CN105312090A - Preparation of (C5H5) Ru/TiO2 organic-inorganic hybrid photocatalyst - Google Patents
Preparation of (C5H5) Ru/TiO2 organic-inorganic hybrid photocatalyst Download PDFInfo
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- CN105312090A CN105312090A CN201510883018.5A CN201510883018A CN105312090A CN 105312090 A CN105312090 A CN 105312090A CN 201510883018 A CN201510883018 A CN 201510883018A CN 105312090 A CN105312090 A CN 105312090A
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Abstract
The invention discloses preparation of a (C5H5) Ru/TiO2 organic-inorganic hybrid photocatalyst, and an application of preparing methane solar fuel by performing photocatalytic reduction on carbon dioxide. According to the invention, a surface organometallic chemistry method is adopted, and dicyclopentadiene-based ruthenium is grafted to the surface of the titanium dioxide by adopting a surface grafting method to obtain a composite material having a similar semi-sandwich structure, wherein the mass percentage of ruthenium is 0.3-5.0%. Compared with dicyclopentadiene-based ruthenium-unmodified titanium dioxide, the (C5H5) Ru/TiO2 composite material prepared by adopting the method not only has relatively wide photoresponse range, but also photon-generated carriers can fast migrate and transmit as surface Ru-O-Ti keys are generated, and therefore, the photocatalytic efficiency of titanium dioxide in a carbon dioxide methanation process can be effectively improved. The method is simple and easy to operate, and has promotion significance on energy crisis mitigation and ecological environment improvement.
Description
Technical field
The invention belongs to photocatalysis field, be specifically related to one (C
5h
5) Ru/TiO
2the preparation of organic inorganic hybridization photochemical catalyst and produce the application in methane solar energy fuel at photocatalytic reduction of carbon oxide.
Background technology
Since 21 century, national development is day by day rapid, national demand is constantly surging.But the fast development that this structure is unbalance to some extent and excess demand inevitably result in increasing energy problem and environmental problem.The energy resource structure problem that China faces at present is main cause---with coal, the traditional energies such as oil are that main energy resource structure is distributed in and sharply changes in the modernization development process of expansion to energy demand, the demand of development cannot be met on the one hand, on the other hand, environmental pollution can be caused, the destruction Of resources, the problems such as dysequilibrium.Therefore, need badly to find and clean, pollution-free, the reproducible energy, to realize the improvement to existing energy resource structure, and final solution energy problem and environmental problem.
Solar energy is not only the clean energy resource of one " inexhaustible ", and is rated as the available power of " inexhaustible ".Therefore, in worldwide, in the process of seeking new forms of energy, science door is all extremely paid close attention to it, and has carried out large quantifier elimination to realize its development and utilization.Wherein, photocatalysis technology has been since 20th century the seventies, is subject to extensive concern and research, and has been proved to be a kind of Solar use approach with tremendous potential.Utilize this technology, can realize various chemical reaction, wherein, catalytic reduction carbon dioxide may be one of main method by solving environmental problems such as " greenhouse effects " and energy problem.
Methane, as fuel, as natural gas and coal gas etc., is widely used in industry and civilian industry; Such as, as industrial chemicals, it can be used for producing acetylene, hydrogen, synthetic ammonia, carbon black, nitre chloro methane, carbon disulfide, monochloro methane, carrene, chloroform, carbon tetrachloride and hydrogen cyanide etc.Therefore its synthesis and preparative occupies very important status at chemical field.Carbon dioxide methanation, not only can prepare the methane with significant application value, and the conversion of carbon dioxide can be realized, the important catalytic reaction of a class, however traditional thermocatalytic chemical synthesis process to there is power consumption large, accessory substance is indefinite, contaminated environment, etching apparatus problem, at the society that environmental problem and energy problem are more and more given prominence to, its development is very restricted.And photo catalytic reduction technology, by the selection of reaction condition, regulation and control can realize by the conversion of carbon dioxide to methane, a kind of clean, non-secondary pollution, safety, simple to operate, efficient green energy resource new preparation technology, is just showing huge potentiality in the synthesis of methane.
In numerous photochemical catalysts, titanium dioxide is stablized because of it, and nontoxic, production cost is low, the advantage such as to can be mass, and has unique advantage, has obtained investigation and application widely.In the last thirty years, at photodissociation aquatic products hydrogen, carbon dioxide reduction, in the reaction of organic matter degradation photocatalytic conversion, titanium dioxide is all study hotspot.But the greater band gap (E of titanium dioxide
g=3.2eV) ultraviolet light accounting for sunshine spectrum 5% can only be responded, thus photocatalysis efficiency is low.From the photocatalysis technology mechanism of action and the factor analysis affecting photocatalysis efficiency, the photocatalysis efficiency that titanic oxide material is lower is improved by following two kinds of paths: (1) expands photoresponse scope; (2) accelerate carrier transfer, suppress the compound in light induced electron and hole.
The organometallic ruthenium compound with unique physicochemical property has good electrochemical properties, photochemical properties, excellent photoelectric conversion performance, and Recent study finds as sensitising agent, has excellent performance equally.On the one hand, it can absorb visible ray effectively, produces photo-generated carrier; On the other hand, its organic ligand can provide one " express passway " for the transmission of photo-generated carrier and migration, thus accelerate photo-generated carrier by being excited the migration of point (sensitising agent) to reaction site (catalyst), suppress the transmission of photohole and electronics, finally improve photocatalysis efficiency.Therefore, utilize the photoelectric conversion ability of organometallic ruthenium compound excellence, by itself and titanium dioxide compound, the object improving optically catalytic TiO 2 efficiency can be realized.
The people such as LiulianJun report under UV-irradiation, and titanium dioxide carbon dioxide produces methane carbon monoxide, compares the photocatalytic activity (PhotocatalyticCO of the titanium dioxide of three kinds of different crystalline phases simultaneously
2reductionwithH
2oonTiO
2nanocrystals:Comparisonofanatase, rutile, andbrookitepolymorphsandexplorationofsurfacechemistry.AC SCatalysis, 2012,2 (8): 1817-1828).But the band gap of titanium dioxide limits it to the absorption of light and utilization---the titanium dioxide of which kind of crystalline phase all can only selective absorbing ultraviolet light, and cannot absorb and utilize visible ray.And the people such as T.W.Woolerton find, with ruthenium base photosensitizer ([Ru
iI(bipy)
2(4,4 '-(PO
3h
2)
2-bipy)] Br
2) and carbon monoxide dehydrogenase (carbonmonoxidedehydrogenase) and titanium dioxide (TiO
2) compound prepares photochemical catalyst, and study the performance (EfficientandCleanPhotoreductionofCO of its photocatalytic reduction of carbon oxide
2toCObyEnzyme-ModifiedTiO
2nanoparticlesUsingVisibleLight
,j.Am.Chem.Soc.2010,132,2132-2133).The method first by titanium dioxide ultrasonic disperse in MES, subsequently under anhydrous and oxygen-free condition with carbon monoxide dehydrogenase (with [Ni
4fe
4s]) stir within 20 minutes, mix, then by with ruthenium base photosensitizer ([Ru
iI(bipy)
2(4,4 '-(PO
3h
2)
2-bipy)] Br
2) stir within 20 minutes, obtain RuP/TiO
2/ CODH.The composite catalyst that modification obtains can reducing carbon dioxide under visible light illumination.The titanium dioxide that the method obtains the modification of organic ruthenium sensitising agent by the mode of surface coordination key bonding has expanded the light abstraction width of titanium dioxide, but surface coordination key bonding pattern is transmitted to light induced electron titanium deoxide catalyst from sensitizer, effectively can not carry out the reaction of generation polyelectron, limit the generation efficiency of methane.
Above document respectively using titanium dioxide and composite after modifying as catalyst, utilize photocatalysis technology, achieve carbon dioxide methanation, but the main problem that there are following two aspects:
(1) titanium dioxide without modification is adopted only to have response to ultraviolet light, so on the low side to the utilization rate of sunshine as photochemical catalyst.
(2) adopt through modifying, though the composite titanium dioxide that area load contains a certain amount of Organometallic ruthenium can absorb as photochemical catalyst and utilize visible ray, its quantum efficiency is under visible light still on the low side.
Summary of the invention
The object of the invention is to the deficiency for existing in TiO 2-base optical catalyst chemical recycling of carbon dioxide process as above, a kind of novel organic inorganic hybridization photochemical catalyst (C having high light catalytic efficiency is provided
5h
5) Ru/TiO
2and Synthesis and applications.Prepared (C
5h
5) Ru/TiO
2not only there is wider photoresponse scope, and effectively improve the photocatalysis efficiency of titanium dioxide in catalysis carbon dioxide methanation process.Preparation (the C adopted
5h
5) Ru/TiO
2the method of the surface organometallic chemistry grafting of composite photo-catalyst, simple and easy to operate, and to the promotion meaning that alleviating energy crisis is improved the ecological environment important.
For achieving the above object, the present invention adopts following technical scheme:
(C
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is the material with half sandwich structure obtained by grafting by titanium dioxide and bicyclic pentadiene ruthenium, and wherein the mass fraction of ruthenium is 0.3-5.0%.
Adopt surface organometallic chemistry method, bicyclic pentadiene ruthenium passed through the method grafting of surface grafting to titanium dioxide surface, obtain the composite with similar half sandwich structure, specifically comprise the following steps:
(1) 0.01-10 gram of commercial titanium dioxide (TiO is got
2) be placed in Pyrex glass reactor, between 250-500 degree Celsius, under oxygen atmosphere, calcine 0.5-20 hour, obtain white pigmented samples A;
(2) the white pigmented samples A that step (1) obtains is calcined 0.5-4 hour under 250-500 degree Celsius of high vacuum condition, obtain canescence sample B;
(3) add 3-50 milligram bicyclic pentadiene ruthenium in the sample B that step (2) obtains under anhydrous and oxygen-free condition, under 100-180 degree Celsius, react 10-40 hour, obtain dark yellow Sample C;
(4) sample C step (3) obtained is at 100-180 degree Celsius, and under high vacuum condition, heating 0.5-4 hour, is cooled to room temperature after terminating, obtains (the C that mass fraction is 0.3-5% under vacuum condition
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst.
Step (2) and the high vacuum pressure range described in step (4) are: 10
-1-10
-4handkerchief.
(C
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is used for the photocatalysis methanation reaction of carbon dioxide, and concrete steps are as follows:
(1) C that 10-40 milligram said method prepares is taken
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is in Pyrex glass reactor;
(2) with mechanical pump, degassed process is carried out to the above-mentioned Pyrex glass reactor adding catalyst;
(3) in above-mentioned Pyrex glass reactor, be filled with 10-50 milliliter carbon dioxide with carbon dioxide airbag, inject 10-50 microliters of deionized water with micro syringe to it, and seal further;
(4) the Pyrex glass reactor of above-mentioned sealing being placed in wave-length coverage is illumination 4 hours under the xenon lamp of 200-800 nanometer, or illumination 4 hours under the xenon lamp being placed in 420-800 nanometer.
Described wave-length coverage is the xenon source of 200-800 nanometer is common xenon source.
Described wave-length coverage is the xenon source of 420-800 nanometer is common xenon source, and the optical filter of adapted 420 nanometer is to filter the light lower than 420 nano wavebands.
The present invention with bicyclic pentadiene ruthenium and anatase titania for presoma, adopt the method for organic metal surface grafting, pass through organic metal---the reaction between bicyclic pentadiene ruthenium and titanium dioxide surface hydroxyl, to achieve bicyclic pentadiene ruthenium by the object of covalent bonding in titanium dioxide surface, obtain (the C with similar half sandwich structure
5h
5) Ru/TiO
2organic inorganic hybridization catalysis material.The more important thing is, result of study shows that this composite photocatalyst material shows excellent photocatalysis performance in the photocatalysis methanation of carbon dioxide.This is mainly because by surface grafting method by after the hydroxyl grafting of bicyclic pentadiene ruthenium and titanium dioxide surface, bicyclic pentadiene ruthenium can be used as sensitising agent, widens the light abstraction width of carbon dioxide; Meanwhile, transmission and the migration of photo-generated carrier can also be accelerated.(C prepared by the present invention
5h
5) Ru/TiO
2organic inorganic hybridization catalysis material is expected to have more development prospects in the photocatalysis methanation reaction of carbon dioxide.
beneficial effect of the present invention is:
(1) the present invention by bicyclic pentadiene ruthenium well grafting in titanium dioxide matrix, formed C
5h
5-Ru-O-Ti surface texture, due to the optical sensibilization of the monocyclopentadienyl ruthenium of surface graft, (C
5h
5) Ru/TiO
2composite photo-catalyst can farthest absorb and utilize sunshine, its photoresponse scope easily extensible to 800 nanometer;
(2) the organic inorganic hybridization photochemical catalyst (C prepared by
5h
5) Ru/TiO
2composite is as photochemical catalyst, under visible light illumination, can by Ru-O-Ti rapidly from the transmission of cyclopentadienyl group ruthenium with migrate to titanium dioxide surface after electronics on monocyclopentadienyl ruthenium is excited, thus restrained effectively the compound of electron hole pair, improve the photocatalysis efficiency of photochemical catalyst;
(3) the organic inorganic hybridization photochemical catalyst (C prepared by
5h
5) Ru/TiO
2, can the photocatalysis methanation of catalysis carbon dioxide effectively, its AQY is issued to 0.56% at 420 nanometer Single wavelength;
(4) adopt for the preparation of (C
5h
5) Ru/TiO
2the method of the surface organometallic chemistry grafting of composite photo-catalyst, simple and easy to operate, and to the promotion meaning that alleviating energy crisis is improved the ecological environment important.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Comparative example 1
Take 10 milligrams of business TiO
2in Pyrex glass reactor, carry out degassed process to make for vacuum state in glass reactor, be then filled with 50 milliliters of high-purity carbon dioxide gases wherein with airbag, in triplicate to guarantee that air is by Ex-all.Then, then with micro syringe 20 microliters of deionized water are injected wherein.Further encapsulation process is carried out to glass reactor, under being then placed on dark condition, stir half an hour, then illumination 4 hours under the simulated solar irradiation of 200-800 nanometer.
Comparative example 2
The photocatalysis methanation of carbon dioxide is identical with comparative example 1, carries out under visible ray (>=420 nanometer) illuminate condition unlike photocatalytic process.
Embodiment 1
Take 1 gram of commodity titanium dioxide (TiO
2) be placed in Pyrex glass reactor, calcine 0.5 hour in 250 degrees Celsius of oxygen atmospheres, then this device is connected with high-vacuum installation, 250 degrees Celsius of lower high vacuum (10
-1handkerchief) process 0.5 hour coldly to go to room temperature under condition.In anhydrous and oxygen-free glove box, be dissolved in n-hexane by a certain amount of ruthenocene, the concentration obtaining ruthenocene is the hexane solution of the ruthenocene of 10 milligrams every milliliter.Then, in glove box, get the hexane solution of the ruthenocene that 0.3 milliliter prepares with syringe, and inject Pyrex glass reactor.Subsequently Pyrex glass reactor is placed in and tube furnace is heated to 100 degrees Celsius and maintains 10 hours, later high vacuum 10 at such a temperature
-1handkerchief process 0.5 hour is cold goes to room temperature, and the mass fraction obtaining ruthenium is the bicyclic pentadiene ruthenium grafting titanium oxide (CpRu of 0.3%
0.3/ TiO
2) material.Take 10 milligrams of CpRu prepared
0.3/ TiO
2material, in Pyrex glass reactor, carries out degassed process to make for vacuum state in glass reactor, is then filled with 50 milliliters of high-purity carbon dioxide gases wherein with airbag, in triplicate to guarantee that air is by Ex-all.Then, then with micro syringe 20 microliters of deionized water are injected wherein.Further encapsulation process is carried out to glass reactor, under being then placed on dark condition, stir half an hour, then illumination 4 hours under the simulated solar irradiation of 200-800 nanometer.
Embodiment 2
Take 1 gram of commodity titanium dioxide (TiO
2) be placed in Pyrex glass reactor, calcine 10 hours in 400 degrees Celsius of oxygen atmospheres, then this device is connected with high-vacuum installation, 400 degrees Celsius of lower high vacuum (10
-2handkerchief) process 2 hours coldly to go to room temperature under condition.In anhydrous and oxygen-free glove box, be dissolved in n-hexane by a certain amount of ruthenocene, the concentration obtaining ruthenocene is the hexane solution of the ruthenocene of 10 milligrams every milliliter.Then, in glove box, get the hexane solution of the ruthenocene that 0.6 milliliter prepares with syringe, and inject Pyrex glass reactor.Subsequently Pyrex glass reactor is placed in and tube furnace is heated to 150 degrees Celsius and maintains 24 hours, later high vacuum 10 at such a temperature
-2handkerchief process 2 hours is cold goes to room temperature, and the mass fraction obtaining ruthenium is the bicyclic pentadiene ruthenium grafting titanium oxide (CpRu of 0.6%
0.6/ TiO
2) material.Take 10 milligrams of CpRu prepared
0.6/ TiO
2material, in Pyrex glass reactor, carries out degassed process to make for vacuum state in glass reactor, is then filled with 50 milliliters of high-purity carbon dioxide gases wherein, in triplicate to guarantee that air is by Ex-all.Then, then with micro syringe 20 microliters of deionized water are injected wherein.Further encapsulation process is carried out to glass reactor, under being then placed on dark condition, stir half an hour, then illumination 4 hours under the simulated solar irradiation of 200-800 nanometer.
Embodiment 3
Take 1 gram of commodity titanium dioxide (TiO
2) be placed in Pyrex glass reactor, calcine 20 hours in 500 degrees Celsius of oxygen atmospheres, then this device is connected with high-vacuum installation, 500 degrees Celsius of lower high vacuum (10
-4handkerchief) process 4 hours coldly to go to room temperature under condition.In anhydrous and oxygen-free glove box, be dissolved in n-hexane by a certain amount of ruthenocene, the concentration obtaining ruthenocene is the hexane solution of the ruthenocene of 10 milligrams every milliliter.Then, in glove box, get the hexane solution of the ruthenocene that 1 milliliter prepares with syringe, and inject Pyrex glass reactor.Subsequently Pyrex glass reactor is placed in and tube furnace is heated to 180 degrees Celsius and maintains 40 hours, later high vacuum 10 at such a temperature
-4handkerchief process 4 hours is cold goes to room temperature, and the mass fraction obtaining ruthenium is the bicyclic pentadiene ruthenium grafting titanium oxide (CpRu of 1%
1.0/ TiO
2) material.Take 10 milligrams of CpRu prepared
1.0/ TiO
2material, in Pyrex glass reactor, carries out degassed process to make for vacuum state in glass reactor, is then filled with 50 milliliters of high-purity carbon dioxide gases wherein with airbag, in triplicate to guarantee that air is by Ex-all.Then, then with micro syringe 20 microliters of deionized water are injected wherein.Further encapsulation process is carried out to glass reactor, under being then placed on dark condition, stir half an hour, then illumination 4 hours under the simulated solar irradiation of 200-800 nanometer.
Embodiment 4
Take 1 gram of commodity titanium dioxide (TiO
2) be placed in Pyrex glass reactor tubes, calcine 24 hours in 400 degrees Celsius of oxygen atmospheres, then this device is connected with high-vacuum installation, 400 degrees Celsius of lower high vacuum (10
-2handkerchief) process 2 hours coldly to go to room temperature under condition.In anhydrous and oxygen-free glove box, be dissolved in n-hexane by a certain amount of ruthenocene, the concentration obtaining ruthenocene is the hexane solution of the ruthenocene of 10 milligrams every milliliter.Then, in glove box, get the hexane solution of the ruthenocene that 5 milliliters prepare with syringe, and inject Pyrex glass reactor.Subsequently Pyrex glass reactor is placed in and tube furnace is heated to 150 degrees Celsius and maintains 24 hours, later high vacuum (10 at such a temperature
-2) handkerchief process 2 hours is cold goes to room temperature, the mass fraction obtaining ruthenium is the bicyclic pentadiene ruthenium grafting titanium oxide (CpRu of 5%
5.0/ TiO
2) material.Take 10 milligrams of CpRu prepared
5.0/ TiO
2material, in Pyrex glass reactor, carries out degassed process to make for vacuum state in glass reactor, is then filled with 50 milliliters of high-purity carbon dioxide gases wherein, in triplicate to guarantee that air is by Ex-all.Then, then with micro syringe 20 microliters of deionized water are injected wherein.Further encapsulation process is carried out to glass reactor, under being then placed on dark condition, stir half an hour, then illumination 4 hours under the simulated solar irradiation of 200-800 nanometer.
Embodiment 5
The preparation of catalyst and the photocatalysis methanation of carbon dioxide identical with this part embodiment 1, carry out under visible ray (>=420 nanometer) illuminate condition unlike photocatalytic process.
Embodiment 6
The preparation of catalyst and the photocatalysis methanation of carbon dioxide identical with this part embodiment 2, carry out under visible ray (>=420 nanometer) illuminate condition unlike photocatalytic process.
Embodiment 7
The preparation of catalyst and the photocatalysis methanation of carbon dioxide identical with this part embodiment 3, carry out under visible ray (>=420 nanometer) illuminate condition unlike photocatalytic process.
Embodiment 8
The preparation of catalyst and the photocatalysis methanation of carbon dioxide identical with this part embodiment 4, carry out under visible ray (>=420 nanometer) illuminate condition unlike photocatalytic process.
Embodiment and ruthenium content, xenon lamp wavelength and corresponding methane-generated quantity in comparative example are as following table:
According to above-mentioned data, compared with the titanium dioxide of unmodified ruthenocene, (the C in embodiment
5h
5) Ru/TiO
2the methane content that organic inorganic hybridization photochemical catalyst catalysis carbon dioxide produces is more, shows effectively to improve the photocatalysis efficiency of titanium dioxide in catalysis carbon dioxide methanation process.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. (a C
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst, is characterized in that: described (C
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is the material with half sandwich structure obtained by compound by titanium dioxide and bicyclic pentadiene ruthenium, and wherein the mass fraction of ruthenium is 0.3-5.0%.
2. prepare (C as claimed in claim 1 for one kind
5h
5) Ru/TiO
2the method of organic inorganic hybridization photochemical catalyst, is characterized in that: adopt surface organometallic chemistry method, bicyclic pentadiene ruthenium is passed through the method grafting of surface grafting to titanium dioxide surface, obtains the composite with similar half sandwich structure.
3. (C according to claim 2
5h
5) Ru/TiO
2the preparation method of organic inorganic hybridization photochemical catalyst, is characterized in that: comprise the following steps:
(1) get 0.01-10 gram of commodity titanium dioxide and be placed in Pyrex glass reactor, between 250-500 degree Celsius, under oxygen atmosphere, calcine 0.5-20 hour, obtain white pigmented samples A;
(2) the white pigmented samples A that step (1) obtains is processed under 250-500 degree Celsius of lower high vacuum 0.5-4 hour, obtain canescence sample B;
(3) add 3-50 milligram bicyclic pentadiene ruthenium in the sample B obtained to step (2) under anhydrous and oxygen-free condition, under 100-180 degree Celsius, react 10-40 hour, obtain dark yellow Sample C;
(4) sample C step (3) obtained, at 100-180 degree Celsius, under high vacuum condition, heats 0.5-4 hour, and be cooled to room temperature under vacuum condition, obtain (the C that mass fraction is 0.3-5%
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst.
4. the method according to right 3, is characterized in that: step (2) and the high vacuum pressure range described in step (4) are: 10
-1-10
-4handkerchief.
5. (a C as claimed in claim 1
5h
5) Ru/TiO
2the application of organic inorganic hybridization photochemical catalyst, is characterized in that:
Described (C
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is used for the photocatalysis methanation reaction of carbon dioxide.
6. (C according to claim 5
5h
5) Ru/TiO
2the application of organic inorganic hybridization photochemical catalyst, is characterized in that: the photocatalysis methanation reaction of described photocatalysis carbon dioxide, and concrete steps are as follows:
(1) C that 10-40 milligram said method prepares is taken
5h
5) Ru/TiO
2organic inorganic hybridization photochemical catalyst is in Pyrex glass reactor;
(2) with mechanical pump, degassed process is carried out to the above-mentioned Pyrex glass reactor adding catalyst;
(3) in above-mentioned Pyrex glass reactor, be filled with 10-50 milliliter carbon dioxide with carbon dioxide airbag, inject 10-50 microliters of deionized water with micro syringe to it, and seal further;
(4) the Pyrex glass reactor of above-mentioned sealing being placed in wave-length coverage is illumination 4 hours under the xenon lamp of 200-800 nanometer, or illumination 4 hours under the xenon lamp being placed in 420-800 nanometer.
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| CN112359376A (en) * | 2020-10-27 | 2021-02-12 | 福州大学 | Preparation method of metal oxide-insulator-semiconductor structure photo-anode |
| CN112517082A (en) * | 2021-01-18 | 2021-03-19 | 福州大学 | Organic metal compound modified inorganic semiconductor composite photocatalyst and preparation method and application thereof |
| CN112725771A (en) * | 2021-01-25 | 2021-04-30 | 福州大学 | Ti-based photo-anode, preparation method thereof and application thereof in preparing oxygen by photoelectrocatalysis total hydrolysis |
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| CN112725771B (en) * | 2021-01-25 | 2021-11-26 | 福州大学 | Ti-based photo-anode, preparation method thereof and application thereof in preparing oxygen by photoelectrocatalysis total hydrolysis |
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