CN108947785B - Method for synthesizing benzophenone by photocatalysis - Google Patents
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000012965 benzophenone Substances 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 title abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 8
- -1 silver-melamine-cyanuric acid Chemical compound 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- NGGLNLKWNZCULR-UHFFFAOYSA-N silver;1,3,5-triazine-2,4,6-triamine Chemical compound [Ag].NC1=NC(N)=NC(N)=N1 NGGLNLKWNZCULR-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 230000001706 oxygenating effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 7
- 229910002701 Ag-Co Inorganic materials 0.000 description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- CIVCELMLGDGMKZ-UHFFFAOYSA-N 2,4-dichloro-6-methylpyridine-3-carboxylic acid Chemical compound CC1=CC(Cl)=C(C(O)=O)C(Cl)=N1 CIVCELMLGDGMKZ-UHFFFAOYSA-N 0.000 description 1
- WAASLNJSONWCGI-UHFFFAOYSA-N 4,4-dicyclohexylpiperidine Chemical compound C1(CCCCC1)C1(CCNCC1)C1CCCCC1 WAASLNJSONWCGI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- GPHGLYLDASNBBU-UHFFFAOYSA-N cobalt(2+) dinitrate pentahydrate Chemical compound O.O.O.O.O.[Co++].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPHGLYLDASNBBU-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960000525 diphenhydramine hydrochloride Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229960002036 phenytoin Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
Abstract
The invention provides a method for synthesizing benzophenone by high selectivity photocatalysis, which has the advantages of high selectivity, low energy consumption and low pollution. The preparation method of the high-efficiency photocatalyst comprises the following steps: the melamine solution and the silver salt solution are uniformly mixed, and then are aged, filtered, washed and dried. Then placing the mixture into a cyanuric acid solution and a cobalt salt solution in sequence, stirring, filtering, drying, roasting to finally obtain Ag-Co3O4‑C3N4A composite photocatalyst is provided. And dispersing the composite photocatalyst in a solvent and a reaction solution, introducing oxygen, and irradiating to obtain the benzophenone. The invention can control Ag-Co3O4‑C3N4The activity of the composite photocatalyst is improved by the synthesis conditions, and the yield of the prepared benzophenone is as high as 70.2%.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a method for synthesizing benzophenone by photocatalysis.
Background
Benzophenone is a multipurpose chemical product and can be used as an ultraviolet absorbent, a photoinitiator and a photosensitizer for a thin film coating in a high polymer material. Can be used for producing dicyclohexylpiperidine, phenytoin hydrobromide, diphenhydramine hydrochloride and the like in the pharmaceutical industry. It has special smell and is widely used in various perfumes and essences. In recent years, with the increasingly high-speed development of the polymer material industry in China, benzophenone is used as an important light stabilizer in plastics, but the production process is laggard. Therefore, the development of green benzophenone technology becomes a current research hotspot.
The currently reported path for synthesizing benzophenone mainly comprises phosgeneThe method, the benzoyl chloride method, the carbon tetrachloride method, the benzyl chloride method, and the like. The benzoyl chloride process is the most common industrial process, and takes benzene, anhydrous aluminum trichloride and benzoyl chloride as raw materials, and can obtain about 90% yield. However, a large amount of AlCl is needed in the preparation process3The method has strong corrosivity, the product is obtained by hydrolysis with an acid solution, and a large amount of waste acid containing aluminum salt is generated, so that serious environmental pollution and economic waste are caused. Therefore, green and efficient methods for synthesizing benzophenone are becoming increasingly important. In recent years, organic compounds are synthesized in a green way through photocatalysis, and the method utilizes solar energy as an energy source and has the advantages of low reaction temperature, less energy consumption, simple equipment and the like; however, most of the existing photocatalysts for synthesizing organic compounds are homogeneous catalysts, and the catalyst recycling rate is low, so that the difficulty of product separation is increased. Therefore, the use of heterogeneous photocatalysts for organic synthesis is of interest.
Among the numerous semiconductor catalysts, graphite-like carbon nitride (g-C)3N4) The forbidden band value of the carbon nitride is 2.7eV, the carbon nitride is the most stable allotrope in the carbon nitride, has a laminated structure, and has good application prospects in the aspects of biology, catalysis and energy storage. But a single g-C3N4The recombination rate of the photogenerated electrons and the holes is high, so that the photocatalysis effect is not ideal. To inhibit the recombination of photo-generated electron-hole pairs, g-C may be added3N4The photocatalyst is compounded with other materials, and the photocatalytic activity of the photocatalyst and the other materials is improved by utilizing the synergistic effect of the two materials. Co3O4P-type semiconductors are attracting attention because of their excellent electrical and magnetic properties. It is with C3N4The recombination can well transfer the hole and inhibit the recombination of the photo-generated electron-hole pair. In addition, noble metal loading is one of the effective methods for improving photocatalytic performance. The load of the noble metal can well transfer electrons, and the photocatalytic activity is improved. Thus, Co is simultaneously compounded3O4The photocatalyst can well inhibit the recombination of photo-generated electron-hole pairs with noble metals, thereby being hopeful to improve the photocatalytic activity.
Disclosure of Invention
The invention provides a method for synthesizing benzophenone by photocatalysis, which has the advantages of high selectivity, low energy consumption and low pollution. The preparation method comprises the following steps:
uniformly mixing a melamine solution and a silver salt solution, and then aging, filtering, washing and drying to obtain a silver-melamine precursor;
putting the silver-melamine precursor into a cyanuric acid solution, stirring, filtering and drying to obtain a silver-melamine-cyanuric acid precursor;
putting the silver-melamine-cyanuric acid precursor into a cobalt salt solution, stirring, filtering, drying and roasting to finally obtain Ag-Co3O4-C3N4A composite photocatalyst is provided.
And (3) dispersing the composite photocatalyst in a solvent, toluene and iodobenzene, introducing oxygen, and irradiating to obtain the benzophenone.
Preferably, the silver salt solution is a silver nitrate or silver ammonia solution.
Preferably, the cobalt salt solution is a cobalt nitrate or cobalt sulfate solution.
Preferably, the aging time is 1-12 h.
Preferably, the roasting temperature is 300-600 ℃, and the roasting time is 1-5 h.
Preferably, the molar ratio of the toluene to the iodobenzene is 1: [0.5 to 10 ].
Preferably, the solvent is trifluorotoluene, acetone, acetonitrile, N-dimethylformamide or dimethylsulfoxide.
Preferably, the speed of introducing the oxygen is 1-30 mL/min/g based on the mass of the catalyst.
Preferably, the irradiation wavelength is visible light of more than or equal to 400 nanometers, and the irradiation time is 1-24 hours.
Preferably, the Ag-Co3O4-C3N4Ag and Co in composite photocatalyst3O4、C3N4In a molar ratio of 1: [1 to 10]]：[1～10]。
The invention can change Ag-Co3O4-C3N4Preparation conditions of (2) to synthesize Ag-Co3O4-C3N4The composite photocatalyst is used in the reaction of synthesizing benzophenone. The synthesis method has the characteristics of high selectivity, low energy consumption, low corrosion to equipment, low environmental pollution and the like, and the conversion rate of the benzophenone is high.
Detailed Description
Example 1
Uniformly mixing 1000mL of 20mM melamine solution and 200mL of 20mM silver nitrate solution, aging for 3h, filtering, washing and drying to obtain a silver-melamine precursor;
placing the prepared silver-melamine precursor into 1000mL of 20mM cyanuric acid solution, stirring for 3h, filtering and drying to obtain a silver-melamine-cyanuric acid precursor;
putting the silver-melamine-cyanuric acid precursor into 50mL ethanol solution of 2mmol cobalt nitrate pentahydrate, stirring for 3h, filtering, drying, roasting at 550 ℃ under nitrogen for 4h to finally obtain Ag-Co3O4-C3N4A composite photocatalyst is provided.
Under visible light, molecular oxygen is used as an oxidant, and benzophenone prepared from toluene and iodobenzene is used as a model reaction to investigate the catalytic activity of the prepared photocatalyst. Taking 100mg of the prepared composite photocatalytic material, adding 0.1mmol of toluene, 0.3mmol of iodobenzene and 1mL of benzotrifluoride, controlling the flow rate of oxygen to be 10mL/min/g, performing dark treatment for 30min, turning on a light source (a 300W xenon lamp, adding an optical filter to filter out light with the wavelength of less than 400 nanometers) to perform illumination for 5h, turning on condensed water, and controlling the temperature of the reaction liquid to be room temperature. After the illumination is finished, sampling and centrifugally separating out the catalyst. The product was qualitatively analyzed by gas chromatography-mass spectrometer, quantitatively analyzed by gas chromatograph (GC2010, hydrogen flame ionizer detector, shimadzu corporation), and quantitatively analyzed by biphenyl as an internal standard, with a yield of benzophenone product of 70.8%.
Examples 2 to 5
Investigating different Co3O4Content of Ag-Co3O4-C3N4The catalytic activity of the composite photocatalyst is similar to that of example 1, the addition amount of the cobalt nitrate in the composite material is changed, the other conditions are not changed, and the samples are numbered as ACCN-1, ACCN-2, ACCN-3 and ACCN-5. The conditions and reaction results of the composite catalysts prepared in examples 2 to 5 are shown in Table 1.
TABLE 1 Ag-Co of different Cobaltosic oxides3O4-C3N4Reaction result of composite photocatalyst
As can be seen from Table 1, Ag-Co at various tricobalt tetroxide contents3O4-C3N4Different benzophenone yields are obtained under the composite photocatalyst, wherein the benzophenone yield is 68.8% when the adding amount of the cobaltosic oxide is 2mmol, and the photocatalytic effect is best.
Examples 6 to 10
According to the steps of the best effect example 1, the rest conditions are not changed, only the aging time for preparing the composite photocatalyst is changed, the composite photocatalyst is aged for 1h, 5h, 7h, 9h and 12h, and the samples are numbered as T1, T2, T3, T4 and T5. The conditions and reaction results of the composite catalysts prepared in examples 6 to 10 are shown in Table 2.
TABLE 2 Ag-Co obtained at different ageing times3O4-C3N4Reaction result of composite photocatalyst
As can be seen from Table 2, the yield of benzophenone obtained under different aging times is substantially unchanged by continuing to prolong the aging time after aging for 5 hours, and the yield of benzophenone is the highest under the condition of aging for 3 hours, compared with example 1, so that the best photocatalysis effect is achieved.
Examples 11 to 13
The procedure of example 1 was followed, with the remaining conditions being unchanged, in accordance with the respective calcination temperatures of 300 deg.C, 400 deg.C, 500 deg.C, and 600 deg.C, and the samples were designated as C1, C2, C3, and C4. The preparation conditions and the reaction results of the composite photocatalysts of examples 11 to 13 are shown in Table 3.
TABLE 3 Ag-Co with different calcination temperatures3O4-C3N4Reaction result of composite photocatalyst
As can be seen from Table 3, the yield of benzophenone at various catalyst calcination temperatures was dramatically increased at 500 ℃ as compared with example 1, and the best photocatalytic effect was obtained at 550 ℃.
Examples 15 to 18
The influence of the change of the calcination time on the photocatalytic effect of the composite photocatalyst was investigated according to the procedure of example 1, with the remaining conditions being unchanged. The roasting time is 1h, 2h, 3h and 5h, and the numbers are CT1, CT2, CT3 and CT4 respectively. The corresponding reaction results obtained in examples 15 to 18 are shown in Table 4.
TABLE 4 different calcination time vs. Ag-Co3O4-C3N4Effect of the Performance of the composite photocatalyst
As can be seen from Table 4, different yields of benzophenone were obtained at different calcination times, and the best photocatalytic effect was found at 4 hours calcination time as compared with example 1.
Examples 19 to 22
Ag-Co optimized according to reaction effect3O4-C3N4The composite material is a catalyst, the other reaction conditions are the same as those in example 1, and the influence of the molar ratio of iodobenzene to toluene on the photocatalytic effect is researched. The molar ratios of iodobenzene to toluene were 4:1, 2:1, 1:1, and 1:2, respectively, and the numbers thereof were designated as A1, A2, A3, and A4, respectively, and the reaction results obtained in examples 19 to 22 are shown in Table 5.
TABLE 5 influence of iodobenzene to toluene molar ratio on composite photocatalyst
From the benzophenone yields obtained in table 5 under different molar ratios of iodobenzene to toluene, the molar ratio of iodobenzene to toluene was 4:1, but the difference is not great compared with example 1, and the amount of iodobenzene is large, so that the ratio of iodobenzene to toluene is 3:1 as the reaction condition.
Examples 23 to 26
According to the method, the composite material with the optimal effect is used as a catalyst, and the influence of a solvent on the photocatalytic effect is researched. Acetonitrile, N-dimethyl formyl, acetone and dimethyl sulfoxide are respectively used as solvents, and the numbers are B, C, D and E respectively. The rest of the reaction conditions are the same as those in example 1, and the corresponding reaction results obtained in examples 23 to 26 are shown in Table 6.
TABLE 6 solvent vs. Ag-Co3O4-C3N4Influence of photocatalytic performance of composite photocatalyst
As compared with example 1, it is understood that the catalyst has the best photocatalytic effect when the solvent is trifluorotoluene.
Examples 27 to 30
The composite photocatalyst is selected as the catalyst with the optimal effect, and the influence of the oxygen flow rate on the photocatalytic effect is researched. The reaction conditions were the same as in example 1 except that oxygen flow rates of 5mL/min/g, 15mL/min/g, 20mL/min/g and 30mL/min/g were respectively used as F1, F2, F3 and F4, and the corresponding reaction results were obtained as shown in Table 7.
TABLE 7 oxygen flow Rate vs. Ag-Co3O4-C3N4Influence of photocatalytic performance of composite photocatalyst
As is clear from Table 7, the photocatalyst effect of the catalyst was the best when the oxygen flow rate was 10 mL/min/g.
Comparative example 1
Carbon nitride (g-C)3N4) The preparation method comprises the following steps: 3g of melamine are taken and roasted for 4 hours at 550 ℃ under nitrogen to finally obtain the compound C3N4A photocatalyst.
Under visible light, molecular oxygen is used as an oxidant, and benzophenone prepared from toluene and iodobenzene is used as a model reaction to investigate the catalytic activity of the prepared photocatalyst. Taking 100mg of the prepared composite photocatalytic material, adding 0.1mmol of toluene, 0.3mmol of toluene and 1mL of benzotrifluoride, controlling the flow rate of oxygen to be 10mL/min/g, performing dark treatment for 30min, turning on a light source (a 300W xenon lamp, adding an optical filter to filter out light with the wavelength of less than 400 nanometers) to illuminate for 5h, and turning on condensed water to control the temperature of the reaction solution to be room temperature. After the illumination is finished, sampling and centrifugally separating out the catalyst. The product was qualitatively analyzed by gas chromatography-mass spectrometer, quantitatively analyzed by gas chromatograph (GC2010, hydrogen flame ionizer detector, shimadzu corporation), and quantitatively analyzed by biphenyl as an internal standard with benzophenone yield of 2.8%.
The above examples and comparative examples can be seenThe Ag-Co prepared by the method of the invention3O4-C3N4The composite photocatalyst has high catalytic activity in photocatalytic synthesis of benzophenone.
Claims (9)
1. A process for the photocatalytic synthesis of benzophenone comprising the steps of:
uniformly mixing a melamine solution and a silver salt solution, aging, filtering, washing and drying to obtain a silver-melamine precursor;
putting the silver-melamine precursor into a cyanuric acid solution, stirring, filtering and drying to obtain a silver-melamine-cyanuric acid precursor;
putting the silver-melamine-cyanuric acid precursor into a cobalt salt solution, stirring, filtering, drying, and roasting to obtain Ag-Co3O4-C3N4A composite photocatalyst;
taking Ag-Co3O4-C3N4The composite photocatalyst is dispersed in toluene, iodobenzene and a solvent, wherein the solvent is trifluorotoluene, acetonitrile, N-dimethylformamide or dimethyl sulfoxide, oxygen is introduced, and the benzophenone is prepared by illumination.
2. The method of synthesis according to claim 1, wherein the silver salt solution is silver nitrate or silver ammonia solution.
3. The synthesis method according to claim 1, wherein the cobalt salt solution is a cobalt nitrate or sulfate solution.
4. The synthesis method according to claim 1, wherein the aging time is 1-12 h.
5. The synthesis method according to claim 1, wherein the roasting temperature is 300-600 ℃ and the roasting time is 1-5 h.
6. The synthesis method according to claim 1, wherein the molar ratio of toluene to iodobenzene is 1: (0.5 to 10).
7. The synthesis method according to claim 1, wherein the oxygen introduction rate is 1-30 mL/min/g based on the mass of the catalyst.
8. The synthesis method according to claim 1, wherein the illumination is visible light with a wavelength of 400 nm or more, and the illumination time is 1-24 h.
9. The method for synthesizing according to claim 1, wherein the ratio of Ag: co3O4：C3N4In a molar ratio of 1: (1-10): (1-10).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134819C (en) * | 1960-12-19 | |||
| WO2002092547A1 (en) * | 2001-05-17 | 2002-11-21 | Studiengesellschaft Kohle Mbh | Method for producing ketones from carboxylic acid anhydrides |
| CN102942463A (en) * | 2012-11-20 | 2013-02-27 | 浙江常山科润化学有限公司 | Preparation method for benzophenone compound |
| CN107032938A (en) * | 2017-04-19 | 2017-08-11 | 常州工程职业技术学院 | The synthesis technique of diaryl ketone derivatives |
| CN108409516A (en) * | 2018-03-07 | 2018-08-17 | 江南大学 | A kind of method of continuous current micro-reactor synthesis benzophenone derivates |
-
2017
- 2017-05-25 CN CN201710377720.3A patent/CN108947785B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134819C (en) * | 1960-12-19 | |||
| WO2002092547A1 (en) * | 2001-05-17 | 2002-11-21 | Studiengesellschaft Kohle Mbh | Method for producing ketones from carboxylic acid anhydrides |
| CN102942463A (en) * | 2012-11-20 | 2013-02-27 | 浙江常山科润化学有限公司 | Preparation method for benzophenone compound |
| CN107032938A (en) * | 2017-04-19 | 2017-08-11 | 常州工程职业技术学院 | The synthesis technique of diaryl ketone derivatives |
| CN108409516A (en) * | 2018-03-07 | 2018-08-17 | 江南大学 | A kind of method of continuous current micro-reactor synthesis benzophenone derivates |
Non-Patent Citations (4)
| Title |
|---|
| 2-羟基-4-苄氧基二苯甲酮的合成;胡应喜等;《化学工业与工程》;20090915(第05期);377-380 * |
| 二芳基甲酮化合物合成研究进展(待续);林晶等;《化工生产与技术》;20080625(第03期);33-38 * |
| 多羟基二苯甲酮类化合物合成方法的研究进展;王光辉等;《生物质化学工程》;20090115(第01期);36-40 * |
| 本期推荐――二苯甲酮类系列化合物;刘长令;《精细与专用化学品》;20070306(第05期);33-34 * |
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