CN115181010A - Method for coupling ether compound through photocatalysis - Google Patents
Method for coupling ether compound through photocatalysis Download PDFInfo
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- CN115181010A CN115181010A CN202110367094.6A CN202110367094A CN115181010A CN 115181010 A CN115181010 A CN 115181010A CN 202110367094 A CN202110367094 A CN 202110367094A CN 115181010 A CN115181010 A CN 115181010A
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- catalyst
- titanium dioxide
- tio
- anisole
- argon
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- 238000000034 method Methods 0.000 title claims abstract description 69
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- -1 ether compound Chemical class 0.000 title claims abstract description 25
- 230000008878 coupling Effects 0.000 title claims abstract description 12
- 238000010168 coupling process Methods 0.000 title claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 291
- 239000003054 catalyst Substances 0.000 claims abstract description 135
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 150000002170 ethers Chemical class 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 252
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 87
- 239000011259 mixed solution Substances 0.000 claims description 80
- 229910052697 platinum Inorganic materials 0.000 claims description 51
- 238000013032 photocatalytic reaction Methods 0.000 claims description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 44
- 239000001301 oxygen Substances 0.000 claims description 44
- 229910052760 oxygen Inorganic materials 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003107 substituted aryl group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 160
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 146
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 123
- 239000000203 mixture Substances 0.000 description 105
- 229910010413 TiO 2 Inorganic materials 0.000 description 99
- 229910052786 argon Inorganic materials 0.000 description 80
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 74
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 64
- 239000002105 nanoparticle Substances 0.000 description 43
- 239000002253 acid Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 42
- 239000012298 atmosphere Substances 0.000 description 40
- 238000004817 gas chromatography Methods 0.000 description 40
- 238000004458 analytical method Methods 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 39
- 229910021641 deionized water Inorganic materials 0.000 description 39
- 238000000151 deposition Methods 0.000 description 39
- 239000010453 quartz Substances 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- 239000012300 argon atmosphere Substances 0.000 description 38
- 230000008021 deposition Effects 0.000 description 38
- 230000001678 irradiating effect Effects 0.000 description 37
- 238000003756 stirring Methods 0.000 description 37
- 238000001291 vacuum drying Methods 0.000 description 36
- 238000005406 washing Methods 0.000 description 36
- ACPMBFXZRAOHTI-UHFFFAOYSA-N anisole;hydrate Chemical compound O.COC1=CC=CC=C1 ACPMBFXZRAOHTI-UHFFFAOYSA-N 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- KZBKJQBEPKVVSX-UHFFFAOYSA-N methoxyethane;hydrate Chemical compound O.CCOC KZBKJQBEPKVVSX-UHFFFAOYSA-N 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AWRUKIQHUKYALU-UHFFFAOYSA-N (1,2-dimethoxy-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(OC)C(OC)C1=CC=CC=C1 AWRUKIQHUKYALU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- MFJMZOUFSWSBNV-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenoxy)benzene Chemical compound ClC1=CC=CC=C1OC1=CC=CC=C1Cl MFJMZOUFSWSBNV-UHFFFAOYSA-N 0.000 description 1
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 description 1
- DWJKILXTMUGXOU-UHFFFAOYSA-N 2-(2-methoxyphenyl)acetonitrile Chemical compound COC1=CC=CC=C1CC#N DWJKILXTMUGXOU-UHFFFAOYSA-N 0.000 description 1
- YYGRRRBCAPNFRK-UHFFFAOYSA-N 2-chloro-1-methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1Cl YYGRRRBCAPNFRK-UHFFFAOYSA-N 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- VDYDAUQHTVCCBX-UHFFFAOYSA-N 4-chloro-1-methoxy-2-methylbenzene Chemical compound COC1=CC=C(Cl)C=C1C VDYDAUQHTVCCBX-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for coupling ether compounds through photocatalysis. The method adopts an ether compound as a substrate, prepares a bimolecular C-C coupled product under the irradiation of an ultraviolet lamp under the action of a titanium dioxide semiconductor photocatalyst loaded with noble metal, simultaneously generates hydrogen, the catalyst after reaction is easy to separate and recover, the selectivity of the bimolecular C-C coupled product is more than 90%, and the yield is more than 70%. The catalyst has high catalytic activity, long service life and easy preparation, can greatly reduce the production cost and has potential application prospect.
Description
Technical Field
The invention relates to an ether compound, in particular to a method for coupling the ether compound through photocatalysis.
Background
The ether compound is an important chemical raw material, and is further converted to synthesize C-C coupled products such as glycol ether compounds and the like, so that the C-C coupled products have important application values, such as solvents, spray paint fuel anti-icing agents, brake fluids, chemical intermediates and the like. Currently, the catalyst is mainly prepared by reacting ethylene oxide or substituted ethylene oxide with corresponding anhydrous alcohols (such as methanol, ethanol, butanol and the like) by the traditional thermal catalysis means under the action of an acid or alkaline catalyst. The process is generally high in technical difficulty, harsh in reaction conditions, low in yield, high in energy consumption and insufficient in safety in the product separation process, and the requirements for the current glycol ether compounds at home and abroad are greatly increased, so that the glycol ether compounds are difficult to economically and efficiently synthesize in a large scale.
Therefore, a green and sustainable synthesis method for bimolecular C-C bond coupling of the ether compound is developed, the C-H bond of the ether compound is activated through photocatalysis, the C-C bond coupling is directly realized in one step, the technical problem of product separation in the traditional thermocatalysis process can be well avoided, and the method is economical and efficient in batch production.
Disclosure of Invention
The invention aims to provide a method for coupling ether compounds through photocatalysis, which has the characteristics of high yield of target products, simple technical requirements, green, economic and efficient process and the like. The reaction process is as follows:
wherein R is 1 Alkyl, benzene ring, substituted aryl, etc.; r 2 H, alkyl, benzene ring, substituted aryl and the like; r 3 H, alkyl, benzene ring, substituted aryl and the like.
Adding a titanium dioxide semiconductor catalyst modified by noble metal and an ether compound into a solvent, removing oxygen in the system, and then starting an ultraviolet light source to perform photocatalytic reaction to obtain a bimolecular C-C coupled product accompanied with the generation of hydrogen. The noble metal in the noble metal modified titanium dioxide catalyst can be Pt, pd, au, ag and the like, and is preferably Pt or Pd; the loading of the noble metal is 0.1 to 10.0, preferably 0.1 to 0.5, based on the mass ratio.The titanium dioxide may be in the anatase phase, the rutile phase, either as a single phase or as a mixed phase. Preferably a mixture of anatase and rutile phases; the mass ratio of anatase to rutile in the mixed phase of anatase and rutile is from 0.1 to 10.0, preferably from 1.0 to 4.0. The ether compound is represented by the formula (I) when R 1 、R 2 、R 3 When one or more of them is an alkyl group, it may be C n H 2n+1 (n =1 to 4); when R is 1 、R 2 、R 3 When one or more of them is a substituted aryl group, it may be C 6 H 4 X and X are substituent groups and can be halogen, nitro, amino, alkyl (such as C) n H 2n+1 (n =1 to 4)), and the substitution position may be ortho, meta, or para to the substituted aryl group. The light source of the photocatalytic reaction is ultraviolet light, the wavelength of the light source is preferably 220-390 nm, and the light intensity of the light source is preferably 6-18W. The mass ratio of the titanium dioxide semiconductor catalyst to the solvent is 0.001-0.1, preferably 0.005-0.01. The solvent is one or two of water and acetonitrile, preferably a mixed solution of water and acetonitrile; the mass ratio of water to acetonitrile is 0.1 to 10.0, preferably 0.1 to 0.5. The time of the photocatalytic reaction is 1 to 72 hours, preferably 3 to 18 hours. The oxygen in the system can be removed by pumping or introducing inert gas.
Pt or Pd and titanium dioxide are combined to construct a metal-oxide interface in close contact, so that the separation of a photoproduction electron-hole pair is better promoted, and the characteristic that surface hydroxyl conducts a photoproduction hole is utilized to activate the breakage of a C-H bond, so that the coupling of the C-C bond is promoted and the generation of hydrogen is accompanied. The glycol ether compound is generated by converting the ether compound, and the method has the characteristics of high yield of target products, easy separation of the catalyst from a system, simple technical requirement, green, economic and efficient process and the like.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The modified titanium dioxide semiconductor photocatalyst has low precious metal loading, is easy to prepare, is environment-friendly and has long cycle life.
(2) The invention adopts the photocatalysis process to replace the traditional thermocatalysis process, thereby avoiding the problem of overhigh energy consumption and further reducing the production cost.
(3) The photocatalytic reaction is a heterogeneous catalytic reaction, the catalyst can be recovered and recycled, and meanwhile, the method has the advantages of simple technical requirements, green, economic and efficient process and the like.
(4) The process of the invention can obtain bimolecular C-C coupling products and simultaneously obtain gas product hydrogen with equimolar amount, is easy to separate from the products, and can be used as clean energy.
The catalyst after reaction is easy to separate and recycle, the selectivity of bimolecular C-C coupling products is more than 90 percent, and the yield is more than 70 percent. The catalyst prepared by the method has high catalytic activity, long service life and easy preparation, can greatly reduce the production cost and has potential application prospect.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and more obvious, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
0.1％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.1% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.1% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.1% of Pt/TiO 2 Adding catalyst into 1.5ml anisole-water/acetonitrile mixed solution (water/acetonitrile mass ratio is 0.1) with anisole mass percentage content of 30%, removing oxygen in the system, turning on 18W ultraviolet LED lamp, and performing ultraviolet irradiationThe light source is used for carrying out photocatalytic reaction for 3 hours under the condition of 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 81%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 73%.
Example 2
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 85%, the selectivity of ethylene glycol diphenyl ether was 92%, and the yield of ethylene glycol diphenyl ether was 78%.
Example 3
0.5％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.5% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.5% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.5% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent by mass, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 82%, the selectivity of ethylene glycol diphenyl ether was 91%, and the yield of ethylene glycol diphenyl ether was 75%.
Example 4
1.0％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 1.0% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 1.0% of Pt/TiO 2 A catalyst. 10mg of 1.0% of Pt/TiO prepared above 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 76%, the selectivity of ethylene glycol diphenyl ether was 89%, and the yield of ethylene glycol diphenyl ether was 68%.
Example 5
2.0％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 2.0% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, and irradiating for 2 hours at 365nm of 40W ultraviolet light under the conditions of normal temperature, normal pressure and argon atmospherePhoto-deposition followed by 3 washes, 12h in a vacuum oven at 60 ℃ and collection under inert atmosphere (argon) to yield 2.0% Pt/TiO 2 A catalyst. 10mg of the above-obtained 2.0% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent by mass, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 68%, the selectivity of ethylene glycol diphenyl ether was 86%, and the yield of ethylene glycol diphenyl ether was 58%.
Example 6
5.0％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 5.0% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 5.0% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 5.0% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 59%, the selectivity of ethylene glycol diphenyl ether was 87%, and the yield of ethylene glycol diphenyl ether was 51%.
Example 7
10.0％Pt/TiO 2 The catalyst is obtained by the following process: 1.0g of titanium dioxide nanoparticles (mass ratio: 20% in rutile phase, 80% in anatase phase) were added to 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), and a certain amount of chloroplatinic acid, which was chloroplatinic acid, was addedThe mass of middle Pt is 10.0% of the mass of titanium dioxide relative to the mass of titanium dioxide, the mixture is evenly stirred and transferred to a quartz kettle, after 3 times of replacement by argon, under the conditions of normal temperature, normal pressure and argon atmosphere, 40W ultraviolet light 365nm is irradiated for 2h for light deposition, then the light deposition is washed for 3 times, the mixture is placed in a vacuum drying box at 60 ℃ for 12h, and the mixture is collected under inert atmosphere (argon) to obtain 10.0% of Pt/TiO 2 A catalyst. 10.0% of the above-obtained Pt/TiO content 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 42%, the selectivity of ethylene glycol diphenyl ether was 83%, and the yield of ethylene glycol diphenyl ether was 35%.
Example 8
0.3％Pd/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloropalladate, wherein the mass of Pd is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the Pd/TiO nanoparticles under the inert atmosphere (argon) to obtain 0.3% of Pd/TiO 2 A catalyst. 10mg of the above-obtained 0.3% Pd/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 83%, the selectivity of ethylene glycol diphenyl ether was 93%, and the yield of ethylene glycol diphenyl ether was 77%.
Example 10
0.3％Pt/TiO 2 Catalyst is passed throughThe following process is obtained: adding 1.0g of titanium dioxide nanoparticles (anatase phase 100%) into a mixed solution of 30mL of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring into a quartz kettle, replacing for 3 times with argon, irradiating for 2 hours by 40W ultraviolet light 365nm under the conditions of normal temperature, normal pressure and argon atmosphere for carrying out light deposition, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent by mass, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 80%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 72%.
Example 11
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (rutile phase 100%) into a mixed solution of 30mL of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide relative to titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, irradiating 40W ultraviolet light 365nm for 2h for carrying out light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, subsequently washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO nanoparticles 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography showed that the conversion of anisole was 78%, the selectivity of ethylene glycol diphenyl ether was 88%, and that of ethylene glycol diphenyl etherThe yield thereof was found to be 69%.
Example 12
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of anisole-water solution with the mass percentage of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 76%, the selectivity of ethylene glycol diphenyl ether was 85%, and the yield of ethylene glycol diphenyl ether was 65%.
Example 13
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of anisole-acetonitrile solution with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition of an ultraviolet light source of 365 nm. After the reaction liquid is filteredGas chromatography analysis shows that the conversion rate of anisole is 82%, the selectivity of ethylene glycol diphenyl ether is 82%, and the yield of ethylene glycol diphenyl ether is 67%.
Example 14
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.3) with the anisole mass percentage content of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 89%, the selectivity of ethylene glycol diphenyl ether was 89%, and the yield of ethylene glycol diphenyl ether was 79%.
Example 15
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Catalyst is added into 1.5ml of anisole with the mass percentage content of 30 percentAfter removing oxygen in the system in the mixed solution of anisole-water/acetonitrile (the mass ratio of water/acetonitrile is 0.5), an 18W ultraviolet LED lamp is started, and the photocatalytic reaction is carried out for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 92%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 83%.
Example 16
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 1.0) with the anisole mass percentage content of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 88%, the selectivity of ethylene glycol diphenyl ether was 89%, and the yield of ethylene glycol diphenyl ether was 78%.
Example 17
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, and performing true vacuum evaporation at 60 DEG CLeft in an air-drying oven for 12h, collected under an inert atmosphere (argon) to obtain a content of 0.3% Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 2.0) with the anisole content of 30 percent by mass, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 86%, the selectivity of ethylene glycol diphenyl ether was 88%, and the yield of ethylene glycol diphenyl ether was 76%.
Example 18
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 5.0) with the anisole mass percentage content of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 81%, the selectivity of ethylene glycol diphenyl ether was 89%, and the yield of ethylene glycol diphenyl ether was 72%.
Example 19
0.3％Pt/TiO 2 The catalyst is obtained by the following process: taking 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase), adding the titanium dioxide nanoparticles into 30mL of mixed solution of anhydrous methanol and deionized water (v/v = 1/1), and adding a certain amount of chloroplatinic acid, wherein the mass of Pt is diplatinic acid relative to the mass of the titanium dioxide0.3 percent of the titanium oxide by mass is transferred into a quartz kettle after being evenly stirred, is replaced by argon for 3 times, is irradiated by 40W ultraviolet light 365nm for 2 hours to carry out light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, is washed by water for 3 times, is placed in a vacuum drying oven at 60 ℃ for 12 hours, and is collected under inert atmosphere (argon) to obtain 0.3 percent of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 10.0) with the anisole mass percentage content of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 78%, the selectivity of ethylene glycol diphenyl ether was 86%, and the yield of ethylene glycol diphenyl ether was 67%.
Example 20
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 1h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 83%, the selectivity of ethylene glycol diphenyl ether was 82%, and the yield of ethylene glycol diphenyl ether was 68%.
Example 21
0.3％Pt/TiO 2 The catalyst is obtained by the following process: taking 1.0g of titanium dioxide nano-particlesAdding particles (mass ratio: 20% rutile phase and 80% anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide relative to titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2h under the conditions of normal temperature, normal pressure and argon atmosphere, subsequently washing 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting 0.3% Pt/TiO under an inert atmosphere (argon) to obtain the final product 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 5 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 93%, the selectivity of ethylene glycol diphenyl ether was 91%, and the yield of ethylene glycol diphenyl ether was 85%.
Example 22
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent by mass, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 12 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution is filtered, gas chromatography analysis shows that the conversion rate of anisole is 96 percent, the selectivity of ethylene glycol diphenyl ether is 92 percent,the yield of ethylene glycol diphenyl ether was 88%.
Example 23
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 18h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 97%, the selectivity of ethylene glycol diphenyl ether was 92%, and the yield of ethylene glycol diphenyl ether was 89%.
Example 24
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding catalyst into 1.5ml anisole-water/acetonitrile mixed solution (water/acetonitrile mass ratio is 0.1) with anisole mass percentage content of 30%, removing oxygen in the systemAnd then, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 36h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 97%, the selectivity of ethylene glycol diphenyl ether was 92%, and the yield of ethylene glycol diphenyl ether was 89%.
Example 25
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 72 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 98%, the selectivity of ethylene glycol diphenyl ether was 92%, and the yield of ethylene glycol diphenyl ether was 90%.
Example 26
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 Catalyst and process for producing the same. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of methyl ethyl ether was 89%, the selectivity of 1, 2-dimethyl glycol dimethyl ether was 93%, and the yield of 1, 2-dimethyl glycol dimethyl ether was 83%.
Example 27
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of an ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction mixture was filtered, gas chromatography analysis showed that the conversion of diethyl ether was 86%, the selectivity to 1, 2-dimethylglycol diethyl ether was 92%, and the yield of 1, 2-dimethylglycol diethyl ether was 79%.
Example 28
0.3％Pt/TiO 2 The catalyst is obtained by the following process: 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) were added to 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), a certain amount of chloroplatinic acid was added, wherein the mass of Pt was 0.3% of the mass of titanium dioxide with respect to the mass of titanium dioxide, and the mixture was stirred uniformly and transferred to a transfer tankReplacing 3 times with argon in quartz kettle, irradiating 40W ultraviolet light 365nm for 2h under normal temperature, normal pressure and argon atmosphere conditions for light deposition, washing with water for 3 times, standing in 60 deg.C vacuum drying oven for 12h, and collecting under inert atmosphere (argon) to obtain 0.3% Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of a methyl anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of methyl anisole was 88%, the selectivity of 1, 2-diphenylethylene glycol dimethyl ether was 90%, and the yield of 1, 2-diphenylethylene glycol dimethyl ether was 79%.
Example 29
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of a mixed solution (the mass ratio of water to acetonitrile is 0.1) of methyl o-chloro anisole-water/acetonitrile with the mass percentage of anisole of 30 percent, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of methyl o-chloroanisole was 89%, the selectivity of 1, 2-di-o-chlorophenylethylene glycol dimethyl ether was 93%, and the yield of 1, 2-di-o-chlorophenylethylene glycol dimethyl ether was 83%.
Example 30
0.3％Pt/TiO 2 Catalyst carrierThe method comprises the following steps: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of methyl m-anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percent of anisole being 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of methyl m-chloroanisole was 82%, the selectivity of 1, 2-m-chlorophenyl ethylene glycol dimethyl ether was 91%, and the yield of 1, 2-m-chlorophenyl ethylene glycol dimethyl ether was 75%.
Example 31
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of methyl p-chloroanisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30 percent, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction under the condition of an ultraviolet light source of 365nmAnd 3h. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of methyl p-chlorophenyl methyl ether was 92%, the selectivity of 1, 2-di-p-chlorophenyl ethylene glycol dimethyl ether was 96%, and the yield of 1, 2-di-p-chlorophenyl ethylene glycol dimethyl ether was 88%.
Example 32
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of o-chloroanisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of o-chlorophenyl ether was 88%, the selectivity of ethylene glycol di-o-chlorophenyl ether was 92%, and the yield of ethylene glycol di-o-chlorophenyl ether was 81%.
Example 33
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg above0.3% of Pt/TiO obtained as described above 2 Adding a catalyst into 1.5ml of a mixed solution (the mass ratio of water to acetonitrile is 0.1) of m-chloroanisole-water/acetonitrile with the anisole mass percentage content of 30%, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of m-chlorophenylmethyl ether was 84%, the selectivity of ethylene glycol di-m-chlorophenylether was 88% and the yield of ethylene glycol di-m-chlorophenylether was 74%.
Example 34
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of p-chloroanisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole content of 30 percent, removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of p-anisole was 93%, the selectivity of ethylene glycol di-p-chlorophenyl ether was 96%, and the yield of ethylene glycol di-p-chlorophenyl ether was 89%.
Example 35
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide relative to the mass of titanium dioxide, uniformly stirring, and transferring to a quartz kettleAfter 3 times of replacement with argon, 40W ultraviolet light at 365nm was irradiated at room temperature under normal pressure under argon atmosphere for 2 hours to carry out the photo-deposition, followed by 3 times of water washing, and the resulting mixture was placed in a vacuum oven at 60 ℃ for 12 hours and collected under inert atmosphere (argon) to obtain 0.3% Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 290 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 82%, the selectivity of ethylene glycol diphenyl ether was 86%, and the yield of ethylene glycol diphenyl ether was 70%.
Example 36
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 325 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 86%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 77%.
Example 37
0.3％Pt/TiO 2 The catalyst is obtained by the following process: taking 1.0g of titanium dioxide nano particles (mass ratio: 20 percent of rutile phase and 80 percent of anatase phase),adding into a mixed solution of 30mL anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide relative to titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing for 3 times with argon, irradiating for 2h under normal temperature, normal pressure and argon atmosphere conditions by 40W ultraviolet light 365nm for light deposition, washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting under inert atmosphere (argon) to obtain 0.3% Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of a methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30 percent, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 390 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 86%, the selectivity of ethylene glycol diphenyl ether was 89%, and the yield of ethylene glycol diphenyl ether was 77%.
Example 38
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 5mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of a methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30 percent, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition that an ultraviolet light source is 290 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 56%, the selectivity of ethylene glycol diphenyl ether was 93%, and the yield of ethylene glycol diphenyl ether was 82%.
Example 39
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring the mixture into a quartz kettle, replacing the mixture with argon for 3 times, irradiating 40W ultraviolet light 365nm for 2 hours for light deposition under the conditions of normal temperature, normal pressure and argon atmosphere, then washing the mixture for 3 times, placing the mixture in a vacuum drying box at 60 ℃ for 12 hours, and collecting the mixture under the inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. Taking 20mg of the above-obtained 0.3% 2 Adding a catalyst into 1.5ml of methyl ethyl ether-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the mass percentage of anisole being 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 290 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 93%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 84%.
Example 40
0.3％Pt/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of a mixed solution of anhydrous methanol and deionized water (v/v = 1/1), adding a certain amount of chloroplatinic acid, wherein the mass of Pt is 0.3% of that of titanium dioxide, uniformly stirring, transferring to a quartz kettle, replacing for 3 times with argon, performing light deposition by irradiating 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and argon atmosphere, then washing for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 0.3% of Pt/TiO 2 A catalyst. 50mg of 0.3% of Pt/TiO prepared above 2 Adding catalyst into 1.5ml methyl ethyl ether-water/acetonitrile mixed solution (water/acetonitrile mass ratio is 0.1) with anisole mass percentage content of 30%, removing oxygen in the system, turning on 18W ultraviolet LED lamp, and irradiating with ultraviolet light at 290nmCarrying out photocatalytic reaction for 3h. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 92%, the selectivity of ethylene glycol diphenyl ether was 90%, and the yield of ethylene glycol diphenyl ether was 83%.
Comparative example 1
1.0g of titanium dioxide nanoparticles (mass ratio: 20% of rutile phase and 80% of anatase phase) are added into 30mL of anhydrous methanol, a certain amount of chloroplatinic acid is added, wherein the mass of Pt is 0.3% of that of titanium dioxide, the mixture is stirred for 2h until the mixture is uniformly stirred, and then the mixture is placed on a heating stirring disc at 80 ℃ until the mixture is completely dried. After thorough grinding, the mixture was placed in a roasting tube and collected under hydrogen conditions at 400 ℃ for 2h (5 ℃/min) in an inert atmosphere (argon) to a content of 0.3% Pt/TiO 2 A catalyst. Taking 10mg of the above-obtained 0.3% of Pt/TiO 2 Adding a catalyst into 1.5ml of an anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after removing oxygen in the system, starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3h under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 31%, the selectivity of ethylene glycol diphenyl ether was 62%, and the yield of ethylene glycol diphenyl ether was 19%.
Comparative example 2
10mg of titanium dioxide nanoparticles (the mass ratio is 20% of rutile phase and 80% of anatase phase) are added into 1.5ml of anisole-water/acetonitrile mixed solution (the mass ratio of water to acetonitrile is 0.1) with the anisole mass percentage content of 30%, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalytic reaction is carried out for 3 hours under the condition that an ultraviolet light source is 365 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anisole was 2.0%, the selectivity of ethylene glycol diphenyl ether was 3.5%, and the yield of ethylene glycol diphenyl ether was 0%.
Through the above experimental results of example 2 and comparative examples 1 and 2, the method of the present invention significantly improves the conversion of anisole and the selectivity and yield of ethylene glycol diphenyl ether, without loading noble metal-containing TiO 2 The reaction for preparing bimolecular C-C coupling products under UV light has little effect.
Claims (10)
1. A method for coupling ether compounds through photocatalysis is characterized in that:
adding a titanium dioxide catalyst modified by noble metal and an ether compound into a solvent, removing oxygen in a system, and then carrying out ultraviolet light catalytic reaction to obtain a bimolecular C-C coupled product accompanied with the generation of hydrogen.
2. The method of claim 1, wherein:
the reaction process is as follows:
wherein R is 1 Is alkyl, benzene ring or substituted aryl; r is 2 Is H, alkyl, benzene ring or substituted aryl; r 3 Is H, alkyl, benzene ring or substituted aryl.
3. The method of claim 1 or 2, wherein: the noble metal in the noble metal modified titanium dioxide catalyst can be one or more than two of Pt, pd, au, ag and the like, and is preferably one or two of Pt and Pd; the loading of the noble metal is 0.1 to 10.0 percent of the mass of the carrier, preferably 0.1 to 0.5 percent.
4. A method as claimed in claim 1,2 or 3, characterized by: the titanium dioxide of the noble metal modified titanium dioxide catalyst can be a single phase of anatase phase and rutile phase or a mixed phase of the anatase phase and the rutile phase.
5. A method as claimed in claim 1,2 or 3, characterized by: in the noble metal modified titanium dioxide catalyst, the titanium dioxide is preferably a mixed phase of an anatase phase and a rutile phase; the mass ratio of anatase to rutile in the mixed phase of anatase and rutile is from 0.1 to 10.0, preferably from 1.0 to 4.0.
6. The method of claim 2, wherein: the ether compound is represented by the formula (I) when R 1 、R 2 、R 3 When one or more of them is an alkyl group, each of the alkyl groups may be C n H 2n+1 (n =1 to 4); when R is 1 、R 2 、R 3 When one or more of them is a substituted aryl group, the substituted aryl group may be C 6 H 4 X and X are substituent groups, and can be halogen, nitro, amino or alkyl, and the like, and the substitution position can be on the ortho-position, meta-position or para-position of the substituted aryl.
7. The method of claim 1 or 2, wherein: the light source of the photocatalytic reaction is ultraviolet light, the wavelength of the light source is preferably 220-390 nm, and the light intensity of the light source is preferably 6-18W.
8. The method of claim 1 or 2, wherein: the mass ratio of the titanium dioxide catalyst to the solvent is 0.001 to 0.1, preferably 0.005 to 0.01.
9. The method of claim 1 or 2, wherein: the solvent is one or two of water and acetonitrile, preferably a mixed solution of water and acetonitrile; the mass ratio of water to acetonitrile is 0.1 to 10.0, preferably 0.1 to 0.5.
10. The method of claim 1 or 2, wherein: the time of the photocatalytic reaction is 1 to 72 hours, preferably 3 to 18 hours.
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| CN102070406A (en) * | 2011-01-25 | 2011-05-25 | 中国科学院山西煤炭化学研究所 | Method for synthesizing 3,4-dimethyl-3,4-hexamethylene glycol through photocatalysis |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| CN102964211A (en) * | 2012-11-19 | 2013-03-13 | 太原科技大学 | Photocatalytic synthesis method for 2,5-dimethyl-2,5-hexanediol |
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| CN102070406A (en) * | 2011-01-25 | 2011-05-25 | 中国科学院山西煤炭化学研究所 | Method for synthesizing 3,4-dimethyl-3,4-hexamethylene glycol through photocatalysis |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
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