CN108187729B - Composite catalyst film and preparation method and application thereof - Google Patents
Composite catalyst film and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 39
- 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 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 10
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000010408 film Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 metal doping Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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Abstract
The invention provides a preparation method of a composite catalyst film, which comprises the following steps: mixing metal acid ester and alcohol to prepare a precursor; coating a matrix with a porous material solution; coating the precursor; calcining to obtain the composite catalyst film. The preparation method and the catalyst obtained by the preparation method disclosed by the invention are used for photocatalytic conversion of carbon dioxide, have higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a composite catalyst film, and a preparation method and application thereof.
Background
Due to the gradual increase of the greenhouse effect, people have more and more intensive research on the catalytic conversion of carbon dioxide. Currently, widely studied carbon dioxide reduction methods mainly include catalytic hydrogenation reduction, photocatalytic reduction, thermochemical reduction, biological reduction, and the like. Wherein the thermochemical reduction has higher requirements on reaction equipment; the photocatalytic reduction of carbon dioxide is more attractive from the viewpoint of clean and sustainable solar energy utilization. Unlike other forms of carbon dioxide conversion processes, photocatalytic reduction can directly utilize sunlight to induce the reduction of carbon dioxide. Under the irradiation of sunlight, the photocatalyst can convert carbon dioxide into available fuels and chemical substances, and has great potential in solving the problems of environment and energy.
The most studied photocatalysts are mainly metal oxides, among which titanium dioxide is taken as a representative. Titanium dioxide has the advantages of high photocatalytic activity, strong corrosion resistance, stable optical property, no toxicity, relatively low price and the like, so that the titanium dioxide is a photocatalyst applied more. The nano titanium dioxide can greatly shorten the time for a photon-generated carrier to migrate to the surface due to the reduction of the particle size, thereby reducing the recombination probability of an electron-hole in a bulk phase and hopefully improving the efficiency of photocatalytic reduction.
However, the single metal oxide also has the disadvantages of small specific surface area, low sunlight utilization rate and the like, and finding a photocatalyst with high catalytic activity and high selectivity for improving the conversion rate of carbon dioxide is a future development direction. The common methods at present are to modify metal oxides, including metal doping, non-metal doping, metal oxide compounding, organic matter compounding, etc., which can effectively reduce the particle size of the metal oxides and increase the specific surface area, thereby greatly improving the photocatalytic activity, while the low utilization rate of sunlight is still a problem to be solved.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention is directed to a composite catalyst thin film, a method for preparing the same, and a use of the same, which are used to solve the problems of low catalytic conversion efficiency and poor selectivity of carbon dioxide in the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of a composite catalyst film, which comprises the following steps:
1) mixing metal acid ester and alcohol to prepare a precursor;
2) coating a matrix with a porous material solution;
3) coating the precursor;
4) calcining to obtain the composite catalyst film.
Preferably, in step 1), the metal acid ester is one or more selected from the group consisting of tetraethyl titanate, tetrabutyl zirconate, molybdate ester, and aluminate ester.
Preferably, in step 1), the alcohol is one or more selected from methanol, ethanol, propanol and isopropanol.
Preferably, in the step 1), the mass ratio of the metal acid ester to the alcohol is (1.5-20): 40.
preferably, in step 1), the mixing is carried out under an inert atmosphere. The inert atmosphere comprises one or more of nitrogen, argon and helium. Because the raw material component of the metal acid ester is unstable and is easy to react with substances in the air to generate chemical change, the inert atmosphere is adopted for protection during mixing in the application.
Preferably, in step 1), mixing is performed using ultrasound.
Preferably, in the step 2), the porous material is one or more selected from the group consisting of an ETS-10 molecular sieve, a ZSM-5 molecular sieve, a SAPO-34 molecular sieve and an MCM-68 molecular sieve.
Preferably, in step 2), the solvent of the solution of the porous material is ethylene glycol.
Preferably, in the step 2), the concentration of the porous material solution is 1 wt% to 5 wt%. More preferably, in the step 2), the concentration of the porous material solution is 3 wt% to 5 wt%.
Preferably, in step 2), the substrate is a glass plate.
Preferably, the volume ratio of the precursor to the porous material solution is (1-7): 10.
preferably, the coating in step 2) and step 3) is performed by spin coating. More preferably, the spin coating rate is 1000 to 9000 r/min.
Preferably, in the step 4), the calcining temperature is 400-500 ℃.
Preferably, in step 4), the calcination time is not less than 0.5 hour.
The invention also provides a composite catalyst film prepared by the method.
The invention also provides application of the composite catalyst film in the photocatalytic reaction and the photoelectrocatalysis reaction of carbon dioxide.
According to the method and the application of the composite catalyst film provided by the invention, the single metal oxide nanoparticles are modified to prepare the composite system film of the metal oxide nanoparticles and the porous material, so that the carbon dioxide adsorption performance of the composite system can be improved, the utilization rate of sunlight is increased, the surface active sites and the contact area of the uniformly dispersed film can be greatly increased, and the photocatalytic activity of carbon dioxide is further effectively improved. The process is simple to operate, and the prepared catalyst film has good photocatalytic activity, high selectivity, good reproducibility and high stability. The catalyst can be applied to the processes of photocatalytic conversion and photoelectric catalytic conversion of carbon dioxide, particularly in the process of photocatalytic conversion of carbon dioxide, can greatly improve the generation rate of methanol and ethanol, has high selectivity, can solve the problems of the prior art, and has good application prospect.
Drawings
FIG. 1 is a TEM image of a composite catalyst thin film in example 6 of the present invention.
FIG. 2 shows an XPS plot of a composite catalyst thin film in example 6 of the present invention.
FIG. 3 is a schematic structural diagram of a carbon dioxide photocatalytic reaction apparatus according to an embodiment of the present invention.
Wherein the reference numerals in fig. 3 are as follows:
1 carbon dioxide gas supply device
2 steam mixing device
3 carbon dioxide light reaction device
4 carbon dioxide reaction product detection device
11 carbon dioxide gas storage unit
12 gas flowmeter
21 water container
22 water bath pot
211 inlet port
212 outlet port
31 reactor
32 catalyst carrier
33 light source
311 inlet
312 outlet
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Example 1
Weighing high-purity tetraethyl titanate and isopropanol in a glove box, wherein the mass ratio of the tetraethyl titanate to the isopropanol is 1.5:40, ultrasonically mixing for 10min in a nitrogen atmosphere to form a precursor, subpackaging in small bottles, and taking out for later use. 0.05g of molecular sieve ETS-10 is added into 1.5g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature to prepare a molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, spin-coating 200 mu L of porous material solution by using an injector, adjusting to a certain rotating speed, spin-coating at a rotating speed of 1000r/min for 20s, then spin-coating at a high rotating speed of 3000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; then 100 μ L of the precursor is taken and spun on the molecular sieve film at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 60min, and naturally cooling to room temperature to obtain the titanium dioxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Example 2
Weighing high-purity tetraethyl titanate and isopropanol in a glove box, wherein the mass ratio of the tetraethyl titanate to the isopropanol is 20:40, ultrasonically mixing for 90min in a nitrogen atmosphere to form a precursor, subpackaging in small bottles, and taking out for later use. 0.05g of ZSM-5 molecular sieve is added into 1.5g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature to prepare a molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, spin-coating 200 mu L of porous material solution by using an injector, adjusting to a certain rotating speed, spin-coating at a rotating speed of 1500r/min for 20s, then spin-coating at a high rotating speed of 9000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; and then 20 mu L of precursor is taken and is coated on the molecular sieve film in a spin mode at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at the heating rate of 30 ℃/min, keeping the temperature for 180min, and naturally cooling to room temperature to obtain the titanium dioxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Example 3
Weighing high-purity tetrabutyl zirconate and ethanol in a glove box, wherein the mass ratio of the tetrabutyl zirconate to the ethanol is 3.36:40, ultrasonically mixing for 30min in a nitrogen atmosphere to form a precursor, subpackaging in small bottles, and taking out for later use. 0.07g of SAPO-34 molecular sieve is added into 1.4g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature to prepare molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, taking 200 mu L of porous material solution by using an injector, spin-coating at a certain rotating speed for 20s at 1500r/min, then spin-coating at a high rotating speed of 8000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; then 60 μ L of the precursor is taken and spun on the molecular sieve film at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the zirconium dioxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Example 4
Weighing high-purity molybdate and propanol in a glove box, wherein the mass ratio of the molybdate to the propanol is 3.36:40, ultrasonically mixing for 30min in a nitrogen atmosphere to form a precursor, subpackaging in small bottles, and taking out for later use. 0.07g of MCM-68 molecular sieve is added into 1.4g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature, so as to prepare molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, taking 200 mu L of porous material solution by using an injector, spin-coating at a certain rotating speed for 20s at 1500r/min, then spin-coating at a high rotating speed of 8000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; then 100 μ L of the precursor is taken and spun on the molecular sieve film at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the molybdenum dioxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Example 5
Weighing high-purity aluminate and isopropanol in a glove box, wherein the mass ratio of the aluminate to the isopropanol is 2:40, ultrasonically mixing the aluminate and the isopropanol in a nitrogen atmosphere for 30min to form a precursor, subpackaging the precursor into small bottles, and taking out the small bottles for later use. 0.07g of ETS-10 molecular sieve is added into 1.4g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature to prepare a molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, taking 200 mu L of porous material solution by using an injector, spin-coating at a certain rotating speed for 20s at 1500r/min, then spin-coating at a high rotating speed of 8000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; and then 140 mu L of mixed solution of aluminate and isopropanol is taken to be spin-coated on the molecular sieve film at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the aluminum oxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
Example 6
Weighing high-purity tetraethyl titanate and isopropanol in a glove box, wherein the mass ratio of the tetraethyl titanate to the isopropanol is 2:40, ultrasonically mixing for 30min in a nitrogen atmosphere to form a precursor, subpackaging in small bottles, and taking out for later use. 0.07g of ETS-10 molecular sieve is added into 1.4g of ethylene glycol, and ultrasonic mixing is carried out for 30min at room temperature to prepare a molecular sieve solution. Putting a cleaned transparent glass sheet in the center of a sucker of a spin coater, taking 200 mu L of molecular sieve solution by using an injector, spin-coating at a certain rotating speed for 20s at 1500r/min, then spin-coating at a high rotating speed of 8000r/min for 30s, and repeating for 3-4 times to obtain a molecular sieve film with proper thickness; then 100 mul of tetraethyl titanate and isopropanol mixed solution is taken to be spin-coated on the molecular sieve film at the same rotating speed. And then taking out the spin-coated glass sheet, standing at room temperature for about 10min, placing the glass sheet into a muffle furnace, carrying out temperature programming calcination in the air atmosphere, heating to 450 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 100min, and naturally cooling to room temperature to obtain the titanium dioxide and molecular sieve composite catalyst film. The catalyst is used for the photocatalytic conversion of carbon dioxide, has higher photoactivity, and can generate products such as methanol, ethanol and the like with high selectivity.
The composite catalyst film prepared in examples 1 to 6 is used in a photocatalytic reaction of carbon dioxide, and a specific reaction system is shown in fig. 3, and the reaction system includes a carbon dioxide gas supply device 1, a water vapor mixing device 2, a carbon dioxide photoreaction device 3, and a carbon dioxide reaction product detection device 4, which are sequentially in airflow communication.
As shown in fig. 3, the carbon dioxide gas supply device 1 in the figure comprises a carbon dioxide gas storage unit 11 and a gas flow meter 12; the water vapor mixing device 2 comprises a closed water containing container 21, a water bath 22 and a gas conduit, wherein the water containing container 21 is provided with an inlet 211 and an outlet 212, the carbon dioxide gas supply device 1 extends into water through the gas conduit and the inlet 211 of the water containing container, the water containing container 21 is placed in the water bath 22, and the outlet 212 of the water containing container is communicated with the carbon dioxide photoreaction device 3 through the gas conduit; the carbon dioxide photoreaction device 3 comprises a reactor 31, a catalyst bearing part 32 and a light source 33, wherein the reactor is provided with an inlet 311 and an outlet 312, the catalyst bearing part 32 is arranged in a cavity of the reactor 31, the light source 33 is arranged vertically above the catalyst bearing part 32, and effluent gas in the water vapor mixing device 2 flows into the catalyst bearing part 32 through a gas conduit and the inlet 311 of the carbon dioxide photoreaction device; the outlet gas flow in the carbon dioxide photoreaction device 3 enters the carbon dioxide reaction product detection device 4 through the outlet 312 via a gas conduit. In a preferred embodiment, the carbon dioxide light reaction device 3 further comprises a quartz window, and the window is convenient for the xenon lamp light to pass through.
First, the process is reversedHigh purity CO of reaction gas2The flow rate of the reaction is 10ml/min, and the reaction solution enters a closed reaction system with water vapor after passing through a constant-temperature 60 ℃ water bath device. The reaction device is a quartz reactor and is provided with an air inlet, an air outlet and a quartz window, and the window is convenient for xenon lamp light to pass through. Introducing CO under the condition of illumination2And the gas and the water vapor react on the surface of the composite catalyst film, and the product is directly connected to chromatographic analysis and detection through a gas outlet and a gas conduit.
The catalytic performance of the composite catalyst thin films of examples 1 to 6 is shown in the following table:
as can be seen from the above table: the catalyst prepared in the embodiment 1-6 has high ethanol generation rate and high ethanol selectivity.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The application of the composite catalyst film in the photocatalytic reaction of carbon dioxide comprises the following steps:
1) mixing metal acid ester and alcohol to prepare a precursor;
2) coating a matrix with a porous material solution;
3) coating the precursor;
4) calcining to obtain the composite catalyst film;
wherein, the coating adopts a spin coating mode;
in the step 1), the metal acid ester is one or two selected from tetraethyl titanate and tetrabutyl zirconate;
in the step 2), the porous material is one or more selected from an ETS-10 molecular sieve, a ZSM-5 molecular sieve, a SAPO-34 molecular sieve and an MCM-68 molecular sieve.
2. The use according to claim 1, wherein in step 1), the alcohol is one or more selected from the group consisting of methanol, ethanol, propanol and isopropanol.
3. The use according to claim 1, wherein in the step 1), the mass ratio of the metal acid ester to the alcohol is (1.5-20): 40.
4. use according to claim 1, wherein in step 1) the mixing is carried out in an inert atmosphere.
5. Use according to claim 1, wherein in step 2) the solvent of the porous material solution is ethylene glycol.
6. The use according to claim 1, wherein in step 2), the concentration of the porous material solution is 1 to 5 wt.%.
7. The use according to claim 1, wherein the volume ratio of the precursor to the porous material solution is (1-7): 10.
8. the use according to claim 1, wherein in step 4), the calcination temperature is 400 to 500 ℃.
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