CN105312090B - One kind (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst - Google Patents
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Abstract
The invention discloses one kind (C5H5)Ru/TiO2The preparation of organic-inorganic heterozygosis photochemical catalyst and its application in methane solar energy fuel is produced using photocatalytic reduction of carbon oxide.Using surface organometallic chemistry method, bicyclic pentadiene ruthenium is grafted onto titanium dioxide surface by the method for surface grafting, the composite with similar half sandwich structure is obtained, the wherein mass fraction of ruthenium is 0.3 5.0%.Compared with the titanium dioxide of unmodified bicyclic pentadiene ruthenium, (C is prepared by this method5H5)Ru/TiO2Composite, not only with wider photoresponse scope, and due to the formation of surface Ru O Ti keys, photo-generated carrier rapidly can be migrated and transmitted, therefore be effectively improved photocatalysis efficiency of the titanium dioxide during catalysis carbon dioxide methanation.The method is simple and easy to operate, and alleviating energy crisis is improved the ecological environment has important promotion meaning.
Description
Technical field
The invention belongs to photocatalysis field, and in particular to one kind (C5H5)Ru/TiO2The system of organic inorganic hybridization photochemical catalyst
The standby and its application in photocatalytic reduction of carbon oxide produces methane solar energy fuel.
Background technology
Since 21 century, national development increasingly rapid, national demand is constantly surging.However, this structure is unbalance
Fast-developing and excess demand has inevitably led to increasing energy problem and environmental problem.What China faced at present
Energy resource structure problem is main cause --- with coal, the energy resource structure based on the traditional energy such as oil is distributed in energy demand
During the modernization development for drastically changing expansion, the demand of development on the one hand can not be met, on the other hand, environment can be caused dirty
The problems such as dye, the destruction Of resources, dysequilibrium.Therefore, searching cleaning, pollution-free, the reproducible energy, to realize to existing are needed badly
Energy resource structure improvement, and finally solve energy problem and environmental problem.
Solar energy is not only the clean energy resource of a kind of " inexhaustible ", and be rated as " it is inexhaustible, use it
It is inexhaustible " the available energy.Therefore, in worldwide, during new energy is sought, science door is all extremely closed to it
Note, and carried out substantial amounts of research to realize to its development and utilization.Wherein, photocatalysis technology is from 70 years 20th century
Since generation, receive significant attention and studied, and have proved to be a kind of Solar use approach with tremendous potential.Utilize this
Technology, it is possible to achieve various chemical reactions, wherein, catalysis reduction carbon dioxide is probably to solve " greenhouse effects " in the future
Etc. one of environmental problem and the main method of energy problem.
Methane is widely used in industrial and civilian industry as fuel, such as natural gas and coal gas；For example, conductization
Work raw material, it can be for production acetylene, hydrogen, synthesis ammonia, carbon black, nitre chloro methane, carbon disulfide, monochloro methane, dichloro
Methane, chloroform, carbon tetrachloride and hydrogen cyanide etc..Therefore its synthesis and preparation occupies very important ground in chemical field
Position.Carbon dioxide methanation, can not only prepare the methane with significant application value, and can realize turning for carbon dioxide
Change, be the important catalytic reaction of a class, but traditional thermocatalytic chemical synthesis process has power consumption greatly, accessory substance is indefinite,
Pollute environment, etching apparatus problem, in environmental problem and energy problem more and more prominent today's society, it develops by very big
Limitation.And photo catalytic reduction technology, by the selection of reaction condition, regulation and control can be achieved by carbon dioxide to methane
Conversion, is a kind of cleaning, non-secondary pollution, safety, simple to operate, efficient green energy resource new preparation technology, in the conjunction of methane
Cheng Zhongzheng shows huge potentiality.
In numerous photochemical catalysts, titanium dioxide is stable because of it, and nontoxic, production cost is low, the advantages of can be mass,
With unique advantage, extensive research and application have been obtained.In the late three decades, in 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 of titanium dioxide（Eg=
3.2 eV）The ultraviolet light for accounting for sunshine spectrum 5% can only be responded, thus photocatalysis efficiency is low.From the photocatalysis technology mechanism of action with
And the factor analysis of photocatalysis efficiency is influenceed, the relatively low photocatalysis efficiency of titanic oxide material can be obtained by following two paths
Improve：（1）Expand photoresponse scope；（2）Accelerate carrier transfer, suppress the compound of light induced electron and hole.
Organometallic ruthenium compound with unique physicochemical property has good electrochemical properties, photochemical properties, excellent
Different photoelectric conversion performance, Recent study is found as sensitising agent, equally with excellent performance.On the one hand, it can have
Effect ground absorbs visible ray, produces photo-generated carrier；On the other hand, its organic ligand can be the transmission of photo-generated carrier and move
Move and one " express passway " is provided, so as to accelerate photo-generated carrier by being excited a little（Sensitising agent）To reaction site（Catalyst）Move
Move, suppress the transmission of photohole and electronics, finally improve photocatalysis efficiency.Therefore, it is excellent using organometallic ruthenium compound
Photoelectric conversion ability, it is combined with titanium dioxide, can be achieved improve optically catalytic TiO 2 efficiency purpose.
Liulian Jun et al. are reported under ultraviolet light, and titanium dioxide carbon dioxide produces the oxygen of methane one
Change carbon, while comparing the photocatalytic activity of the titanium dioxide of three kinds of different crystalline phases（Photocatalytic CO2
reduction with H2O on TiO2 nanocrystals: Comparison of anatase, rutile, and
brookite polymorphs and exploration of surface chemistry. ACS Catalysis,
2012, 2(8): 1817-1828）.However, the band gap of titanium dioxide limits its absorption and utilization to light --- no matter what
The titanium dioxide of kind of crystalline phase all can only selective absorbing ultraviolet light, and can not absorb and utilize visible ray.And T. W.
Woolerton et al. has found, uses ruthenium base photosensitizer（[RuII(bipy)2(4,4′-(PO3H2)2-bipy)]Br2）And one oxidation
Carbon dehydrogenase（carbon monoxide dehydrogenase）With titanium dioxide（TiO2）It is compound to prepare photochemical catalyst, and grind
Study carefully performance (the Efficient and Clean Photoreduction of CO of its photocatalytic reduction of carbon oxide2 to CO
by Enzyme-Modified TiO2 Nanoparticles Using Visible Light, J. Am. Chem. Soc.
2010, 132, 2132-2133).This method first by titanium dioxide ultrasonic disperse in MES, then anhydrous
With carbon monoxide dehydrogenase under oxygen free condition（With [Ni4Fe4S]）Stirring 20 minutes be well mixed, then by with ruthenium base photosensitizer
（[RuII(bipy)2(4,4’-(PO3H2)2-bipy)]Br2）Stirring obtains RuP/TiO in 20 minutes2/CODH.It is compound that modification is obtained
Catalyst can reduce carbon dioxide under visible light illumination.This method obtains organic ruthenium by way of surface coordination key is bonded
The titanium dioxide of sensitising agent modification has expanded the light abstraction width of titanium dioxide, but surface coordination key bonding pattern is photoproduction electricity
Son is transmitted on titanium deoxide catalyst from sensitizer, it is impossible to effective to carry out occurring polyelectron reaction, limits methane
Generation efficiency.
Document above respectively using titanium dioxide and its modification after composite as catalyst, utilize photocatalysis skill
Art, realizes carbon dioxide methanation, but the problem of be primarily present following two aspects：
（1）Only there is response to ultraviolet light as photochemical catalyst using the titanium dioxide without modification, so to sunshine
Utilization rate it is relatively low.
（2）Using by modification, area load contains the composite titanium dioxide of a certain amount of Organometallic ruthenium as photocatalysis
Though agent can absorb and utilize visible ray, its quantum efficiency under visible light is still relatively low.
The content of the invention
It is an object of the invention to for being deposited during TiO 2-base optical catalyst chemical recycling of carbon dioxide as described above
Not enough there is provided a kind of organic inorganic hybridization photochemical catalyst (C for possessing high light catalytic efficiency5H5)Ru/TiO2And its prepare
And application.Prepared (C5H5)Ru/TiO2Not only there is wider photoresponse scope, and be effectively improved titanium dioxide
Photocatalysis efficiency during catalysis carbon dioxide methanation.Preparation (the C used5H5)Ru/TiO2Composite photo-catalyst
The method of surface organometallic chemistry grafting, it is simple and easy to operate, and alleviating energy crisis is improved the ecological environment have important
Promotion meaning.
To achieve the above object, the present invention is adopted the following technical scheme that：
(C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst is to pass through grafting by titanium dioxide and bicyclic pentadiene ruthenium
The obtained material with half sandwich structure, the wherein mass fraction of ruthenium are 0.3-5.0%.
Using surface organometallic chemistry method, bicyclic pentadiene ruthenium is grafted onto dioxy by the method for surface grafting
Change titanium surface, obtain the composite with similar half sandwich structure, specifically include following steps：
（1）Take 0.01-10 grams of commercial titanium dioxide（TiO2）It is placed in Pyrex glass reactors, at 250-500 degrees Celsius
Between, calcined 0.5-20 hours under oxygen atmosphere, obtain white pigmented samples A；
（2）By step（1）Obtained white pigmented samples A is calcined 0.5-4 hours under 250-500 degrees Celsius of high vacuum condition,
Obtain canescence sample B；
（3）The step under the conditions of anhydrous and oxygen-free（2）3-50 milligrams of bicyclic pentadiene rutheniums are added in obtained sample B, in
Reacted 10-40 hours under 100-180 degrees Celsius, obtain dark yellow Sample C；
（4）By step（3）Obtained sample C is heated 0.5-4 hours under 100-180 degrees Celsius, high vacuum condition, knot
Beam obtains the (C that mass fraction is 0.3-5% after being cooled to room temperature under vacuum condition5H5)Ru/TiO2Organic inorganic hybridization light is urged
Agent.
Step（2）And step（4）Described in high vacuum pressure range be：10-1-10-4Handkerchief.
(C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst is used for the photocatalysis methanation reaction of carbon dioxide, specifically
Step is as follows：
（1）Weigh the C that the 10-40 milligrams of above methods are prepared5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst in
In Pyrex glass reactors；
（2）Processing is de-gassed to the Pyrex glass reactors of above-mentioned addition catalyst with mechanical pump；
（3）10-50 milliliters of carbon dioxide are filled with into above-mentioned Pyrex glass reactors with carbon dioxide airbag, are used
Micro syringe injects 10-50 microlitres of deionized water to it, and is further sealed；
（4）Above-mentioned sealed Pyrex glass reactors are placed in illumination 4 under the xenon lamp that wave-length coverage is 200-800 nanometers
Individual hour, or it is placed in 4 hours of illumination under 420-800 nanometers of xenon lamp.
Described wave-length coverage is common xenon source for 200-800 nanometers of xenon source.
Described wave-length coverage is common xenon source, the filter that 420 nanometers of adapted for 420-800 nanometers of xenon source
Mating plate is less than the light of 420 nano wavebands to filter.
The present invention is using bicyclic pentadiene ruthenium and anatase titania as presoma, using organic metal surface grafting
Method, passes through organic metal --- and the reaction between bicyclic pentadiene ruthenium and titanium dioxide surface hydroxyl, realizing will be bicyclic
Pentadienyl ruthenium, in the purpose of titanium dioxide surface, obtains (the C with similar half sandwich structure by covalent bonding5H5)
Ru/TiO2Organic inorganic hybridization catalysis material.Importantly, result of study shows the composite photocatalyst material in titanium dioxide
Excellent photocatalysis performance is shown in the photocatalysis methanation of carbon.This is primarily due to will be double by surface grafting method
After the hydroxyl grafting of cyclopentadienyl group ruthenium and titanium dioxide surface, bicyclic pentadiene ruthenium can widen titanium dioxide as sensitising agent
The light abstraction width of carbon；At the same time it can also accelerate the transmission and migration of photo-generated carrier.(C prepared by the present invention5H5)Ru/
TiO2Organic inorganic hybridization catalysis material is expected in the photocatalysis methanation reaction of carbon dioxide have more development prospects.
The beneficial effects of the present invention are：
（1）By bicyclic pentadiene ruthenium, grafting in titanium dioxide matrix, forms C to the present invention well5H5- Ru-O-Ti tables
Face structure, due to the optical sensibilization of the monocyclopentadienyl ruthenium of surface graft, (C5H5)Ru/TiO2Composite photo-catalyst can
Farthest absorb and utilize sunshine, its photoresponse scope can be extended to 800 nanometers；
（2）Prepared organic inorganic hybridization photochemical catalyst (C5H5)Ru/TiO2Composite is as photochemical catalyst, can
See under light irradiation, the electronics on monocyclopentadienyl ruthenium can be by Ru-O-Ti rapidly from cyclopentadienyl group ruthenium after being excited
Transmit and migrate to titanium dioxide surface, so as to restrained effectively the compound of electron hole pair, improve the light of photochemical catalyst
Catalytic efficiency；
（3）Prepared organic inorganic hybridization photochemical catalyst (C5H5)Ru/TiO2, can effectively be catalyzed carbon dioxide
Photocatalysis methanation, its AQY is issued to 0.56% in 420 nanometers of Single wavelengths；
（4）Used be used for prepare (C5H5)Ru/TiO2The side of the surface organometallic chemistry grafting of composite photo-catalyst
Method, it is simple and easy to operate, and alleviating energy crisis is improved the ecological environment have important promotion meaning.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Comparative example 1
Weigh 10 milligrams of business TiO2In Pyrex glass reactors, processing is de-gassed so as to be in glass reactor
Vacuum state, is then filled with 50 milliliters of high-purity carbon dioxide gases thereto with airbag, in triplicate to ensure that air is cleared.
Then 20 microlitres of deionized waters, then with micro syringe are injected thereto.Encapsulation process further is carried out to glass reactor, so
After be placed under dark condition and stir half an hour, 4 hours of illumination under 200-800 nanometers of simulated solar irradiation.
Comparative example 2
The photocatalysis methanation of carbon dioxide is identical with comparative example 1, the difference is that photocatalytic process is in visible ray
（>=420 nanometers）Carried out under the conditions of irradiation.
Embodiment 1
Weigh 1 gram of commodity titanium dioxide（TiO2）It is placed in Pyrex glass reactors, in 250 degrees Celsius of oxygen atmospheres
The device, is then connected, in 250 degrees Celsius of lower high vacuum by calcining 0.5 hour with high-vacuum installation（10-1Handkerchief）Under the conditions of handle
0.5 hour and cold go to room temperature.In anhydrous and oxygen-free glove box, a certain amount of ruthenocene is dissolved in n-hexane, two cyclopentadienyls are obtained
The concentration of ruthenium is the hexane solution of 10 milligrams every milliliter of ruthenocene.Then, in glove box, 0.3 milliliter is taken with syringe
The hexane solution of the ruthenocene prepared, and inject in Pyrex glass reactors.Pyrex glass reactors are then placed in pipe
100 degrees Celsius are heated on formula stove and 10 hours are maintained, later high vacuum 10 at such a temperature-1Handkerchief is handled 0.5 hour and cold gone
To room temperature, it is 0.3% bicyclic pentadiene ruthenium grafting titanium oxide to obtain the mass fraction of ruthenium（CpRu0.3/TiO2）Material.Weigh
10 milligrams of CpRu for preparing0.3/TiO2Material is de-gassed processing so that glass reactor in Pyrex glass reactors
Interior is vacuum state, is then filled with 50 milliliters of high-purity carbon dioxide gases thereto with airbag, in triplicate to ensure air quilt
It is cleared.Then 20 microlitres of deionized waters, then with micro syringe are injected thereto.Further glass reactor is carried out at sealing
Reason, is then placed under dark condition and stirs half an hour, 4 hours of illumination under 200-800 nanometers of simulated solar irradiation.
Embodiment 2
Weigh 1 gram of commodity titanium dioxide（TiO2）It is placed in Pyrex glass reactors, in 400 degrees Celsius of oxygen atmospheres
The device, is then connected, in 400 degrees Celsius of lower high vacuum by calcining 10 hours with high-vacuum installation（10-2Handkerchief）Under the conditions of handle 2
Hour and cold go to room temperature.In anhydrous and oxygen-free glove box, a certain amount of ruthenocene is dissolved in n-hexane, ruthenocene is obtained
Concentration is the hexane solution of 10 milligrams every milliliter of ruthenocene.Then, in glove box, 0.6 milliliter is taken to prepare with syringe
Ruthenocene hexane solution, and inject in Pyrex glass reactors.Pyrex glass reactors are then placed in tube furnace
On be heated to 150 degrees Celsius and maintain 24 hours, high vacuum 10 at such a temperature later-2Handkerchief handle 2 hours it is cold go to room temperature,
It is 0.6% bicyclic pentadiene ruthenium grafting titanium oxide to obtain the mass fraction of ruthenium（CpRu0.6/TiO2）Material.Weigh 10 milligrams
The CpRu prepared0.6/TiO2Material is de-gassed processing so as to be true in glass reactor in Pyrex glass reactors
Dummy status, is then filled with 50 milliliters of high-purity carbon dioxide gases thereto, in triplicate to ensure that air is cleared.Then, then
Inject 20 microlitres of deionized waters thereto with micro syringe.Encapsulation process further is carried out to glass reactor, then by it
It is placed under dark condition and stirs half an hour, 4 hours of illumination under 200-800 nanometers of simulated solar irradiation.
Embodiment 3
Weigh 1 gram of commodity titanium dioxide（TiO2）It is placed in Pyrex glass reactors, in 500 degrees Celsius of oxygen atmospheres
The device, is then connected, in 500 degrees Celsius of lower high vacuum by calcining 20 hours with high-vacuum installation（10-4Handkerchief）Under the conditions of handle 4
Hour and cold go to room temperature.In anhydrous and oxygen-free glove box, a certain amount of ruthenocene is dissolved in n-hexane, ruthenocene is obtained
Concentration is the hexane solution of 10 milligrams every milliliter of ruthenocene.Then, in glove box, 1 milliliter is taken to prepare with syringe
The hexane solution of ruthenocene, and inject in Pyrex glass reactors.Then Pyrex glass reactors are placed on tube furnace
It is heated to 180 degrees Celsius and maintains 40 hours, later high vacuum 10 at such a temperature-4Handkerchief handle 4 hours it is cold go to room temperature, obtain
The bicyclic pentadiene ruthenium for being 1% to the mass fraction of ruthenium is grafted titanium oxide（CpRu1.0/TiO2）Material.Weigh 10 milligrams of preparations
Obtained CpRu1.0/TiO2Material is de-gassed and handled so as to be vacuum shape in glass reactor in Pyrex glass reactors
State, is then filled with 50 milliliters of high-purity carbon dioxide gases thereto with airbag, in triplicate to ensure that air is cleared.Then,
Inject 20 microlitres of deionized waters thereto with micro syringe again.Encapsulation process further is carried out to glass reactor, then will
It is placed under dark condition and stirs half an hour, 4 hours of illumination under 200-800 nanometers of simulated solar irradiation.
Embodiment 4
Weigh 1 gram of commodity titanium dioxide（TiO2）It is placed in Pyrex glass reactor tubes, in 400 degrees Celsius of oxygen atmospheres
The device, is then connected, in 400 degrees Celsius of lower high vacuum by middle calcining 24 hours with high-vacuum installation（10-2Handkerchief）Under the conditions of locate
Reason 2 hours simultaneously cold is gone to room temperature.In anhydrous and oxygen-free glove box, a certain amount of ruthenocene is dissolved in n-hexane, two cyclopentadienyls are obtained
The concentration of ruthenium is the hexane solution of 10 milligrams every milliliter of ruthenocene.Then, in glove box, 5 milliliters are taken to match somebody with somebody with syringe
The hexane solution of good ruthenocene, and inject in Pyrex glass reactors.Pyrex glass reactors are then placed in tubular type
150 degrees Celsius are heated on stove and 24 hours are maintained, later high vacuum at such a temperature（10-2）Handkerchief handle 2 hours it is cold go to
Room temperature, it is 5% bicyclic pentadiene ruthenium grafting titanium oxide to obtain the mass fraction of ruthenium（CpRu5.0/TiO2）Material.Weigh 10 millis
Gram CpRu prepared5.0/TiO2Material is de-gassed processing so as to be in glass reactor in Pyrex glass reactors
Vacuum state, is then filled with 50 milliliters of high-purity carbon dioxide gases thereto, in triplicate to ensure that air is cleared.Then,
Inject 20 microlitres of deionized waters thereto with micro syringe again.Encapsulation process further is carried out to glass reactor, then will
It is placed under dark condition and stirs half an hour, 4 hours of illumination under 200-800 nanometers of simulated solar irradiation.
Embodiment 5
The preparation of catalyst and the photocatalysis methanation of carbon dioxide are identical with this part embodiment 1, unlike
Photocatalytic process is in visible ray（>=420 nanometers）Carried out under the conditions of irradiation.
Embodiment 6
The preparation of catalyst and the photocatalysis methanation of carbon dioxide are identical with this part embodiment 2, unlike
Photocatalytic process is in visible ray（>=420 nanometers）Carried out under the conditions of irradiation.
Embodiment 7
The preparation of catalyst and the photocatalysis methanation of carbon dioxide are identical with this part embodiment 3, unlike
Photocatalytic process is in visible ray（>=420 nanometers）Carried out under the conditions of irradiation.
Embodiment 8
The preparation of catalyst and the photocatalysis methanation of carbon dioxide are identical with this part embodiment 4, unlike
Photocatalytic process is in visible ray（>=420 nanometers）Carried out under the conditions of irradiation.
Embodiment and ruthenium content, xenon lamp wavelength and corresponding methane-generated quantity such as following table in comparative example：
It can be seen from above-mentioned data, compared with the titanium dioxide of unmodified ruthenocene, (the C in embodiment5H5)Ru/TiO2
The methane content that organic inorganic hybridization photochemical catalyst catalysis carbon dioxide is produced is more, shows that being effectively improved titanium dioxide is urging
Change the photocatalysis efficiency during carbon dioxide methanation.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (3)
1. one kind (C5H5)Ru/TiO2The preparation method of organic inorganic hybridization photochemical catalyst, it is characterised in that：Described (C5H5)
Ru/TiO2Organic inorganic hybridization photochemical catalyst is that have half three by what titanium dioxide and bicyclic pentadiene ruthenium were obtained by being combined
The mass fraction of the material of Mingzhi's structure, wherein ruthenium is 0.3-5.0%；Using surface organometallic chemistry method, by bicyclic penta 2
Alkenyl ruthenium is grafted onto titanium dioxide surface by the method for surface grafting, obtains the composite wood with similar half sandwich structure
Material, specifically includes following steps：
（1）0.01-10 grams of commodity titanium dioxide is taken to be placed in Pyrex glass reactors, between 250-500 degrees Celsius, oxygen
Calcined 0.5-20 hours under atmosphere, obtain white pigmented samples A；
（2）By step（1）Obtained white pigmented samples A handles 0.5-4 hour under 250-500 degrees Celsius of lower high vacuum, obtains
Canescence sample B；
（3）To step under the conditions of anhydrous and oxygen-free（2）3-50 milligrams of bicyclic pentadiene rutheniums are added in obtained sample B, in
10-40 hour is reacted under 100-180 degrees Celsius, dark yellow Sample C is obtained；
（4）By step（3）Obtained sample C is heated 0.5-4 hour under 100-180 degrees Celsius, high vacuum condition, and in
Room temperature is cooled under vacuum condition, the mass fraction for obtaining ruthenium is 0.3-5% (C5H5)Ru/TiO2Organic inorganic hybridization photocatalysis
Agent.
2. (C made from a kind of preparation method as claimed in claim 15H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst should
With, it is characterised in that：Described (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst is used for the photocatalysis methane of carbon dioxide
Change reaction.
3. application according to claim 2, it is characterised in that：The photocatalysis methanation of described photocatalysis carbon dioxide is anti-
Should, comprise the following steps that：
（1）Weigh the C that the 10-40 milligrams of above methods are prepared5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst is in Pyrex
In glass reactor；
（2）Processing is de-gassed to the Pyrex glass reactors of above-mentioned addition catalyst with mechanical pump；
（3）10-50 milliliters of carbon dioxide are filled with into above-mentioned Pyrex glass reactors with carbon dioxide airbag, with micro
Syringe injects 10-50 microlitres of deionized water to it, and is further sealed；
（4）Above-mentioned sealed Pyrex glass reactors are placed in illumination under the xenon lamp that wave-length coverage is 200-800 nanometers 4 small
When, or it is placed in 4 hours of illumination under 420-800 nanometers of xenon lamp.
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