheet.
Background
Titanium dioxide (TiO) as an important oxide semiconductor material2) Has been widely applied in a plurality of fields such as environment, energy, chemical industry, life science, etc. For TiO2In the case of photocatalysts, many physical and chemical processes occur on a surface, and photocatalytic performance depends largely on its surface structure. It has been shown that anatase TiO2The photocatalytic performance of a material in terms of degradation of organic contaminants and water decomposition, etc., depends to a large extent on the type and proportion of crystal exposed surfaces. Generally speaking, anatase TiO2Has the lowest surface energy (0.44 Jm)-2) And better kinetic stability, so it is easier to expose on the outer surface of the crystal, forming truncated octahedral bipyramidal structure with {101} plane as the dominant. In contrast, the {001} crystal plane has a higher surface energy (0.90J m)-2) And cannot be exposed on a large scale to the surface. However, recent studies have found that TiO2The 001 crystal plane of the crystal also plays a key role in the selective separation of photo-generated electrons and holes. Therefore, how to prepare TiO with high {001} crystal face exposure ratio and stable structure and excellent photocatalytic performance2The nano-sheet becomes a hot problem in the field of current photocatalytic research.
To address this difficulty, hydrofluoric acid is often used as a capping agent to stabilize anatase TiO2And thus a {001} crystal plane of high exposure ratio is obtained. This anatase type TiO2The crystal has important research value and application potential in the fields of solar cells, photocatalysis, photon and photoelectric devices and the like. Although different hydrothermal and solvothermal (ethanol or isopropanol) systems have been developed to control this anatase TiO2The growth of the nano-sheets, however, the existing preparation technologies still have the defects of high danger, complicated preparation process, long time and appearance of the obtained productOr poor performance. Therefore, there is an urgent need to develop a simple, efficient and safe method for preparing TiO with regular morphology and excellent performance2Nanosheets.
Disclosure of Invention
The invention aims to provide a preparation method and application of a {001} crystal face exposed porous titanium dioxide nanosheet, and solves the problems of high risk, long time, complex process and poor appearance or performance of an obtained product in a common preparation method.
The purpose of the invention is realized as follows: the preparation method comprises the steps of dissolving a certain amount of titanium source in cyclohexanol to obtain a uniform solution; transferring the solution into a closed homogeneous reaction container, and carrying out solvothermal reaction on a titanium source in a cyclohexanol solvent; after the reaction is finished, the porous anatase TiO with high purity, good dispersity and high {001} crystal face exposure ratio is finally obtained through quick cooling, separation, washing and drying2Nanosheets.
The method comprises the following specific steps:
step (1), adding a certain amount of titanium source into cyclohexanol, stirring and dissolving to obtain a milky white solution (1);
step (2), transferring the milky white solution (1) to a sealed and pressure-resistant homogeneous reaction vessel for reaction;
after the reaction is finished, taking out the product, separating, washing and drying to obtain white porous TiO2Nanosheets.
In the step (1), the titanium source is a mixture of hexafluorotitanic acid and tetrabutyl titanate; the total molar concentration of titanium in the solution is 0.01-0.5 mol/L; the molar ratio of the hexafluorotitanic acid to the tetrabutyl titanate is 2: 1-1: 10;
in the step (1), the stirring time is 1-30 min, and the stirring speed is 200-800 rpm.
In the step (2), the temperature during the reaction is 150-220 ℃; the reaction time is 30-200 min; the rotation speed of the homogeneous reaction vessel is 150-500 rpm.
In the step (3), the separation mode is centrifugation or suction filtration; the washing solvent is deionized water, absolute ethyl alcohol or acetone; the drying mode is natural drying, freeze drying or vacuum drying.
In the step (3), the obtained TiO2The length and width range of the nano sheet is 500-950 nm, and the thickness range is 5-20 nm; the nano sheet has high dispersibility, uniform and controllable size distribution and a porous structure; the aperture range is 1-20 nm; the exposure proportion of the {001} crystal face reaches 95-99%.
Based on TiO2The application of the nano-sheets in photocatalytic hydrogen production and pollutant degradation: based on porous TiO2Nanosheet, made into TiO2Pt photocatalyst, the TiO2The Pt photocatalyst is used for catalyzing water to decompose and produce hydrogen, and excellent photocatalytic hydrogen production performance is obtained.
Subjecting the obtained porous TiO2Preparing TiO by nano-sheet supported Pt2The Pt photocatalyst is prepared by the following specific steps:
firstly, TiO is respectively weighed according to a certain mass ratio2Nanosheets and chloroplatinic acid;
secondly, adding a proper amount of absolute ethyl alcohol into the mixture, and fully stirring the mixture to obtain a solution;
thirdly, the solution is placed in the light for a period of time, and then washed and vacuum dried;
finally, porous TiO loaded with Pt is obtained2A nanosheet photocatalyst.
The obtained TiO is2The method for preparing hydrogen by applying Pt photocatalyst to photocatalysis comprises the following steps:
and step 4, the reaction time is 2.5 h. During the period, every 30min, 1mL of gas is taken to pass through a molecular sieve of a gas chromatograph for hydrogen production test.
Has the advantages that the adoption ofAccording to the scheme, in a cyclohexanol solvothermal system, hexafluorotitanic acid and tetrabutyl titanate are used as raw materials to prepare TiO with high purity, good dispersity, a nano porous structure and a high {001} crystal face exposure ratio2Nanosheets. Compared with solvents such as water, isopropanol and the like used in the traditional method, the cyclohexanol has the characteristics of low polarity, high viscosity and the like, and is more favorable for the stable existence of a {001} crystal face. Hexafluorotitanic acid can be used as a part of titanium source and can also be used as porous TiO2Compared with hydrofluoric acid used in the traditional method, the structure control agent of the nano-sheet has the advantages of low toxicity, milder reaction and the like. TiO prepared by the invention2The nano-sheet has a nano-porous structure, so that more reaction sites are provided for photocatalytic hydrogen production, and more excellent photocatalytic performance is obtained. The TiO being2The nano-sheet is applied to photocatalytic degradation of organic pollutants, photocatalytic hydrogen production and related fields in a single or composite mode.
Solves the problems of high danger, long time, complex process and poor appearance or performance of the obtained product in the common preparation method, and achieves the aim of the invention.
Compared with the prior art, the invention has the following advantages:
(1) the porous TiO is prepared by using cyclohexanol as solvent and hexafluorotitanic acid and tetrabutyl titanate as raw materials for the first time2Nanosheets; the obtained product has regular appearance, high purity, large size, high dispersion and extremely high {001} crystal face exposure ratio; the preparation method is simple, good in repeatability and easy to operate, and is expected to be applied to large-scale industrial production.
(2) Compared with solvents such as water, isopropanol and the like used in the traditional method, the cyclohexanol has the characteristics of low polarity, high viscosity and the like, and is more favorable for the stable existence of a {001} crystal face. Hexafluorotitanic acid can be used as a part of titanium source and can also be used as porous TiO2A structural control agent for the nanosheets. Compared with hydrofluoric acid used in the traditional method, the method has the advantages of low toxicity, milder reaction and the like. In addition, the cyclohexanol solvent can react with TiO2The white powder is completely separated, so the cyclohexanol solvent can be recycled, energy is effectively saved, and environmental pollution is reduced.
(3) The TiO has unique structural advantages of porosity, extremely high {001} face exposure percentage and the like2The nano-sheet loaded with platinum shows excellent photocatalytic hydrogen production performance when used as a photocatalytic material. When the Pt content is 4 wt%, the hydrogen production rate can reach 2239 mu mol h at most-1g-1. Furthermore, Pt/TiO2The catalyst also exhibits long-lasting cycling stability during the photocatalytic process.
(4) TiO prepared by the invention2The nano sheet has the advantages in the nano porous structure, the {001} crystal face exposure proportion and the application aspect of photocatalytic hydrogen production, so that the nano sheet has good economic benefit and wide market prospect.
Drawings
FIG. 1 shows TiO prepared in example 1 of the present invention2X-ray powder diffraction pattern of the nanoplatelets.
FIG. 2 shows TiO prepared in example 1 of the present invention2Scanning electron microscopy of nanoplates.
FIG. 3 shows TiO prepared in example 1 of the present invention2High resolution transmission electron microscopy of the nanoplatelets.
FIG. 4 shows TiO prepared in example 1 of the present invention2And (3) a photocatalytic hydrogen evolution rate graph after the nano sheets are loaded with platinum particles with different mass percentages.
FIG. 5 shows TiO prepared in example 1 of the present invention2And (3) a photocatalytic hydrogen evolution circulation stability test chart after the nano-sheet loads platinum particles.
Detailed Description
The preparation method comprises the steps of dissolving a certain amount of titanium source in cyclohexanol to obtain a uniform solution; transferring the solution into a closed homogeneous reaction container, and carrying out solvothermal reaction on a titanium source in a cyclohexanol solvent; after the reaction is finished, the porous anatase TiO with high purity, good dispersity and high {001} crystal face exposure ratio is finally obtained through quick cooling, separation, washing and drying2Nanosheets.
The method comprises the following specific steps:
step (1), adding a certain amount of titanium source into cyclohexanol, stirring and dissolving to obtain a milky white solution (1);
step (2), transferring the milky white solution (1) to a sealed and pressure-resistant homogeneous reaction vessel for reaction;
after the reaction is finished, taking out the product, separating, washing and drying to obtain white porous TiO2Nanosheets.
In the step (1), the titanium source is a mixture of hexafluorotitanic acid and tetrabutyl titanate; the total molar concentration of titanium in the solution is 0.01-0.5 mol/L; the molar ratio of the hexafluorotitanic acid to the tetrabutyl titanate is 2: 1-1: 10;
in the step (1), the stirring time is 1-30 min, and the stirring speed is 200-800 rpm.
In the step (2), the temperature during the reaction is 150-220 ℃; the reaction time is 30-200 min; the rotation speed of the homogeneous reaction vessel is 150-500 rpm.
In the step (3), the separation mode is centrifugation or suction filtration; the washing solvent is deionized water, absolute ethyl alcohol or acetone; the drying mode is natural drying, freeze drying or vacuum drying.
In the step (3), the obtained TiO2The length and width range of the nano sheet is 500-950 nm, and the thickness range is 5-20 nm; the nano sheet has high dispersibility, uniform and controllable size distribution and a porous structure; the aperture range is 1-20 nm; the exposure proportion of the {001} crystal face reaches 95-99%.
Based on TiO2The application of the nano-sheets in photocatalytic hydrogen production and pollutant degradation: based on porous TiO2Nanosheet, made into TiO2Pt photocatalyst, the TiO2The Pt photocatalyst is used for catalyzing water to decompose and produce hydrogen, and excellent photocatalytic hydrogen production performance is obtained.
Subjecting the obtained porous TiO2Preparing TiO by nano-sheet loaded platinum (Pt)2The Pt photocatalyst is prepared by the following specific steps:
firstly, TiO is respectively weighed according to a certain mass ratio2Nanosheets and chloroplatinic acid;
secondly, adding a proper amount of absolute ethyl alcohol into the mixture, and fully stirring the mixture to obtain a solution;
thirdly, the solution is placed in the light for a period of time, and then washed and vacuum dried;
finally, porous TiO loaded with Pt is obtained2A nanosheet photocatalyst.
The obtained TiO is2The method for preparing hydrogen by applying Pt photocatalyst to photocatalysis comprises the following steps:
and step 4, the reaction time is 2.5 h. During the period, every 30min, 1mL of gas is taken to pass through a molecular sieve of a gas chromatograph for hydrogen production test.
The technical scheme of the invention is further explained by combining specific examples.
Example 1: accurately measuring 20mL of cyclohexanol, sequentially adding 2mmol of hexafluorotitanic acid and 2.5mmol of tetrabutyl titanate, and stirring to dissolve to obtain a milky solution; transferring the solution into a sealed and pressure-resistant homogeneous reaction vessel, and reacting at the rotation speed of 300rpm and the temperature of 180 ℃ for 150 min; and (3) rapidly cooling the product to room temperature, repeatedly washing the product with deionized water and absolute ethyl alcohol, centrifuging the product, and drying the product in vacuum to obtain a pure white powder product.
The product was subjected to Bruker D8 ADVANCE X-ray powder diffractometer (Cu K α rays, wavelength)
Scanning pace of 0.08 °/sec) was identified as anatase type TiO2The powder (FIG. 1), which matches the JCPDS card standard (No.21-1272), no other impurity peaks appear.
Adopting SU-8200 scanning electron microscope to observe anatase TiO2The morphology of the nanosheets is shown in figure 2. The obtained product consists of nanosheets with the size range of 500-900 nm and the thickness of 5-10 nm, and the nanosheetsHas high dispersibility, regular shape and obvious porous structure. The high resolution TEM image in FIG. 3 shows that the obtained product is TiO with exposed {001} crystal face2Nanosheets. The exposure ratio of the {001} crystal face reaches 99 percent through calculation.
Testing the photocatalytic hydrogen production performance:
first, a certain amount of chloroplatinic acid and 0.1g of TiO were added2Sequentially adding the nanosheets into 100mL of absolute ethyl alcohol, and fully stirring; placing the solution under illumination for 2h, and washing to obtain a reaction product; the product was placed in an oven for vacuum drying. Weighing a certain mass of the obtained product, dispersing the product in a methanol/water mixed solution (volume ratio is 1:4), introducing nitrogen, bubbling for a certain time, and sealing. Then, a photocatalytic reaction test was performed, and the test results are shown in fig. 4 and 5.
The experimental results are as follows: as shown in FIG. 4, TiO obtained in example 12The photocatalytic hydrogen production activity of the nanosheet under the simulated solar lamp is very low and is about 45 mu mol g-1h-1. After deposition of the Pt particles, the Pt/TiO obtained2The hydrogen production activity of the photocatalyst gradually increases with the increase of the Pt content. At a Pt content of 4 wt.% (PT 4 sample in FIG. 4), up to 2239. mu. mol h can be achieved-1g-1. Subsequently, as the Pt content increases, the Pt/TiO2The photocatalytic hydrogen production activity is reduced.
The results in FIG. 5 show that, in addition to having significant photocatalytic hydrogen production activity, Pt/TiO2Also exhibit long-lasting cycling stability during the photocatalytic process. After 4 days of circulation for more than 2.5 hours, the photocatalytic performance of the PT4 sample is stable, and no obvious attenuation is seen.
Example 2: accurately measuring 15mL of cyclohexanol, sequentially adding 1mmol of hexafluorotitanic acid and 3mmol of tetrabutyl titanate, and stirring for dissolving to obtain a milky solution; transferring the solution into a sealed and pressure-resistant homogeneous reaction vessel, and reacting for 180min at the rotation speed of 300rpm and the temperature of 200 ℃; and (3) rapidly cooling the product to room temperature, repeatedly washing the product by using deionized water and acetone, centrifuging the product, and freeze-drying the product to obtain a pure white powder product.
Claims (9)
1. A preparation method of a {001} crystal face exposed porous titanium dioxide nanosheet is characterized by comprising the following steps: the preparation method comprises the steps of dissolving a certain amount of titanium source in cyclohexanol to obtain a uniform solution; transferring the solution into a closed homogeneous reaction container, and carrying out solvothermal reaction on a titanium source in a cyclohexanol solvent; and after the reaction is finished, quickly cooling, separating, washing and drying to finally obtain the porous anatase type titanium dioxide nanosheet with high purity, good dispersibility and high {001} crystal face exposure ratio.
2. The preparation method of the porous titanium dioxide nanosheet with the exposed {001} crystal face, according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following specific steps:
step (1), adding a certain amount of titanium source into cyclohexanol, stirring and dissolving to obtain a milky white solution (1);
step (2), transferring the milky white solution (1) to a sealed and pressure-resistant homogeneous reaction vessel for reaction;
and (3) after the reaction is finished, taking out the product, separating, washing and drying to obtain the white porous titanium dioxide nanosheet.
3. The preparation method of the porous titanium dioxide nanosheet with the exposed {001} crystal face, according to claim 2, wherein the preparation method comprises the following steps: in the step (1), the titanium source is a mixture of hexafluorotitanic acid and tetrabutyl titanate; the total molar concentration of titanium in the solution is 0.01-0.5 mol/L; the molar ratio of the hexafluorotitanic acid to the tetrabutyl titanate is 2: 1-1: 10;
the stirring time is 1-30 min, and the stirring speed is 200-800 rpm.
4. The preparation method of the porous titanium dioxide nanosheet with the exposed {001} crystal face, according to claim 2, wherein the preparation method comprises the following steps: in the step (2), the temperature during the reaction is 150-220 ℃; the reaction time is 30-200 min; the rotation speed of the homogeneous reaction vessel is 150-500 rpm.
5. The preparation method of the porous titanium dioxide nanosheet with the exposed {001} crystal face, according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the separation mode is centrifugation or suction filtration; the washing solvent is deionized water, absolute ethyl alcohol or acetone; the drying mode is natural drying, freeze drying or vacuum drying.
6. The preparation method of the porous titanium dioxide nanosheet with the exposed {001} crystal face, according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the obtained titanium dioxide nanosheet has a length and width range of 500-950 nm and a thickness range of 5-20 nm; the nano sheet has high dispersibility, uniform and controllable size distribution and a porous structure; the aperture range is 1-20 nm; the exposure proportion of the {001} crystal face reaches 95-99%.
7. The application of the {001} crystal face exposed porous titanium dioxide nanosheet based on the claim 1 is characterized in that: the application of the titanium dioxide nanosheet in photocatalytic hydrogen production and pollutant degradation is as follows: preparing the titanium dioxide/platinum photocatalyst based on the porous titanium dioxide nanosheet. The titanium dioxide/platinum photocatalyst is used for catalyzing water to decompose and produce hydrogen, and excellent photocatalytic hydrogen production performance is obtained.
8. The application of the {001} crystal face exposed porous titanium dioxide nanosheet as set forth in claim 7, wherein: the preparation method of the titanium dioxide/platinum photocatalyst by loading platinum on the porous titanium dioxide nanosheet comprises the following steps:
firstly, respectively weighing titanium dioxide nanosheets and chloroplatinic acid according to a certain mass ratio;
secondly, adding a proper amount of absolute ethyl alcohol into the mixture, and fully stirring the mixture to obtain a solution;
thirdly, the solution is placed in the light for a period of time, and then washed and vacuum dried;
finally, the porous titanium dioxide nanosheet photocatalyst loaded with platinum is obtained.
9. The application of the {001} crystal face exposed porous titanium dioxide nanosheet as set forth in claim 7, wherein: the method for applying the obtained titanium dioxide/platinum photocatalyst to photocatalytic hydrogen production comprises the following steps:
step 1, sealing a 50mL glass tube and a rubber plug to prepare the photocatalytic hydrogen production experimental device, wherein a light source is a 350W xenon lamp;
step 2, dispersing 1-10 mg of titanium dioxide/platinum photocatalyst in a methanol/water mixed solution, introducing nitrogen into the device, bubbling for 30-60 min, and sealing;
step 3, turning on a xenon lamp, and placing the photocatalytic hydrogen production experimental device at a position 15cm away from a light source;
step 4, the reaction time is 2.5 h; during the period, every 30min, 1mL of gas is taken to pass through a molecular sieve of a gas chromatograph for hydrogen production test.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112466982A (en) * | 2020-11-03 | 2021-03-09 | 中国科学院海洋研究所 | Nanosheet array composite photoelectric material for photoelectrochemical cathodic protection, and preparation and application thereof |
| CN113265198A (en) * | 2021-05-12 | 2021-08-17 | 华中师范大学 | Catalytic purification coating easy to fix and preparation method and application thereof |
| CN113998668A (en) * | 2021-10-22 | 2022-02-01 | 杭州电子科技大学 | Application of ultrathin titanium dioxide nanosheet as photocatalyst in solar energy decomposition of lignocellulose for hydrogen production |
| CN114956166A (en) * | 2022-05-25 | 2022-08-30 | 中国矿业大学徐海学院 | Preparation method of titanium dioxide nano film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462769A (en) * | 2009-01-09 | 2009-06-24 | 厦门大学 | Titanium dioxide nanoplate and synthesizing method thereof |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN106241865A (en) * | 2016-08-23 | 2016-12-21 | 中国科学院广州地球化学研究所 | The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| CN107285376A (en) * | 2017-07-18 | 2017-10-24 | 浙江大学 | A kind of two-dimentional TiO2Ultrathin nanometer piece and preparation method thereof |
-
2020
- 2020-02-09 CN CN202010083422.5A patent/CN111268725B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462769A (en) * | 2009-01-09 | 2009-06-24 | 厦门大学 | Titanium dioxide nanoplate and synthesizing method thereof |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN106241865A (en) * | 2016-08-23 | 2016-12-21 | 中国科学院广州地球化学研究所 | The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| CN107285376A (en) * | 2017-07-18 | 2017-10-24 | 浙江大学 | A kind of two-dimentional TiO2Ultrathin nanometer piece and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112466982A (en) * | 2020-11-03 | 2021-03-09 | 中国科学院海洋研究所 | Nanosheet array composite photoelectric material for photoelectrochemical cathodic protection, and preparation and application thereof |
| CN113265198A (en) * | 2021-05-12 | 2021-08-17 | 华中师范大学 | Catalytic purification coating easy to fix and preparation method and application thereof |
| CN113998668A (en) * | 2021-10-22 | 2022-02-01 | 杭州电子科技大学 | Application of ultrathin titanium dioxide nanosheet as photocatalyst in solar energy decomposition of lignocellulose for hydrogen production |
| CN114956166A (en) * | 2022-05-25 | 2022-08-30 | 中国矿业大学徐海学院 | Preparation method of titanium dioxide nano film |
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