CN104190470B - A kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst and preparation thereof and application - Google Patents
A kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst and preparation thereof and application Download PDFInfo
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Abstract
The invention provides a kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst and preparation thereof and application, described composite photo-catalyst is by metal organic framework compound Zr-BDC-NH containing zirconium2With Graphene by the compound material with class sandwich structure obtained, wherein the mass fraction of Graphene is 0.5-5.0%.With the graphene oxide presoma as Graphene modified, non-covalent self assembly situ solvent by the use of thermal means is used to be prepared from, compared with the Zr-MOFs of unsupported Graphene, photocatalysis performance significantly improves, it is embodied under the exciting of the visible ray of 420-800 nanometer, aromatic alcohol organic matter highly selective can be converted into the aromatic aldehydes material of correspondence by this composite, and selectivity is 100%, and a conversion ratio is up to 70%.This non-covalent self assembly situ solvent by the use of thermal means simply and easily operates, the Zr-MOFs/ graphene composite material prepared has the ability of the photocatalysis to selectively oxidation aromatic alcohol material of excellence, and the clean and effective chemical industry production to fine chemicals has important promotion meaning.
Description
Technical field
The invention belongs to photochemical catalyst field, be specifically related to a kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst and preparation thereof and its application in aromatic aldehyde chemicals synthesizes.
Background technology
Aromatic aldehyde compound is that a class all has wide variety of important chemical in the industries such as spices, food additives, medicine, dyestuff, agricultural chemicals, coating and liquid crystal material.Its synthesis and preparation occupy very important status at chemical field.Typically can pass through chemical synthesis, electrolytic synthesis and phase transfer catalysis process and prepare Aromatic aldehyde compound, wherein chemical synthesis considers from raw material and route, is broadly divided into direct chemical reactive synthesis and indirect chemical is synthesized.Directly chemical reaction be directly after phenyl ring introduces formoxyl or introduces other groups again after chemical reaction be converted into formoxyl, and indirect chemical reaction is group existing on phenyl ring to be directly over series of chemical be converted into formoxyl.Wherein, directly chemical synthesis process has obtained studying widely; as Reimer-Tiemman reacts; Gattermann-Koch reacts; Vilsmier reacts, friedel-craft formylation reaction etc., and the indirect chemical synthetic method that group existing on aromatic rings is converted into formoxyl aoxidizes because of side-chain radical or reducing degree is difficult to control to; reaction has the biggest uncontrollability and unpredictability, and therefore selectivity is the most relatively low.And, it is indefinite or produce environmentally harmful material and production process can cause the problem such as equipment corrosion and pollution that these traditional chemical synthesis and technique there is also accessory substance, at the society that environmental problem and energy problem increasingly highlight, its development is very restricted.And photocatalysis synthetic technology, by the selection of reaction condition, regulation and control can realize by the high selective conversion of aromatic alcohol material to aromatic aldehyde compound, it it is a kind of cleaning, non-secondary pollution, safety, simple to operate, efficient green syt new technology, is just showing huge potentiality in the synthesis of aromatic aldehyde chemicals.
Metal organic framework compound (MOFs, or claim poroid coordination polymer) material, not only there is bigger specific surface area, abundant pore passage structure, and the Nomenclature Composition and Structure of Complexes is rich and varied, synthesis can be designed according to certain function.Considering from industrial production angle, it synthesizes low cost, can be mass-produced.Therefore, based on these advantages, this material is in storage and the separation of gas, molecular recognition, and the various fields such as biology conducts, chemical sensor, electromagnetism, catalyst are widely applied.As photochemical catalyst, in recent years, MOFs material was at photodissociation aquatic products hydrogen, CO2Reduction, the application of the aspect such as organic selective conversion is obtained for research and explores, but photocatalysis efficiency is low.From the photocatalysis technology mechanism of action and the factor analysis that affects photocatalysis efficiency, the relatively low photocatalysis efficiency of MOFs material can be improved by following two path: recombining of (1) suppression light induced electron and hole；(2) electro transfer between interface is accelerated.
Graphene, a kind of has good physics, heat, chemistry and an electrical stability, and excellent photopermeability and the two-dimension plane structure material of electric conductivity, because of the electron mobility that it is surprising, become the excellent carrier of photochemical catalyst in recent years.It can be the transmission of photo-generated carrier and migrate one " express passway " of offer, thus reaches accelerating space separation of charge, and suppression photo-generate electron-hole, to compound, accelerated the purpose of Charge transfer on interface, and finally improved the quantum efficiency of photochemical catalyst.Therefore, utilize the two-dimension plane structure of Graphene uniqueness and outstanding electron transfer character, it is combined with MOFs material, can realize improving the efficiency of MOFs catalysis material.
Maryam Jahan et al. reports preparation method (the Structure-directing role of graphene in the synthesis of of a kind of MOF-5/ graphene composite material
metal− organic framework nanowires, J. Am. Chem. Soc. 2010, 132,
14487-14495).First graphene oxide is carried out reducing and obtains the graphene oxide of reduction by the method, then is reacted by the diazol between p-aminobenzoic acid and obtain the Graphene that benzoic acid is modified.With the Graphene of this functionalization as presoma, with raw material-slaine and the organic ligand of synthesis MOF-5, through reaction in-situ, finally give MOF-5/ graphene composite material.The method first passes through chemical reaction and fixes a certain amount of carboxyl functional group at graphenic surface, reached the purpose got up with MOFs materials chemistry grafting by Graphene again by the coordination between the fixing carboxyl of metal ion during In-situ reaction and graphenic surface, the also growth to MOFs material of the most this coordination serves the effect of structure directing.Meanwhile, they are also adopted by same method and are prepared for the composite (Electrocatalytically of a kind of ferriporphyrin MOFs and Graphene
active graphene–porphyrin MOF composite for oxygen reduction reaction,J. Am. Chem. Soc.
2012,134,6707-6713), the graphene oxide of the reduction modified using pyridine dye as presoma, obtains Graphene/ferriporphyrin MOFs composite by carrying out In-situ reaction between Graphene and the raw material of MOFs modified.But, by chemical reaction, graphenic surface is modified, inevitably introduces new defect on its surface, therefore affect the electron transfer character of Graphene.
US20130157837 A1 discloses the in-situ preparation method of a kind of MOFs material and nano-carbon material composite, and wherein carbon nanomaterial includes CNT, Graphene, carbon nano-fiber, carbon nanobelts etc..The method is by by CNT, or Graphene, or with the carbon nano-fiber of Activation of Hydrogen Peroxide Solution, or carbon nanobelts etc. joins in the presoma (dissolved with slaine and the solution of organic ligand) of MOFs material, the growth of MOFs material and the forming process of crystal under uniform temperature, finally give MOFs intercalation in the middle of nano-carbon material, outside and marginal composite.In this invention, carbon nano-fiber is simply modified by the preparation method of report, other carbon nanomaterials are then directly added in the precursor solution of MOFs materials synthesis, because the growth course of MOFs material (metal ion and organoligand coordination, the process of MOFs construction unit extension) in, active force between metal and organic ligand is stronger, and and active force between Graphene more weak, it is possible to anchor chain is little at graphenic surface or intercalation MOFs between multi-layer graphene.
Xin Zhou et al. reports the presoma of a kind of graphene oxide through nitrogen high temperature reduction using unmodified and synthesis MIL-101-chromic nitrate and Carboxylic acid ligand etc. and directly carries out method (the A novel MOF/graphene oxide that In-situ reaction prepares Graphene@MIL-101
composite rGO@ MIL-101 with high adsorption capacity for acetone, J. Mater.
Chem. A. 2014,2,4722-4730), in the method, the graphene oxide of reduction is without chemical modification, do not introduce more defect, but without the surface of graphene oxide of the reduction modified because there is no hydroxyl, the existence of the oxygen-containing functional group such as epoxy radicals and carboxyl, and the active force between metal ion and part is more weak, so can not effectively MOFs material be got up with Graphene grafting.
Problem in terms of the preparation method of the MOFs/ graphene composite material of report exists following two in document above and patent of invention: (1) uses the direct raw material (slaine and organic ligand) with synthesis MOFs without the Graphene modified to carry out In-situ reaction, owing to the coordination between metal ion and organic ligand is relatively strong, be easily caused with Graphene is compound undesirable.(2) use through chemical modification, surface contain a certain amount of, the Graphene of functional group of bonded ligand can be carried out as presoma with metal ion, it is carried out In-situ reaction with the raw material (slaine and organic ligand) synthesizing MOFs further, although Graphene and MOFs material can be got up by the coordination grafting between metal ion and the part of graphenic surface, but in the chemical modification process that graphite is dilute, can inevitably introduce more defect, greatly reduce the electrical conductivity of Graphene.
Summary of the invention
It is an object of the invention to provide a kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst and preparation thereof and application, with the graphene oxide presoma as Graphene modified, non-covalent self assembly situ solvent by the use of thermal means is used to be prepared from, compared with the Zr-MOFs of unsupported Graphene, photocatalysis performance significantly improves, it is embodied under the exciting of the visible ray of 420-800 nanometer, aromatic alcohol organic matter highly selective can be converted into the aromatic aldehydes material of correspondence by this composite, selectivity is 100%, and a conversion ratio is up to 70%.This non-covalent self assembly situ solvent by the use of thermal means simply and easily operates, the Zr-MOFs/ graphene composite material prepared has the ability of the photocatalysis to selectively oxidation aromatic alcohol material of excellence, and the clean and effective chemical industry production to fine chemicals has important promotion meaning.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of sandwich structure Zr-MOFs/ graphene composite photocatalyst is by metal organic framework compound Zr-BDC-NH containing zirconium2With Graphene by the compound material with class sandwich structure obtained, wherein the mass fraction of Graphene is 0.5-5.0%.
Described composite photo-catalyst uses non-covalent assembling situ solvent by the use of thermal means to be prepared from, and comprises the following steps:
(1) take aqueous dispersion liquid that 1-10 milliliter concentration is 1.6mg/ml graphene oxide in 150 milliliters of N, N '-dimethyl formamide (DMF), ultrasonic 30-40 minute, obtain brown yellow solution A；
(2) in solution A, 11.43-17.16 milligram trimethyl-(2-oxygen-2-pyrene-1-base-ethyl)-ammonium bromide (pyrene is added+), more ultrasonic 30-40 minute, obtain bright yellow solution B；
(3) in solution B, 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH are added2 -H2BDC), it is stirred overnight under normal temperature；
(4) in the solution that step (3) obtains, 318 milligrams of zirconium chloride (ZrCl are added again4) and 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH2 -H2BDC), stirring at normal temperature 30-60 minute under the stir speed (S.S.) of 600-800 rev/min；
(5) solution by portions obtained after stirring is moved in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, naturally cool to room temperature, by centrifugation, after methyl alcohol exchanges 5-7 days, it is dried in 80 DEG C of vacuum drying ovens, obtains described sandwich structure Zr-MOFs/ graphene composite photocatalyst.
Described composite photo-catalyst is applied to aromatic aldehyde chemicals synthetic reaction.
Under the exciting of visible ray, described composite photo-catalyst can be catalyzed the high-selectivity oxidation of aromatic alcohol material, and oxidation product is aromatic aldehyde.
Described aromatic alcohol material be phenmethylol, p nitrobenzyl alcohol, to fluorine-based phenmethylol, to any one in methylbenzyl alcohol.
The high-selectivity oxidation process of described aromatic alcohol material is specific as follows: weigh 20-40 milligram sandwich structure Zr-MOFs/ graphene composite photocatalyst, add 2-4 milliliter and lead to the aromatic alcohol material of oxygen-saturated benzotrifluoride and 0.1-0.5 mM, seal, with the xenon source illumination that wave-length coverage is 420-800 nanometer.Described logical oxygen-saturated benzotrifluoride is to be passed through pure oxygen in the benzotrifluoride of fixed volume 60-90 minute under air-proof condition.
The present invention is with trimethyl-(2-oxygen-2-pyrene-1-base-ethyl)-ammonium bromide (pyrene+) presoma that graphene oxide is Graphene modified, with zirconium chloride (ZrCl4) and 2-amino terephthalic acid (TPA) (2-NH2-H2BDC) source metal and the ligand sources of MOFs it are respectively, use non-covalent self assembly situ solvent by the use of thermal means, by strengthening the adhesion between Graphene and organic ligand, achieve MOFs material anchor chain well in the purpose of graphenic surface, avoid the introducing of graphenic surface excess defect, obtain the Zr-MOFs/ graphene composite material with similar sandwich structure.The more important thing is, the composite that the method prepares shows the photocatalysis performance of excellence during the photocatalysis of aromatic aldehyde synthesizes, and result of study shows that the addition of Graphene can improve the photocatalysis efficiency of Zr-MOFs material.Zr-MOFs/ Graphene sandwich structure composite photo-catalyst prepared by the present invention has the development prospect of commercial Application in the photocatalysis technology of aromatic aldehyde chemicals synthesizes.
The remarkable advantage of the present invention is:
(1) can be by Zr-MOF anchor chain well on the two dimensional surface of Graphene, form class sandwich structure, therefore, after accepting illumination, light induced electron can be transmitted rapidly by Graphene and be migrated out, thus restrained effectively the compound of electron hole pair, improve the photocatalysis efficiency of MOFs material.
(2) composite photo-catalyst can at utmost low absorption and utilize light, under the radiation of certain energy light, can effectively, highly selective aromatic alcohol organic matter is converted into the aromatic aldehyde compound of its correspondence, selectivity is 100%, and the illumination conversion ratio of 8 hours reaches 70%.
(3) this invention provide not only the preparation method of a kind of sandwich structure Zr-MOFs/graphene composite photocatalyst simple to operation, and the composite photo-catalyst prepared can be effectively realized the photocatalysis method synthesis of aromatic aldehyde chemicals: on the one hand, the highest, efficiently solve in aromatic aldehyde chemicals indirect chemical synthetic method, the uncontrollability of reaction being difficult to control to because of side-chain radical oxidation or reducing degree and causing and unpredictability；The features such as on the other hand, conversion ratio is considerable, and has green, cleaning, non-secondary pollution, safety, simple to operate.
Accompanying drawing explanation
Fig. 1 is Zr-MOFs (a) and Zr-MOFs/Graphene, and Graphene content is the scanning electron microscope (SEM) photograph of 0.5wt.% (b).
Detailed description of the invention
Embodiment
1
Weigh 318 milligrams of zirconium chloride (ZrCl4) and 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH2-H2BDC), join 150 milliliters of DMF(N, N '-dimethyl formamide) in, stirring at normal temperature 60 minutes under the stir speed (S.S.) of 700 revs/min, the solution by portions obtained after stirring moves in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, take out after the time and be cooled to room temperature in atmosphere, by centrifugation, after methyl alcohol exchanges 5 days, it is put in 80 DEG C of vacuum drying ovens dried, obtains the Zr-MOF material containing amino.Weigh 25 milligrams of Zr-MOF materials prepared in glass reactor, add 2.5 milliliters and lead to oxygen-saturated benzotrifluoride and 0.5 mM of (50 microlitre) phenmethylol in advance, seal, use the xenon source illumination 8 hours of wavelength >=420 nanometer.
Embodiment
2
Take 1 milliliter of concentration and be about the aqueous dispersion liquid of graphite oxide of 1.6 milligrams every milliliter in 150 milliliters of DMF(N, N '-dimethyl formamide) in, ultrasonic 30-40 minute, obtain brown yellow solution A；14.3 milligrams of trimethyl-(2-oxygen-2-pyrene-1-base-ethyl)-ammonium bromide (pyrene are added in solution A+), more ultrasonic 30-40 minute, obtain bright yellow solution B；245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH are added in solution B2-H2BDC), it is stirred overnight under normal temperature；318 milligrams of zirconium chloride (ZrCl are added again in the mixed solution obtained4) and 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH2-H2BDC), then stirring at normal temperature 60 minutes under the stir speed (S.S.) of 700 revs/min；The solution by portions obtained after stirring is moved in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, take out after the time and be cooled to room temperature in atmosphere, by centrifugation, after methyl alcohol exchanges 5 days, it is put in 80 DEG C of vacuum drying ovens dried, obtains the Zr-MOF/ graphene composite photocatalyst that mass fraction is 0.5%.Weigh 25 milligrams of composite photo-catalysts prepared in glass reactor, to add 2.5 milliliters lead to oxygen-saturated benzotrifluoride and 0.5 mM of (50 microlitre) phenmethylol in advance, seal, use the xenon source illumination 8 hours of wavelength >=420 nanometer.
Embodiment
3
Take 4 milliliters of concentration and be about the aqueous dispersion liquid of graphite oxide of 1.6 milligrams every milliliter in 150 milliliters of DMF(N, N '-dimethyl formamide) in, ultrasonic 30-40 minute, obtain brown yellow solution A；14.3 milligrams of 3-methyl (2-oxygen-2-pyrene-1-base-ethyl) ammonium bromide (pyrene are added in solution A+), more ultrasonic 30-40 minute, obtain bright yellow solution B；245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH are added in solution B2-H2BDC), it is stirred overnight under normal temperature；318 milligrams of zirconium chloride (ZrCl are added again in the mixed solution obtained4) and 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH2-H2BDC), then stirring at normal temperature 60 minutes under the stir speed (S.S.) of 700 revs/min；The solution by portions obtained after stirring is moved in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, take out after the time and be cooled to room temperature in atmosphere, by centrifugation, after methyl alcohol exchanges 5 days, it is put in 80 DEG C of vacuum drying ovens dried, obtains the Zr-MOF/ graphene composite photocatalyst that mass fraction is 2.0%.Weigh 25 milligrams of composite photo-catalysts prepared in glass reactor, to add 2.5 milliliters lead to oxygen-saturated benzotrifluoride and 0.5 mM of (50 microlitre) phenmethylol in advance, seal, use the xenon source illumination 8 hours of wavelength >=420 nanometer.
Embodiment
4
Take 10 milliliters of concentration and be about the aqueous dispersion liquid of graphite oxide of 1.6 milligrams every milliliter in 150 milliliters of DMF(N, N '-dimethyl formamide) in, ultrasonic 30-40 minute, obtain brown yellow solution A；14.3 milligrams of 3-methyl (2-oxygen-2-pyrene-1-base-ethyl) ammonium bromide (pyrene are added in solution A+), more ultrasonic 30-40 minute, obtain bright yellow solution B；245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH are added in solution B2-H2BDC), it is stirred overnight under normal temperature；318 milligrams of zirconium chloride (ZrCl are added again in the mixed solution obtained4) and 245.2 milligrams of 2-amino terephthalic acid (TPA) (2-NH2-H2BDC), then stirring at normal temperature 60 minutes under the stir speed (S.S.) of 700 revs/min；The solution by portions obtained after stirring is moved in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, take out after the time and be cooled to room temperature in atmosphere, by centrifugation, after methyl alcohol exchanges 5 days, it is put in 80 DEG C of vacuum drying ovens dried, obtains the Zr-MOF/ graphene composite photocatalyst that mass fraction is 5.0%.Weigh 25 milligrams of composite photo-catalysts prepared in glass reactor, to add 2.5 milliliters lead to oxygen-saturated benzotrifluoride and 0.5 mM of (50 microlitre) phenmethylol in advance, seal, use the xenon source illumination 8 hours of wavelength >=420 nanometer.
Embodiment
5
Preparation method and the active testing of catalyst are same as in Example 1, and except for the difference that the substrate of aromatic aldehyde chemicals synthesis changes p nitrobenzyl alcohol into.
Embodiment
6
Preparation method and the active testing of catalyst are same as in Example 2, and except for the difference that the substrate of photocatalytic activity test changes p nitrobenzyl alcohol into.
Embodiment
7
Preparation method and the active testing of catalyst are same as in Example 3, and except for the difference that the substrate of photocatalytic activity test changes p nitrobenzyl alcohol into.
Embodiment
8
Preparation method and the active testing of catalyst are the same as in Example 4, and except for the difference that the substrate of photocatalytic activity test changes p nitrobenzyl alcohol into.
Embodiment
9
Preparation method and the active testing of catalyst are same as in Example 1, and except for the difference that the substrate of photocatalytic activity test changes into fluorine-based phenmethylol.
Embodiment
10
Preparation method and the active testing of catalyst are same as in Example 2, and except for the difference that the substrate of photocatalytic activity test changes into fluorine-based phenmethylol.
Embodiment
11
Preparation method and the active testing of catalyst are same as in Example 3, and except for the difference that the substrate of photocatalytic activity test changes into fluorine-based phenmethylol.
Embodiment
12
Preparation method and the active testing of catalyst are the same as in Example 4, and except for the difference that the substrate of photocatalytic activity test changes into fluorine-based phenmethylol.
Embodiment
13
Preparation method and the active testing of catalyst are same as in Example 1, and except for the difference that the substrate of photocatalytic activity test changes into methylbenzyl alcohol.
Embodiment
14
Preparation method and the active testing of catalyst are same as in Example 2, and except for the difference that the substrate of photocatalytic activity test changes into methylbenzyl alcohol.
Embodiment
15
Preparation method and the active testing of catalyst are same as in Example 3, and except for the difference that the substrate of photocatalytic activity test changes into methylbenzyl alcohol.
Embodiment
16
Preparation method and the active testing of catalyst are the same as in Example 4, and except for the difference that the substrate of photocatalytic activity test changes into methylbenzyl alcohol.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (5)
1. the preparation method of a sandwich structure Zr-MOFs/ graphene composite photocatalyst, it is characterised in that: described composite photo-catalyst is by metal organic framework compound Zr-BDC-NH containing zirconium2With Graphene by the compound material with sandwich structure obtained, wherein the mass fraction of Graphene is 0.5-5.0%；Described composite photo-catalyst uses non-covalent assembling situ solvent by the use of thermal means to be prepared from, and comprises the following steps:
(1) take the aqueous dispersion liquid of the graphene oxide that 1-10 milliliter concentration is 1.6 mg/ml in 150 milliliters of N, in N '-dimethyl formamide, ultrasonic 30-40 minute, obtain brown yellow solution A；
(2) in solution A, 11.43-17.16mg trimethyl-(2-oxygen-2-pyrene-1-base-ethyl)-ammonium bromide is added, more ultrasonic 30-40 minute, obtain bright yellow solution B；
(3) in solution B, add 245.2 milligrams of 2-amino terephthalic acid (TPA)s, be stirred overnight under normal temperature；
(4) in the solution that step (3) obtains, 318 milligrams of zirconium chlorides and 245.2 milligrams of 2-amino terephthalic acid (TPA)s, stirring at normal temperature 30-60 minute under the stir speed (S.S.) of 600-800 rev/min are added again；
(5) solution by portions obtained after stirring is moved in 50 milliliters of autoclaves, react 48 hours in 120 DEG C of baking ovens, naturally cool to room temperature, by centrifugation, after methyl alcohol exchanges 5-7 days, it is dried in 80 DEG C of vacuum drying ovens, obtains described sandwich structure Zr-MOFs/ graphene composite photocatalyst.
2. the application of the sandwich structure Zr-MOFs/ graphene composite photocatalyst that a preparation method as claimed in claim 1 prepares, it is characterised in that: described composite photo-catalyst is applied to aromatic aldehyde chemicals synthetic reaction.
Application the most according to claim 2, it is characterised in that: under the exciting of visible ray, described composite photo-catalyst can be catalyzed the high-selectivity oxidation of aromatic alcohol material, and oxidation product is aromatic aldehyde.
Application the most according to claim 3, it is characterised in that: described aromatic alcohol material be phenmethylol, p nitrobenzyl alcohol, to fluorine-based phenmethylol, to any one in methylbenzyl alcohol.
Application the most according to claim 3, it is characterized in that: the high-selectivity oxidation process of described aromatic alcohol material is specific as follows: weigh 20-40 milligram sandwich structure Zr-MOFs/ graphene composite photocatalyst, add 2-4 milliliter and lead to the aromatic alcohol material of oxygen-saturated benzotrifluoride and 0.1-0.5 mM, seal, with the xenon source illumination that wave-length coverage is 420-800 nanometer.
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| JP2005104940A (en) * | 2003-10-02 | 2005-04-21 | Nippon Shokubai Co Ltd | Method for producing aromatic carbonyl compound |
| CN101940923B (en) * | 2010-07-27 | 2013-07-17 | 同济大学 | Photocatalyst for organic synthesis and preparation method and application thereof |
| CN103599806B (en) * | 2013-12-03 | 2015-04-15 | 福州大学 | Photocatalyst used for synthesis of aromatic aldehyde chemical and preparation method thereof |
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