CN116553607B - Ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 Method for preparing nanosheets and application thereof - Google Patents
Ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 Method for preparing nanosheets and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 32
- 238000010992 reflux Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 48
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000009833 condensation Methods 0.000 title abstract description 20
- 230000005494 condensation Effects 0.000 title abstract description 20
- 239000004408 titanium dioxide Substances 0.000 title abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000002064 nanoplatelet Substances 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- 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
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- 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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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- 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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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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
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Abstract
The invention discloses a method for preparing ultrathin TiO based on a condensation reflux method 2 A method for preparing nano-sheets and application thereof belong to the technical field of catalytic material preparation. Adding a titanium precursor into ethylene glycol, and fully stirring in a three-neck flask to obtain an ethylene glycol solution of titanium; introducing water into the ethylene glycol solution of titanium under the continuous stirring state, and then reacting the solution at 220-250 ℃; washing and centrifuging the white suspension obtained after the reaction for multiple times to obtain white precipitate; and (3) drying the obtained white precipitate in vacuum, cooling to room temperature, and grinding to obtain the ultrathin titanium dioxide nanosheets. The ultrathin nanosheet material is obtained by a condensation reflux method, the preparation process is simple and safe, the cost is low, and the yield of waste byproducts is low; ultrathin TiO prepared 2 The nano-sheet has strong practicability and can reduce CO in photocatalysis 2 Has potential application prospect in the aspect of liquid fuel.
Description
Technical Field
The invention belongs to the technical field of catalytic material preparation, and particularly relates to a catalystAnd preparing ultrathin TiO based on condensation reflux method 2 A method for preparing nanometer sheet and application thereof.
Background
In recent years, CO related to energy demand worldwide 2 The emission amount is increased year by year, and a large amount of CO 2 Emissions can cause serious environmental problems such as global air temperature rise and sea level rise. In the current research, CO 2 The green resource is used as a chemical with high added value, and the approaches mainly include photocatalysis, electrocatalysis, photo-thermal synergistic catalysis and the like. CO is produced by developing and utilizing solar fuel 2 The photo-reduction to high energy compounds (e.g. methanol, ethanol, even high carbon compounds) enables the storage of solar energy in chemical form, which is also essentially a cyclic process of carbon neutralization. CO 2 The molecule is in a linear configuration and has very stable chemical property, which means that CO is added into the molecule 2 Photoreduction is a very difficult reaction to occur. In addition, the reduction products are numerous and occur with side reactions of the reduction of water to hydrogen. Therefore, there is a need to reduce photocatalytic CO by developing suitable photocatalysts 2 The activation energy of the reduction reaction realizes the selective control of the preferred product.
TiO 2 The advantages of stable physical and chemical properties, no toxicity and pollution, low cost and the like are widely applied to the field of photocatalysis. TiO (titanium dioxide) 2 There are mainly four crystalline phases: anatase phase, brookite phase, rutile phase, tiO 2 (B) And (3) phase (C). The first three have been widely studied, while TiO 2 (B) Because of a metastable structure, the problems of high temperature, easy phase change and the like exist, and the application of the metastable structure is limited. Photocatalytic CO with relatively mild reaction conditions 2 Reduction as a probe reaction to synthesize TiO 2 (B) The phase is used as a photocatalyst for exploration, and has good application prospect.
Common TiO 2 The nano-sheet is limited by the problems of thicker thickness, smaller specific surface area and the like, and in order to improve the activity of the catalyst, many researches are conducted to improve the activity from the angles of doping other elements, constructing heterojunction with other semiconductors in a compounding way and the like. By adjusting the synthesis environment of the catalyst, the preparation of the ultrathin nano-sheet with high specific area not only can provide more active sites, but alsoThe light absorption capacity can be effectively enhanced, the recombination rate of photo-generated electron hole pairs can be reduced, and the reduction capacity of a conduction band can be improved. However, no synthesis of ultra-thin TiO in an open system at atmospheric pressure has been employed to date 2 (B) Preparation of phase nanosheets and photocatalytic CO 2 Report of reduction application.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for preparing ultrathin TiO based on a condensation reflux method 2 The method for preparing the nano-sheet has the advantages of green and simple preparation process, low cost and no waste byproducts. Another technical problem to be solved by the invention is to provide a method for preparing ultrathin TiO based on a condensation reflux method 2 The nano sheet material has strong practicability and high environmental stability. The invention aims to provide a method for preparing ultrathin TiO based on a condensation reflux method 2 Catalytic reduction of CO with nanoplatelets 2 The nanosheet material has the advantages of high photo-generated carrier generation and transmission efficiency, high reducing capability and the like in the field of photocatalysis, and has potential application prospects in the aspect of closed-loop carbon fixation.
In order to solve the technical problems, the invention adopts the following technical scheme:
ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 A method of nanoplatelets comprising the steps of: titanium tetrachloride and ethylene glycol are mixed and fully stirred to obtain an ethylene glycol solution of titanium; adding water into the glycol solution of titanium under the continuous stirring state, and introducing the mixture into a condensation reflux device for condensation reflux reaction for 4 to 8 hours under the oil bath condition; washing the obtained product with deionized water and absolute ethyl alcohol, vacuum drying, cooling to room temperature, and grinding to obtain ultrathin TiO 2 A nano-sheet.
Preferably, the method for preparing ultrathin TiO based on the condensation reflux method 2 The volume ratio of titanium tetrachloride to ethylene glycol in the nano-sheet method is 1:10 to 30 percent; the volume ratio of titanium tetrachloride to water is 1:1 to 5.
Preferably, the method for preparing ultrathin TiO based on the condensation reflux method 2 The method of the nano-sheet is that,fully stirring until the solution is light yellow and has no sediment; the stirring time is 0.5-1 h.
Preferably, the method for preparing ultrathin TiO based on the condensation reflux method 2 The method for preparing the nano-sheet is carried out for 12-24 hours.
Preferably, the method for preparing ultrathin TiO based on the condensation reflux method 2 Method for preparing nanosheets with specific surface area of 300-400 m 2 /g。
The ultra-thin TiO 2 Nanosheets for photocatalytic reduction of CO 2 Is applied to the field of the application.
Preferably, the ultra-thin TiO 2 Nanosheets for photocatalytic reduction of CO 2 Is applied to the photocatalytic reduction of CO at normal temperature and normal pressure 2 And methanol and/or ethanol are produced.
The photocatalytic reduction of CO at normal temperature and normal pressure 2 The method for preparing methanol and/or ethanol comprises the steps of firstly taking a precursor ethylene glycol solution of titanium as a raw material, taking water as a solvent, and preparing ultrathin TiO by a condensation reflux method 2 A nanosheet; then ultra-thin TiO is used 2 Nanosheets are used as catalysts for photocatalytic reduction of CO at normal temperature and pressure 2 And methanol and/or ethanol are prepared.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1) The ultra-thin tiO 2 The method for preparing the nano-sheet in the normal pressure open system is simple and easy to operate and low in cost; compared with the traditional method, the method does not need sulfuric acid, has low yield of waste byproducts and is green and clean.
2) The method can synthesize TiO 2 (B) Unlike the common rutile, anatase and brookite phases, the phase structure of TiO 2 (B) The phase has abundant open microporous structure and larger specific surface area, so that more active sites can be exposed for CO 2 Is activated by adsorption.
3) Ultrathin TiO prepared by the method 2 The thickness of the nano sheet is only 0.4-2nm, so that the separation of photo-generated electrons and holes can be accelerated, and the migration distance of photo-generated carriers can be greatly shortened; surface-enriched Ti 3+ Capable of enhancing the reduction of the systemCapability of favoring CO 2 To promote photocatalytic CO 2 The reduction reaction is carried out, and finally, the ultra-thin TiO is effectively prompted 2 Photocatalytic properties of nanoplatelet materials. Therefore, adopting a method based on condensation reflux to prepare the ultrathin TiO 2 The nano sheet material not only has good synthesis application value, but also has wide prospect in the fields of catalytic systems and catalytic practical application.
Drawings
FIG. 1 is an ultra-thin TiO of the present invention 2 TEM image of the nanoplatelets;
FIG. 2 is an ultra-thin TiO of the present invention 2 An (a) XRD pattern and (B) Raman pattern of the nanoplatelets;
FIG. 3 is an ultra-thin TiO of the present invention 2 N2 adsorption and desorption graph of the nanosheets;
FIG. 4 is an ultra-thin TiO of the present invention 2 Water contact angle diagram of the nanosheets;
FIG. 5 is an ultra-thin TiO of the present invention 2 PL (a) spectral plot, (B) photoelectric plot, (C) impedance plot of the nanoplatelets;
FIG. 6 is a photocatalytic CO under full spectrum illumination for the catalyst of the present invention 2 Activity profile of reduction.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are carried out on the basis of the technical solutions of the invention, it being understood that these examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
Ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 A method of nanoplatelets comprising the steps of:
(1) 30mL of ethylene glycol solution is measured and placed in a three-neck flask; 1mL of titanium tetrachloride solution was taken and introduced into 30mL of ethylene glycol, and the mixture was sufficiently stirred for 30 minutes to obtain an ethylene glycol solution of titanium.
(2) Adding 1mL of water into the solution, then introducing into a condensing reflux device, and reacting for 4 hours at 220 ℃ under the oil bath condition;
(3) And (3) alternately washing the white suspension obtained in the step (2) with water and ethanol for 4 times at room temperature, drying the obtained white precipitate in a vacuum drying oven for 12 hours, naturally cooling to room temperature, and grinding to obtain the UT-open material.
Comparison: the method is the same as above, and the difference is that: the titanium glycol solution was transferred into a 50mL polytetrafluoroethylene liner with the remaining conditions unchanged. And obtaining a target product UT after the reaction.
FIG. 1 is a transmission electron microscope image of UT-open material, and the prepared catalyst material is ultrathin nanosheets with thickness of 0.4-2nm, and shows a typical two-dimensional material structure.
FIG. 2 is an X-ray diffraction pattern (XRD) and Raman pattern of UT, UT-open material, combined with the two patterns, showing that the prepared sample has unique TiO 2 (B) Phase structure.
FIG. 3 is an N2 adsorption/desorption curve of materials UT, UT-open, and shows that all samples are IV adsorption isotherms, and have H3 hysteresis loops, indicating that slit-shaped gaps exist; the specific surface area of UT-open is 325m by BET formula 2 /g。
FIG. 4 is a graph of the water contact angle of the materials UT, UT-open, showing that UT-open has a lower water contact angle, indicating better hydrophilicity and more oxygen-containing species adsorbed on the UT-open surface.
FIG. 5 is a PL spectrum (A), a photoelectric graph (B) and an impedance graph (C) of the UT-open material, and as can be seen from FIG. 5A, the PL emission peak intensity of the UT-open is obviously reduced when the excitation wavelength is 325nm, which shows that the UT-open material effectively inhibits the recombination of electron-hole pairs, and more photo-generated electrons can be used for CO 2 And (5) light reduction. As can be seen from FIG. 5B, the photocurrent intensity of the two samples is I UT-open ＞I UT The greater the current intensity, the higher the electron-hole separation efficiency. UT-open has higher photo-induced charge transfer capability in all samples, with better photo-catalytic efficiency. As can be seen from FIG. 5C, the electrochemical impedance spectra further confirm the conclusion that the radius of the Nyquist curve for the UT-open sample is significantly reduced, indicating that UT-open has rapid photo-induced charge transfer and lower charge recombination efficiency.
Example 2
Application of the photocatalyst prepared in example 1 to photocatalysisCO conversion 2 In the reduction, the experimental steps are:
CO 2 the photoreduction reaction is gas-phase CO built by the laboratory 2 The reduction activity evaluation was carried out by a DOI/10.1016/j.jcou.2021.101825.
The specific steps of activity evaluation are as follows:
(1) Weighing 20mg of sample, placing the sample in a quartz tank reactor, introducing 5mL of ultrapure water, and performing ultrasonic treatment for 30min to ensure uniform dispersion of the sample;
(2) Placing the mixture into a 100mL autoclave after uniform mixing, and sealing the reactor by using a flange plate;
(3) High purity CO using partial pressure valve 2 Introducing into autoclave, total 0.4Mpa, and charging and discharging gas for 5 times to ensure pure CO in the reactor 2 An atmosphere;
(4) After the inflation and deflation are completed, introducing high-purity CO 2 To 0.4MPa, the lamp (300W Xe lamp) was turned on, and the whole spectrum was irradiated for 8 hours. The reactor temperature was maintained at 25 ℃. At the same time, the argon gas cylinder and the air cylinder are opened, the hydrogen generator is opened, and the chromatographic instrument and corresponding software on the computer are opened. Regulation of N 2 The partial pressure was 0.3MPa, and the air partial pressure was adjusted to 0.2MPa. Temperature control, ignition and baseline balancing processes are carried out;
(5) The gas in the reactor was detected on-line by gas chromatography. Qualitative and quantitative analysis of the gas in the reactor was performed by standard gas. The liquid in the reactor was detected on the GC-FID using a headspace sampler and quantitatively analyzed by establishing standard curves for high and low concentrations.
FIG. 6 is a graph of the light CO of the prepared sample under full spectrum illumination 2 The reduction effect is shown by the graph, and compared with the ultrathin TiO prepared in a closed environment, the two samples are generated by alcohol substances 2 The light catalytic effect of UT-open is better for the nano sheet material; after 8h of photoreaction, the yields of methanol and ethanol of UT-open were 189.2. Mu. Mol/g and 167.3. Mu. Mol/g, respectively.
Example 3
Ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 A method of nanoplatelets comprising the steps of:
(1) In a three-necked flask, 1mL of titanium tetrachloride was introduced into 30mL of ethylene glycol, and stirred well for 30min;
(2) Adding 1mL of water into the solution, then introducing into a condensing reflux device, and reacting for 6 hours at 240 ℃ under the condition of oil bath;
(3) And (3) alternately washing the white suspension obtained in the step (2) with water and ethanol for 4 times at room temperature, drying the obtained white precipitate in a vacuum drying oven for 12 hours, naturally cooling to room temperature, and grinding to obtain a target product.
Application of the prepared photocatalyst to photocatalytic CO 2 In the reduction, the experimental procedure is the same as in example 2, and the results show that the methanol and ethanol yields of the photocatalyst are respectively: 162.4. Mu. Mol/g, 173.4. Mu. Mol/g
Example 4
Ultra-thin TiO (titanium dioxide) prepared based on condensation reflux method 2 A method of nanoplatelets comprising the steps of:
(1) In a three-necked flask, 1mL of titanium tetrachloride was introduced into 30mL of ethylene glycol, and stirred well for 50min;
(2) Adding 1mL of water into the solution, then introducing into a condensing reflux device, and reacting for 8 hours at 250 ℃ under the condition of oil bath;
(3) And (3) alternately washing the white suspension obtained in the step (2) with water and ethanol for 4 times at room temperature, drying the obtained white precipitate in a vacuum drying oven for 18 hours, naturally cooling to room temperature, and grinding to obtain a target product.
Application of the prepared photocatalyst to photocatalytic CO 2 In the reduction, the experimental procedure is the same as in example 2, and the results show that the methanol and ethanol yields of the photocatalyst are respectively: 178.1. Mu. Mol/g, 159.6. Mu. Mol/g.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. Ultra-thin TiO 2 Photocatalytic reduction of CO at normal temperature by nano-sheet 2 And produceUse of raw methanol and/or ethanol, said ultra-thin TiO 2 The nano-sheet is prepared by the following steps:
(1) In a three-necked flask, 1mL of titanium tetrachloride solution is introduced into 30mL of ethylene glycol, and the mixture is fully stirred for 30min to obtain an ethylene glycol solution of titanium;
(2) Adding 1mL of water into the glycol solution of titanium, then introducing into a condensing reflux device, and reacting for 4 hours at 220 ℃ under the condition of oil bath;
(3) Washing the white suspension obtained in the step (2) with water and ethanol alternately for 4 times at room temperature, drying the obtained white precipitate in a vacuum drying oven for 12h, naturally cooling to room temperature, and grinding to obtain ultrathin TiO 2 A nanosheet;
the ultra-thin TiO 2 The nanosheets are used for photocatalytic reduction of CO at normal temperature 2 And 189.2. Mu. Mol/g of methanol and/or 167.3. Mu. Mol/g of ethanol, in which high-purity CO was introduced 2 Regulating N to 0.4Mpa 2 The partial pressure was 0.3MPa, and the air partial pressure was adjusted to 0.2MPa.
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| CN109837605A (en) * | 2019-01-30 | 2019-06-04 | 中国科学院长春应用化学研究所 | Compound brush filament of a kind of titania modified polyester nano of two-dimensional ultrathin and preparation method thereof |
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