CN109096069B - Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound - Google Patents
Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound Download PDFInfo
- Publication number
- CN109096069B CN109096069B CN201811073699.9A CN201811073699A CN109096069B CN 109096069 B CN109096069 B CN 109096069B CN 201811073699 A CN201811073699 A CN 201811073699A CN 109096069 B CN109096069 B CN 109096069B
- Authority
- CN
- China
- Prior art keywords
- reaction
- solar cell
- photo
- anode
- catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/54—Benzaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses application of a sensitized dye solar cell photo-anode as a catalytic medium in a reaction of synthesizing a small molecular compound through photocatalysis. The sensitized dye solar cell photo-anode can be used for alcohol oxidation reaction, C-H activation reaction, 1, 2-re-functionalization reaction of 1, 3-dicarbonyl compounds and C-O bond construction reaction. The catalytic medium has the advantages of wide applicable reaction type, small using amount of photosensitizer, good inactivation resistance stability, simple and convenient separation of the catalytic medium and solution, high reuse rate and the like, accords with the new concept of atomic economy, environmental protection, energy conservation and emission reduction, and provides a new idea for visible light catalytic reaction.
Description
Technical Field
The invention belongs to the field of ultraviolet-visible light catalytic synthesis, and relates to a novel catalytic means, namely a solar cell photo-anode is used as a catalytic medium to synthesize an organic compound. Specifically, the invention relates to application of a sensitized dye solar cell photo-anode as a catalytic medium in a reaction of a functional small molecular compound through photocatalytic synthesis.
Background
As is well known, with the high-speed consumption of traditional fossil energy (such as petroleum, coal, natural gas, etc.), and the increasing environmental pollution and greenhouse effect, the development and utilization of renewable energy resources are receiving wide attention from researchers at home and abroad. These renewable energy sources include wind, solar, tidal and geothermal energy, among others. The solar energy has the characteristics of direct development and utilization, environmental protection, inexhaustibility and inexhaustibility, and the energy of the sun irradiating the earth for 45 minutes is approximately equal to the sum of the energy used by human beings in one year. Therefore, for synthetic chemists, compared with traditional high-energy-consumption reactions such as heating and high-pressure reactions, the visible light reaction has become one of the hot areas of research of scientists due to its characteristics of cleanness, greenness and no pollution.
Light energy has been studied systematically by mankind for nearly a hundred years as one of pollution-free, green, clean energy sources. Ultraviolet light is generally used as a light source in the traditional photocatalytic reaction (the ultraviolet light in sunlight only accounts for about 2 percent, and the visible light is up to 47 percent), and the introduction of the visible light in the scientific research field not only avoids the damage of high-energy ultraviolet light to organisms, but also makes up the defects of longer infrared wavelength and relatively lower energy. However, most small molecule compounds are not sensitive to visible light waves and cannot directly absorb light waves in the visible light region to perform photochemical reactions. In order to solve the problem, the photosensitizer is used as a visible light catalytic reaction of a bridge. The visible light catalytic synthesis reaction not only abandons the conventional modes of high temperature, complex catalytic system and the like, but also gets rid of the limitations of the traditional light reaction on a light source, a special photoreactor and a reaction substrate, and has the superiority of green sustainable development which is incomparable with other chemical synthesis methods. However, the photosensitizers (such as rose bengal, alizarin red S, etc.) commonly used in the current reactions are usually present: the variety is single, the response range to visible light is narrow, the recovery is difficult, the reutilization rate is low, and the like. In addition, most of researches on visible light heterogeneous catalysis are focused on the photolysis of water to produce hydrogen (reference: Chinese patent document CN103877997A) and the photodegradation of organic matters (reference: Molecules,2012,17,1149 and 1158. Chinese patent document CN102974336A), and the application in the field of photocatalytic synthesis of organic compounds is relatively less.
Disclosure of Invention
The invention aims to provide application of a solar cell photo-anode as a catalytic medium in a reaction of a functional small molecular compound through photo-catalytic synthesis. The catalytic medium should be convenient for separation and recycling, and can realize multiple recycling of trace catalysts.
The invention firstly provides a catalyst which is a sensitized dye solar cell photo-anode and can be applied to photo-catalytic synthesis of functional small molecular compounds.
As a better choice for the above application, the photocatalytic process uses visible light with a wavelength of 254-860 nm. The wavelength used by the photoreaction is remarkably expanded by 254-860nm compared with the existing used photocatalytic process.
As a better choice for the above application, the photocatalytic process uses 380-780nm visible light. The wave band comprises a wave band of visible light, and compared with ultraviolet rays with shorter wavelength and infrared rays with larger wavelength, the wave band avoids the damage of high-energy ultraviolet rays to organisms and also makes up the defects of longer infrared wavelength and lower energy.
As a better choice for the above application, the visible light used in the photocatalytic process is 400-460nm, 460-520nm, 520-560 nm, 560-620nm, 620-680 nm, 680-740 nm or 740-800 nm.
As a better choice for the application, the reaction for synthesizing the functional small molecule compound comprises the participation of free radicals.
As a better choice for the above application, the reaction for synthesizing the functional small molecular compound is an oxidation reaction, a C-H activation reaction, a 1, 2-re-functionalization reaction of a 1, 3-dicarbonyl compound or a C-O bond construction reaction.
The reactions to which the present invention can be applied are listed below.
1) And (3) oxidation reaction: reaction for synthesizing aldehyde compound by oxidizing alcohol compound
As a preference for the substrate suitability of the above-mentioned embodiment under this catalytic system, the R group1When it is benzene (Ph), R2Is hydrogen (H) or benzene (Ph).
2) C-H activation reaction: take the photo-anode of the solar cell to catalyze the reaction of N-methylindole and bromoacetonitrile to construct a carbon heterobond as an example
3)1, 2-refunctionalization of 1, 3-dicarbonyl compounds: taking the synthesis of alpha-ketoester compound by reacting 1-phenyl-1, 3-butanedione with methanol as an example
4) C-O bond building reaction: the superiority of the application method for synthesizing the organic compound by the solar cell photoanode catalysis is detailed by taking the example that the diketone compound reacts with 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) to construct a C-O bond.
The R is 1Is H, CF3Me, OMe, F, Cl or bromine Br, said R2OEt, Me, Ph or OBn.
Said R is1When it is hydrogen (H), R2Ethoxy (OEt), methyl (Me), phenyl (Ph) or benzyloxy (OBn).
As a preference for the substrate suitability of the above-mentioned embodiment under this catalytic system, the R group2In the case of ethoxy (OEt), R1Is trifluoromethyl (CF)3) Methyl (Me), methoxy (OMe), fluorine (F), chlorine (Cl) or bromine(Br)。
As a preferable preference of the substrate applicability of the scheme under the catalytic system, the diketone compound is 2-thiophenecarboxylacetic acid ethyl ester.
Under the catalytic system of the invention, the reusability and the inactivation resistance of the catalyst are researched, and the solar photoanode which is easy to be separated from the reaction liquid can still keep better catalytic activity after being reused for at least 8 times after being simply washed.
Compared with the similar catalytic catalysts, the invention has the characteristics of simple and convenient recovery, small dosage of the photosensitizer, greenness and energy conservation. The invention combines the working principle of the solar cell photo-anode and the photo-catalytic synthesis reaction mechanism, applies the solar cell photo-anode as a catalytic medium to the field of visible light catalytic synthesis reaction, and realizes the synthesis of functional organic micromolecules driven by visible light. The invention develops a new method which is simple in catalytic system and separation method and convenient and rapid in repeated use of catalytic media, and develops an efficient catalytic strategy for synthesizing organic functional small molecular compounds by visible light catalysis.
The invention provides a new idea for synthesizing functional organic micromolecules by solar cell photo-anode catalysis, which not only provides a new method for visible light catalytic synthesis reaction, but also expands the application range of the solar cell photo-anode.
The sensitized dye solar cell photo-anode used as a catalytic medium has the advantages of wide applicable reaction types, small using amount of a photosensitizer, good inactivation resistance stability, simple and convenient separation of the catalytic medium and a solution, high reuse rate and the like, accords with the new concept of atomic economy, environmental protection, energy conservation and emission reduction, and provides a new idea for visible light catalytic reaction.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving an equivalent or similar purpose, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of aiding understanding of the present invention and should not be construed as specifically limiting the present invention.
The solar cell photo-anode used in the invention is obtained by loading a metal oxide or a metal oxide nanocrystalline porous film on a substrate and then sensitizing the metal oxide or metal oxide nanocrystalline porous film by adopting a dye or a photosensitizer. The invention can also directly take out the photo-anode of the sensitized dye solar cell from the solar cell for use, or directly purchase the photo-anode of the solar cell in the market for use.
For the method for synthesizing the photo-anode, see the methods disclosed in chinese patent documents CN100358160C, CN101030607A, CN100533786C, CN101271774B, CN101339851A, CN101593629B, CN102082032B, CN102509623A, CN103903859A, CN105390292A, CN106847518A, CN106098385A and CN107887169A for preparation.
In the above solar cell photo-anode, the substrate is made of conductive glass, quartz glass or common glass.
In the solar cell photo-anode, the metal oxide loaded on the substrate is TiO2、ZnO、SnO2、Nb2O5、NiO、ZrO2、CeO2And Ta2O5Or a combination thereof.
In the solar cell photoanode, the dye is one or more of ruthenium pyridine, iridium pyridine dye, metalloporphyrin dye, perylene derivative, cyanine dye, organic dye with a D-pi-A type structure and organic dye with a D-A-pi-A type structure, wherein D is an electron donor, A is an acceptor unit, pi is a bridge, and electrons given by the electron donor D from excited dye molecules are transferred to the acceptor unit A through the pi bridge.
The structures of typical organic dyes having a D- π -A type structure and D-A- π -A type structure are as follows:
in the dyes, the ruthenium pyridine dyes are N719, N845 and N3Black dye (black dye), MH08, MH09, MH10, K8, C101, C102, One or more of C103, C104, C105, C106, DCP2, JK206, JK207, and the like.
Among the dyes, the metalloporphyrin-based dye is one or more of YD2, YD6, SM315 and the like.
Ruthenium pyridine dyes and metalloporphyrin dyes used in the present invention are common dyes, and their trade names and specific structures are provided below.
The photosensitizer may be an organic photosensitizer or a quantum dot photosensitizer.
The organic photosensitizer is one or more of eosin B, alizarin red S, rose bengal and fluorescein.
The quantum dot photosensitizer can be CdS, CdSe, CdTe, PbS, Ag2Se、InP、Bi2S3、InAs、CuInS2One or more of (a).
The metal oxide supported on the substrate may be obtained by coating a metal oxide slurry on the substrate and heat-treating the coated substrate.
The nanocrystalline porous film is prepared by adopting metal oxide slurry through a screen printing method, a pulling method, a spin coating method, an anodic oxidation method, an electrochemical deposition method, a self-assembly method, a template method or a high-pressure pressing method.
The metal oxide slurry is prepared by coprecipitation method, sol-gel method, microemulsion method, hydrothermal synthesis method, and TiCl4Prepared by a gas-phase oxidation method, a diffusion flame method or an atomization hydrolysis method.
The corresponding photocatalytic reactions were verified as follows.
Example 1C-O bond building reaction: the invention is described with the common titanium dioxide and dye N719 for making a solar cell photoanode support.
A titanium dioxide slurry (either home-made or commercially available) is coated onto a cleaned substrate in the following areas: 0.7cm2Thickness of coatingAbout 10 μm, the substrate is subjected to heat treatment and dye load treatment by adopting a dye solar cell photo-anode preparation method, the dye load capacity of the prepared dye solar cell photo-anode is measured, and the experimental result is as follows: monolithic substrate load N719 of 2.8 x 10-4mmol, i.e. 0.56 mol%.
The prepared solar cell photo-anode is used for catalyzing free radical coupling reaction of diketone compounds and 2,2,6, 6-tetramethyl piperidine-nitrogen-oxide (TEMPO).
Taking ethyl benzoate as an example, 0.1mmol of TEMPO, 0.05mmol of ethyl benzoate and a solar cell photo-anode are placed in a visible light parallel reactor, 1 ml of anhydrous acetonitrile is added, and the reaction is stopped after 48 hours of reaction under the irradiation of 3W of blue light. Through column chromatography separation and purification, the separation yield of the target product can reach 85 percent.
Table 1 simple screening of reaction conditions with ethyl benzoate and TEMPO as raw materials:
| light source | Photo-anode | TEMPO | Time per hour | Yield of |
| Blue light | Is free of | 2.0equiv. | 48h | Is not reacted |
| Is free of | 2 pieces of | 2.0equiv | 48h | Is not reacted |
| Blue light | 1 piece of | 2.0equiv | 48h | 53％ |
| Blue light | 2 pieces of | 2.0equiv | 48h | 85％ |
| Blue light | 3 pieces of | 2.0equiv | 48h | 83％ |
| Blue light | 4 pieces of | 2.0equiv | 48h | 83％ |
From the above condition screens, it can be seen that: when the photo-anode or the light source is removed, the reaction cannot proceed. The experimental results prove that the organic compound synthesized by taking the solar cell photo-anode as a catalytic medium has higher feasibility.
The photo-anode of the solar cell is taken out of the reaction solution, and after the photo-anode is simply washed, the recycling capability of the substrate is tested, and the results are shown in the following table 2:
TABLE 2 results of repeated recycling
The catalytic medium and the reaction liquid are separated simply and conveniently, and the yield can be kept more than medium after 8 times of recycling, which shows that the solar cell photo-anode has better anti-inactivation stability as the catalytic medium.
TABLE 3 comparison of the reuse yields
Compared with the reported similar reactions (literature sources: Green chem.,2010,12,953-956), the catalytic system used in the invention has the following advantages:
(1) 3W visible light is used, the power is lower, and energy is saved.
(2) No stirring is needed, and the energy consumption is low.
(3) The catalytic medium is easy to separate from the reaction liquid and can be simply taken out without operations such as centrifugation and the like.
(4) Can be used repeatedly for at least 8 times.
(5) The catalyst was used in a smaller amount of 1.12 mol%.
(6) The catalytic system has wider application range.
The following list is the exploration of the substrate suitability of the solar cell photoanode as a catalytic mediator to catalyze the reaction of diketones and 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide. The substrate 1 was used to react with the substrate 2 under the preferred conditions described above, and the results are shown in Table 4 below:
TABLE 4 investigation of substrate suitability for reaction of diketones with 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide
As can be seen from the above examples, the photo-anode of the solar cell can be used as a catalytic medium for visible light catalysis and synthesis of functional organic small molecules. The method has the characteristics of less using amount of the photosensitizer, wide application range of the substrate, convenient recovery of the catalytic medium and repeated recycling.
The core of the invention is that the visible light catalysis is used as a catalytic medium to synthesize the organic compound by the solar cell photoanode: the synthesis method is verified by taking diketone and 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) as an example, and the method has the characteristics of good inactivation resistance stability of catalytic media, high atom economy and environmental friendliness.
Example 2 alcohol oxidation reaction:
The invention is illustrated by the preparation of a solar cell photo-anode by in-situ deposition of CdS on titanium dioxide.
Two prepared solar cell photo-anodes, reactant alcohol (0.05mmol) and 1mL of solvent (acetonitrile) are placed in a visible light parallel reactor and react for 24 hours in an oxygen atmosphere under illumination, and then the target products are obtained as shown in Table 5.
TABLE 5 alcohol Oxidation reaction products
Example 3-C-H activation reaction:
this example is illustrated by the preparation of a solar cell photoanode support from a complex of titanium dioxide and metallic iridium. Wherein the metal iridium complex has a structure a;
two prepared solar cell photo-anodes, reactants N-methylindole (0.1mmol), sodium acetate (2equiv.) and solvent acetonitrile (1mL) were placed in a visible light parallel reactor, and illuminated under argon atmosphere for 24 hours to obtain the target product, as shown in table 6.
TABLE 6C-H activation reaction products
Example 4 1, 2-Refunctionalisation of 1, 3-dicarbonyl Compounds:
this example is illustrated with titanium dioxide and dye N719 for making a solar cell photoanode support.
The prepared solar cell photo-anode is used for catalyzing C-C bonds of diketone compounds and alcohol compounds to be broken to synthesize ketone ester compounds. Taking 1-phenyl-1, 3-butanedione as an example, 0.1mmol of 1-phenyl-1, 3-butanedione, tert-butyl hydroperoxide (2equiv.), sodium acetate (2equiv.) and two photo-anodes of the solar cells are placed in a visible light parallel reactor, 1ml of anhydrous methanol is added, and the reaction is stopped after being irradiated by visible light for 24 hours. Separating and purifying by column chromatography to obtain 40% target compound.
The method can be realized by upper and lower limit values of intervals of process parameters (such as temperature, time and the like) and interval values, and embodiments are not listed.
The invention further provides a method for photocatalytic synthesis of organic compounds at different wavelengths of light, which specifically comprises the following steps of 7:
TABLE 7 photocatalytic synthesis of organic compounds at different wavelengths of light
In the experiment, the used solar cell photo-anode is obtained by loading metal oxide on a substrate and sensitizing the metal oxide by adopting dye, wherein the used substrate is ITO glass or FTO glass, and the loaded metal oxide is ZnO or TiO2Or WO3The dye used is ruthenium pyridine, iridium pyridine, organic dye, metalloporphyrin dye, perylene derivative phthalocyanine dye and inorganic quantum dot photosensitizer.
It is obviously impractical to perform all experiments limited by the number of types of solar cell photoanodes in the prior art, but as a general knowledge, for example, a nanocrystalline porous film of metal oxide obviously has properties similar to or better than those of metal oxide, a photosensitizer has properties similar to those of dye, and other solar cell anodes are obviously suitable for such catalytic reactions.
In the above examples, those not described in detail in the present invention may use the conventional technical knowledge in the field.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention may be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered by the scope of the claims of the present invention.
Claims (2)
1. The application of the photoanode of the sensitized dye solar cell in photocatalytic synthesis of a functional small molecular compound is characterized in that the reaction for synthesizing the functional small molecular compound is one of the following reactions:
reacting N-methylindole with bromoacetonitrile under the conditions of alkali and visible light to obtain
；
Reacting 1-phenyl-1, 3-butanedione with methanol under the conditions of tert-butyl hydroperoxide, alkali and visible light to obtain
；
2. The use according to claim 1, characterized in that the wavelength of the light used for photocatalytic synthesis is 380-780 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811073699.9A CN109096069B (en) | 2018-09-14 | 2018-09-14 | Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811073699.9A CN109096069B (en) | 2018-09-14 | 2018-09-14 | Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096069A CN109096069A (en) | 2018-12-28 |
| CN109096069B true CN109096069B (en) | 2022-06-28 |
Family
ID=64866357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811073699.9A Active CN109096069B (en) | 2018-09-14 | 2018-09-14 | Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096069B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957102B (en) * | 2022-05-16 | 2023-11-07 | 湖南大学深圳研究院 | Amide nitroxide free radical modified perylene molecule and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001097894A (en) * | 1999-09-30 | 2001-04-10 | Toshiba Corp | Reduction apparatus for carbon dioxide gas |
| CN102303901A (en) * | 2011-05-24 | 2012-01-04 | 南京大学 | Preparation method, product and use of micro/nano heretically-structured insert octahedral Zn2SnO4 |
| CN102532170A (en) * | 2011-12-21 | 2012-07-04 | 南京大学 | Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell |
| CN105899646A (en) * | 2013-11-26 | 2016-08-24 | 西门子公司 | Proton sponge as supplement to electrolytes for photocatalytic and electrochemical Co2 reduction |
| CN106757136A (en) * | 2016-12-02 | 2017-05-31 | 兰州大学 | A kind of method that methyl alcohol is prepared with carbon dioxide and water |
-
2018
- 2018-09-14 CN CN201811073699.9A patent/CN109096069B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001097894A (en) * | 1999-09-30 | 2001-04-10 | Toshiba Corp | Reduction apparatus for carbon dioxide gas |
| CN102303901A (en) * | 2011-05-24 | 2012-01-04 | 南京大学 | Preparation method, product and use of micro/nano heretically-structured insert octahedral Zn2SnO4 |
| CN102532170A (en) * | 2011-12-21 | 2012-07-04 | 南京大学 | Monovalent copper complex, preparation method thereof, method for catalyzing and reducing carbon dioxide by utilizing visible light and dye-sensitized solar cell |
| CN105899646A (en) * | 2013-11-26 | 2016-08-24 | 西门子公司 | Proton sponge as supplement to electrolytes for photocatalytic and electrochemical Co2 reduction |
| CN106757136A (en) * | 2016-12-02 | 2017-05-31 | 兰州大学 | A kind of method that methyl alcohol is prepared with carbon dioxide and water |
Non-Patent Citations (2)
| Title |
|---|
| Photocatalytic Reduction of Nitro Compounds Using TiO2 Photocatalyst by UV and Vis Dye-sensitized Systems;Chen Shifu等;《Chin. J. Chem.》;20110328;第29卷(第3期);全文 * |
| Photoelectrochemical Catalysis toward Selective Anaerobic Oxidation of Alcohols;Ruikang Zhang等;《Chemistry - A European Journal》;20170509;第23卷(第34期);第8146页实验部分、第8144页右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096069A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Corredor et al. | Comprehensive review and future perspectives on the photocatalytic hydrogen production | |
| Franchi et al. | Applications of sensitized semiconductors as heterogeneous visible-light photocatalysts in organic synthesis | |
| Luo et al. | Selective activation of benzyl alcohol coupled with photoelectrochemical water oxidation via a radical relay strategy | |
| Zhang et al. | Self-assembly of CdS/CdIn2S4 heterostructure with enhanced photocascade synthesis of schiff base compounds in an aromatic alcohols and nitrobenzene system with visible light | |
| Tahir | Well-designed ZnFe2O4/Ag/TiO2 nanorods heterojunction with Ag as electron mediator for photocatalytic CO2 reduction to fuels under UV/visible light | |
| Schilling et al. | Metal-free catalyst for visible-light-induced oxidation of unactivated alcohols using air/oxygen as an oxidant | |
| Zhang et al. | CdS/ZnO: a multipronged approach for efficient reduction of carbon dioxide under visible light irradiation | |
| Shiraishi et al. | Titanium dioxide/reduced graphene oxide hybrid photocatalysts for efficient and selective partial oxidation of cyclohexane | |
| Zhou et al. | Challenges and perspectives in designing artificial photosynthetic systems | |
| Ziarati et al. | Black hollow TiO2 nanocubes: Advanced nanoarchitectures for efficient visible light photocatalytic applications | |
| Wen et al. | Hybrid artificial photosynthetic systems comprising semiconductors as light harvesters and biomimetic complexes as molecular cocatalysts | |
| Song et al. | Photothermocatalytic hydrogen evolution over Ni2P/TiO2 for full-spectrum solar energy conversion | |
| Highfield | Advances and recent trends in heterogeneous photo (electro)-catalysis for solar fuels and chemicals | |
| CN107159313B (en) | A kind of core-shell structure TiO2The preparation method of nanotube@Ti-MOF catalyst | |
| Francis et al. | A review on recent developments in solar photoreactors for carbon dioxide conversion to fuels | |
| CN103028386B (en) | Ti<3+> and carbon codoped TiO2 photocatalyst with visible-light activity and preparation method of TiO2 photocatalyst | |
| Liu et al. | Photothermal effect of infrared light to enhance solar catalytic hydrogen generation | |
| Xia et al. | 3D hollow Bi2O3@ CoAl-LDHs direct Z-scheme heterostructure for visible-light-driven photocatalytic ammonia synthesis | |
| Li et al. | Photoelectrochemical catalysis of waste polyethylene terephthalate plastic to coproduce formic acid and hydrogen | |
| Chiu et al. | Designing dual-functional metal–organic frameworks for photocatalysis | |
| Nikolaou et al. | Antenna effect in BODIPY-(Zn) porphyrin entities promotes H2 evolution in dye-sensitized photocatalytic systems | |
| Saito et al. | Photocatalysis of CO2 reduction by a Ru (II)–Ru (II) supramolecular catalyst adsorbed on Al2O3 | |
| CN109096069B (en) | Application of sensitized dye solar cell photo-anode in photo-catalytic synthesis of functional small molecular compound | |
| Xiao et al. | Visible-light-activated TiO2 photocatalysis regionally modified by SiO2 for lignin depolymerization | |
| Hou et al. | Substituted Ti (IV) in Ce-UiO-66-NH2 Metal–Organic Frameworks Increases H2 and O2 Evolution under Visible Light |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |