CN109096069A - Sensitizing dyestuff solar battery light anode is in photocatalytic synthesis at the application in function small molecule compound - Google Patents
Sensitizing dyestuff solar battery light anode is in photocatalytic synthesis at the application in function small molecule compound Download PDFInfo
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- 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
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- C07C67/00—Preparation of carboxylic acid esters
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- 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
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- 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
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Abstract
Application the invention discloses sensitizing dyestuff solar battery light anode as catalysis medium in the reaction of photocatalysis synthesized micromolecule compound.Sensitizing dyestuff solar battery light anode of the invention can be used for oxidation of alcohols reaction, the reaction of function dough and C-O key construct reaction to the 1,2- of C-H priming reaction, 1,3- dicarbonyl compound again.Catalysis medium of the invention has many advantages, such as that applicable reaction type is higher compared with wide, photosensitizer dosage is few, Anti-Inactivation Stability is good, catalysis medium separates with solution simplicity, reuse rate, meet atom economy, environmentally protective and energy-saving and emission-reduction new concept, provides new thinking for visible light catalytic reaction.
Description
Technical field
The invention belongs to ultraviolet-visible lights to catalyze and synthesize field, use new catalytic means, i.e. solar battery light anode
As catalysis medium anthropogenics.In particular it relates to a kind of sensitizing dyestuff solar battery light anode conduct
It is catalyzed application of the medium in reaction of the photocatalytic synthesis at function small molecule compound.
Background technique
It is well known that as the high speed consumption of traditional fossil energy (such as petroleum, coal, natural gas) and environment are dirty
Dye and greenhouse effects constantly aggravate, and the development and utilization of renewable energy receive the extensive concern of domestic and international researcher.This
A little renewable energy include wind energy, solar energy, tide energy and geothermal energy etc..Wherein, solar energy has and can directly develop and use, is green
Colour circle guarantor, inexhaustible, nexhaustible feature, shining upon 45 minutes energy of the earth and being about as much as the mankind 1 year makes
With the summation of energy.It therefore,, can for the reaction of the high energy consumptions such as traditional heating, high pressure for synthesizing chemist
Light-exposed reaction is due to having the characteristics that clean, green non-pollution has become one of the hot fields of contemporary scientific man research.
Luminous energy is started systematically to study existing last 100 years by the mankind as a kind of one of free of contamination green clean energy resource
History.Traditional light-catalyzed reaction usually using ultraviolet light as light source (ultraviolet light only accounts for 2% or so in sunlight, it is seen that
47%) light is then up to, it is seen that light not only avoids the ultraviolet destruction to organism of high-energy, also more in the introducing of scientific research field
The deficiency that infrared wavelength is longer, energy is relatively low is mended.However, most of small molecule compounds are to visible light wave and unwise
Sense, cannot directly absorb the light wave of visible region and carry out photochemical reaction.In order to solve this problem, photosensitizer is as bridge
Visible light catalytic come into being.It is normal that the synthetic reaction of visible light catalytic has not only abandoned high temperature, catalyst system complexity etc.
Scale formula also gets rid of limitation of traditional light reaction to light source, special Photoreactor, reaction substrate, possesses other chemistry
The superiority of incomparable " green " sustainable development of synthetic method.However photosensitizer common in reaction at present is (such as: rose
Red, alizarin red S etc.) that usually there is: types is more single, to visible light-responded narrow range, recycling is difficult, recycling rate is low
The problems such as.In addition, the research overwhelming majority for visible light heterocatalysis concentrates on photodissociation aquatic products hydrogen (bibliography: Chinese special
Sharp document CN103877997A) and light degradation organic matter (bibliography: Molecules, 2012,17,1149-1158. China
Patent document CN102974336A), the application in photocatalysis anthropogenics field is also relatively fewer.
Summary of the invention
The object of the present invention is to provide a kind of solar battery light anodes to be used as catalysis medium in photocatalytic synthesis at function
Application in the reaction of small molecule compound.The catalytic media should have to be used convenient for separation and recycling, and can be realized micro-
Measure the multiple Ke Xunhuanliyong of catalyst.
Present invention firstly provides a kind of catalyst, which is sensitizing dyestuff solar battery light anode, the catalysis
Agent can be applied to photocatalytic synthesis into function small molecule compound.
A kind of better choice is applied as above-mentioned, photocatalytic process is 254-860nm using the wavelength of visible light.254-
860nm has significantly expanded the wavelength that light reaction uses relative to the existing photocatalytic process used.
A kind of better choice is applied as above-mentioned, photocatalytic process is 380-780nm using visible light.The wave band includes
The wave band of visible light, the ultraviolet light shorter relative to wavelength and the biggish infrared ray of wavelength, the wave-length coverage avoid height
The ultraviolet destruction to organism of energy, also compensates for the deficiency that infrared wavelength is longer, energy is relatively low.
Apply a kind of better choice as above-mentioned, photocatalytic process using visible light be 400-460nm, 460-520nm,
520nm-560nm, 560-620nm, 620nm-680nm, 680nm-740nm or 740nm-800nm.
A kind of better choice is applied as above-mentioned, synthesizing the function small molecule compound reaction includes that free radical is joined
With.
Apply a kind of better choice as above-mentioned, synthesize the function small molecule compound reaction be oxidation reaction,
C-H priming reaction, 1,3- dicarbonyl compound 1,2- again function dough reaction or C-O key construct reaction.
The reaction that the present invention can be applicable in is listed as follows.
1) oxidation reaction: for the reaction of alcohol compound oxidative synthesis aldehyde compound
One kind as substrate applicability of the above scheme under the catalyst system is preferred, the R1When for benzene (Ph), R2For
Hydrogen (H) or benzene (Ph).
2) it C-H priming reaction: is reacted with solar battery light anode catalysis N- methyl indol with bromoacetonitrile and constructs carbon heterodesmic
For
3) 1,2- of 1,3- dicarbonyl compound again react by function dough: being reacted with 1- phenyl -1,3- diacetyl with methanol
For synthesis α -one ester compounds
4) C-O key constructs reaction: anti-with cyclohexadione compounds and 2,2,6,6- tetramethyl piperidine-nitrogen-oxide (TEMPO)
It should construct for C-O key, the application method of organic compound is catalyzed and synthesized to solar battery light anode according to the present invention
Superiority have been described in detail.
The R1For H, CF3, Me, OMe, F, Cl or bromine Br, the R2For OEt, Me, Ph or OBn.
The R1When for hydrogen (H), R2For ethyoxyl (OEt), methyl (Me), phenyl (Ph) or benzyloxy (OBn).
One kind as substrate applicability of the above scheme under the catalyst system is preferred, the R2For ethyoxyl (OEt)
When, R1For trifluoromethyl (CF3), methyl (Me), methoxyl group (OMe), fluorine (F), chlorine (Cl) or bromine (Br).
Preferably, the cyclohexadione compounds are 2- to one kind as substrate applicability of the above scheme under the catalyst system
Thenoyl ethyl acetate.
Under catalyst system of the invention, catalyst repeat performance and resistance to deactivation are studied, easily divide with reaction solution
From solar energy anode simply washed after, after reusing at least 8 times, be still able to maintain preferable catalytic activity.
The present invention is compared to similar catalytic, has the characteristics of recycling is easy, and photosensitizer dosage is few, green energy conservation.
The present invention combines solar battery light anode working principle and photocatalytic synthesis at reaction mechanism, by solar battery light anode
It is applied to visible light catalytic synthetic reaction field as catalytic media, to realize the conjunction of the function small organic molecule of visible optical drive
At.The present invention develops a kind of catalyst system and separation method is simple and catalytic media can the new side that reuses of fast and easy
Method synthesizes organic functions small molecule compound for visible light catalytic and develops a kind of efficient catalysis strategy.
The present invention provides the new approaches that a kind of solar battery light anode catalyzes and synthesizes function small organic molecule, are not only
Visible light catalytic synthetic reaction provides new method, while having expanded the application range of solar battery light anode.
Sensitizing dyestuff solar battery light anode of the present invention has as catalysis medium is applicable in that reaction type is relatively wide, photosensitizer
Dosage is few, Anti-Inactivation Stability is good, catalysis medium separates the advantages that easy, reuse rate is higher with solution, meets atom warp
Ji, environmentally protective and energy-saving and emission-reduction new concept provide new thinking for visible light catalytic reaction.
Specific embodiment
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.Unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.It is described to understand the present invention just for the sake of help, it should not be considered as to concrete restriction of the invention.
The solar battery light anode that the present invention uses is metal oxide-loaded or metal oxide on substrate receives
After rice crystal porous film, metal oxide or metallic oxide nanocrystal porous membrane are sensitized using dyestuff or photosensitizer
It obtains.The present invention can also directly take out the light anode of sensitizing dyestuff solar battery from solar battery to use, or
Directly bought using market solar battery light anode come using.
About the synthetic method of light anode, may refer to Chinese patent literature such as CN100358160C, CN101030607A,
CN100533786C、CN101271774B、CN101339851A、CN101593629B、CN102082032B、
CN102509623A、CN103903859A、CN105390292A、CN106847518A、CN106098385A、CN107887169A
Disclosed in method preparation.
In above-mentioned solar battery light anode, the substrate is electro-conductive glass, quartz glass or simple glass.
In above-mentioned solar battery light anode, the metal oxide loaded in substrate is TiO2、ZnO、SnO2、Nb2O5、
NiO、ZrO2、CeO2And Ta2O5One of or composition.
In above-mentioned solar battery light anode, the dyestuff be pyridine ruthenium, pyridine iridium dyestuff, metalloporphyrin class dyestuff,
Derivative, has one of D- π-A type structure organic dyestuff and D-A- π-A type structure organic dyestuff or more at cyanine type dye
Kind, wherein D is electron donor, and A is receptor unit, and π is bridge, and the dye molecule that is stimulated is passed through by the electronics that electron donor D is provided
π bridge passes to receptor unit A.
It the following is the typical structure with D- π-A type structure organic dyestuff and D-A- π-A type structure organic dyestuff:
In abovementioned dyes, the pyridine ruthenium dye is N719, N845, N3, black dyestuff (black dye), MH08, MH09,
One of MH10, K8, C101, C102, C103, C104, C105, C106, DCP2, JK206, JK207 etc. or a variety of.
In abovementioned dyes, the metalloporphyrin class dyestuff is one of YD2, YD6, SM315 etc. or a variety of.
Used pyridine ruthenium dye and metalloporphyrin class dyestuff are common dyestuff in the present invention, provide its quotient as follows
The name of an article and specific structure.
Photosensitizer above-mentioned can be organic photosensitizer or quantum dot photosensitizer.
Organic photosensitizer above-mentioned is one of Eosin B, alizarin red S, Bengal rose red, fluorescein or a variety of.
The quantum dot photosensitizer above-mentioned can be CdS, CdSe, CdTe, PbS, Ag2Se、InP、Bi2S3、InAs、
CuInS2One of or it is a variety of.
The metal oxide loaded on forgoing substrate can be the coated metal oxide slurry on substrate, be heat-treated
It arrives.
Aforementioned nanocrystalline porous film class be using metal oxide paste by silk screen print method, czochralski method, spin-coating method,
Anodizing, electrochemical deposition method, self-assembly method, template or high pressure pressing are prepared.
Aforementioned metal oxides slurry passes through coprecipitation, sol-gel method, microemulsion method, hydrothermal synthesis method, TiCl4
Vapour phase oxidation process, diffusion flame method or atomization Hydrolyze method are prepared.
It the following is the verifying to corresponding light-catalyzed reaction.
Embodiment 1 --- C-O key constructs reaction: being to prepare solar battery light with common titanium dioxide and dyestuff N719
The present invention will be described for plate-load object.
Titania slurry (self-control or commercially available) is coated in the clean substrate cleaned, coated area
Are as follows: 0.7cm2, coating thickness is about 10 μm, using dye solar cell light anode preparation method to substrate carry out heat treatment and
Dye load processing, and the dye solar cell light anode dye load amount of preparation is measured, experimental result: monolithic base
It is 2.8*10 that piece, which loads N719,-4Mmol, i.e. 0.56mol%.
The above-mentioned solar battery light anode prepared is used to be catalyzed cyclohexadione compounds and 2,2,6,6- tetra- by the present invention
Methyl piperidine-nitrogen-oxide (TEMPO) free radical coupling reaction.
By taking ethyl benzoate as an example, by the ethyl benzoate of TEMPO, 0.05mmol of 0.1mmol and solar battery light
Anode is put into visible light parallel reactor, and 1 milliliter of anhydrous acetonitrile is added, and is reacted 48 hours under the blue light illumination of 3W, reaction
It can stop.Through column chromatographic isolation and purification, the separation yield of object is up to 85%.
Table 1 carries out simple screening to reaction condition using ethyl benzoate and TEMPO as raw material:
| Light source | Light anode | TEMPO | Time/hour | Yield |
| Blue light | Nothing | 2.0equiv. | 48h | It does not react |
| Nothing | 2 | 2.0equiv | 48h | It does not react |
| Blue light | 1 | 2.0equiv | 48h | 53% |
| Blue light | 2 | 2.0equiv | 48h | 85% |
| Blue light | 3 | 2.0equiv | 48h | 83% |
| Blue light | 4 | 2.0equiv | 48h | 83% |
It can be seen that reaction can not carry out when light anode or light source are removed from above-mentioned condition screening.Above-mentioned experimental result
It proves using solar battery light anode as catalysis medium anthropogenics feasibility with higher.
Solar battery light anode is taken out from reaction solution, it is simple rinse after, to the recycling ability of the substrate into
Row test, as a result such as the following table 2:
2 repetitive cycling of table uses result
Catalytic media of the present invention separates simplicity with reaction solution, is recycled 8 times and is still able to maintain the medium above yield, explanation
Solar battery light anode is that catalysis medium has preferable Anti-Inactivation Stability.
Table 3 reuses yield comparison
Compared with reported generic reaction (literature reference: Green Chem., 2010,12,953-956), the present invention
The catalyst system used has the advantages that
(1) 3W visible light is used, power is smaller, more energy saving.
(2) without stirring, low energy consumption.
(3) catalytic media is easily separated with reaction solution, simple to take out, and is not required to carry out the operation such as being centrifuged.
(4) it is recycled reciprocal use at least 8 times or more.
(5) dosage of catalyst is less, is 1.12mol%.
(6) this catalyst system scope of application is wider.
Solar battery light anode is listed as follows as catalysis medium, is catalyzed diketone and 2,2,6,6- tetramethyl piperidines-
Nitrogen-oxide reaction substrate applicability is probed into.It is reacted under the conditions of above-mentioned more excellent using substrate 1 with substrate 2, it is as a result as follows
Shown in table 4:
The substrate applicability that 4 cyclohexadione compounds of table and 2,2,6,6- tetramethyl piperidine-nitrogen-oxide react is probed into
From examples detailed above as can be seen that solar battery light anode can be used for visible light catalytic synthesis as catalysis medium
Function small organic molecule.This method have photosensitizer dosage is few, wide application range of substrates, catalytic media convenient for recycling, can be multiple
The characteristics of recycling.
Core of the invention is to realize that visible light catalytic synthesis is organic using solar battery light anode as catalysis medium
Compound: with diketone and 2, verifying the synthesizing mean for 2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO),
This method has the characteristics that catalysis medium Anti-Inactivation Stability is good, atom economy is high, environmental-friendly.
Embodiment 2 --- oxidation of alcohols reaction:
In-situ deposition CdS prepares solar battery light anode the present invention will be described on the titanium dioxide.
The solar battery light anode that two panels is prepared, reactant alcohol (0.05mmol) and 1mL solvent (acetonitrile) are put into
In visible light parallel reactor, oxygen atmosphere is reacted 24 hours under illumination, and it is as shown in table 5 to can be obtained target product.
5 oxidation of alcohols reaction product of table
Embodiment 3-C-H priming reaction:
Solar battery light anode loaded article is prepared with the complex of titanium dioxide and metal iridium to be illustrated this example.
Wherein, metal iridium complex structure is a；
The solar battery light anode that two panels is prepared, reactant N- methyl indol (0.1mmol), sodium acetate
(2equiv.) and solvent acetonitrile (1mL) are put into visible light parallel reactor, and illumination 24 hours, can be obtained under argon atmosphere
Target product, as shown in table 6.
Table 6C-H activation reaction product
Embodiment 4 --- the 1,2- of 1,3- dicarbonyl compound again react by function dough:
It is to prepare solar battery light anode loaded article to be illustrated this example with titanium dioxide and dyestuff N719.
The above-mentioned solar battery light anode prepared is used to be catalyzed the C-C key of cyclohexadione compounds and alcohol compound
Fracture synthesis ketone ester type compound.By taking 1- phenyl -1,3- diacetyl as an example, by 1- phenyl -1,3- diacetyl of 0.1mmol, uncle
Butylhydroperoxide (2equiv.), sodium acetate (2equiv.) and two panels solar battery light anode are put into visible light parallel reaction
In device, 1 milliliter of anhydrous methanol is added, it is seen that light irradiation lower reaction 24 hours, reaction can stop.Column chromatographic isolation and purification, can
Obtain 40% target compounds.
Technological parameter (such as temperature, time) section bound value of the invention and interval value can realize this law,
Embodiment numerous to list herein.
Invention further provides under different optical wavelength carry out photocatalysis anthropogenics, specifically include as
The following table 7:
Table 7 carries out photocatalysis anthropogenics under different optical wavelength
When carrying out above-mentioned experiment, used solar battery light anode is metal oxide-loaded on substrate, use
Dyestuff is sensitized obtaining to metal oxide, used in substrate be ito glass, FTO glass, load metal oxidation
Object is ZnO, TiO2Or WO3, used dyestuff be pyridine ruthenium, pyridine iridium dyestuff, organic dyestuff, metalloporphyrin class dyestuff,
Derivative cyanine type dye living and inorganic matter quantum dot photosensitizer.
It is confined to the type of solar battery light anode more in the prior art, carrying out all experiments obviously is not
Reality, but as common sense, as the nanocrystalline porous film of metal oxide obviously have it is approximate with metal oxide or
Better properties, photosensitizer has obviously to be suitable for such with the approximate property of dyestuff, other solar photocell anodes
Catalysis reaction, solar battery light anode other kinds of for part carried out similar experiment, show it is other similar too
Positive energy battery light anode is suitable for such catalysis reaction.
In above-described embodiment, ordinary skill in the art knowledge is can be used in the unspecified content of the present invention.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (5)
1. sensitizing dyestuff solar battery light anode is in photocatalytic synthesis at the application in function small molecule compound.
2. application according to claim 1, which is characterized in that photocatalytic synthesis is 254-860nm at the wavelength of light is used.
3. application according to claim 1, which is characterized in that synthesize the reaction process packet of the function small molecule compound
Include free radical participation.
4. application according to claim 3, which is characterized in that synthesize the reaction of the function small molecule compound as oxidation
Reaction, C-H priming reaction, 1,3- dicarbonyl compound 1,2- again function dough reaction or C-O key construct reaction.
5. application according to claim 4, which is characterized in that the oxidation reaction is oxidation of alcohols reaction.
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| CN114957102A (en) * | 2022-05-16 | 2022-08-30 | 湖南大学深圳研究院 | Perylene molecule modified by amido nitroxide free radical, preparation and application thereof |
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