CN109622040B - Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof - Google Patents
Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof Download PDFInfo
- Publication number
- CN109622040B CN109622040B CN201910061963.5A CN201910061963A CN109622040B CN 109622040 B CN109622040 B CN 109622040B CN 201910061963 A CN201910061963 A CN 201910061963A CN 109622040 B CN109622040 B CN 109622040B
- Authority
- CN
- China
- Prior art keywords
- tio
- visible light
- trichlorotoluene
- ester
- photosensitizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000002148 esters Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 17
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002077 nanosphere Substances 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- -1 ester compound Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229930003270 Vitamin B Natural products 0.000 claims description 13
- 239000011720 vitamin B Substances 0.000 claims description 13
- 235000019156 vitamin B Nutrition 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000011715 vitamin B12 Substances 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 229940095102 methyl benzoate Drugs 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001867 cobalamins Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- FDJOLVPMNUYSCM-UVKKECPRSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2,7, Chemical compound [Co+3].N#[C-].C1([C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)[N-]\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O FDJOLVPMNUYSCM-UVKKECPRSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a visible light catalyst for catalyzing trichlorotoluene to be converted into ester, and a preparation method and application thereof. The technical scheme is as follows: mixing vitamin B12The derivative and photosensitizer ruthenium complex N3 are adsorbed together on TiO2The composite photocatalyst with catalytic activity under the induction of visible light is obtained on the surface of the nanospheres, and the catalyst can catalyze trichlorotoluene to be completely dechlorinated under the irradiation of visible light and is converted into an environment-friendly ester compound.
Description
Technical Field
The invention belongs to the field of catalyst materials, and particularly relates to a photocatalyst with catalytic activity in a visible light region, and a preparation method and application thereof.
Background
Trichlorotoluene is an important organic intermediate and has wide application in printing, agriculture, organic synthesis and the like. In the prior art, the reaction for synthesizing the methyl benzoate by converting trichlorotoluene can be obtained by a series of refluxing and distilling at high temperature, the reaction is difficult to control, and a plurality of side reactions are caused. At present, the organic synthesis by visible light catalysis is widely concerned by people, is usually carried out at normal temperature and normal pressure, is easy to operate, generally does not produce secondary pollution, and opens up a new synthetic route for organic synthesis. Vitamin B 12And the derivatives thereof are widely used in the field of photocatalysis, and are selected appropriatelyThe carrier and the photosensitizer improve the utilization rate of the system to sunlight, so that the improvement of the catalytic efficiency is the current research focus.
Disclosure of Invention
The object of the present invention is to utilize vitamin B12The carboxyl in the structure of the derivative and the ruthenium complex simultaneously loads two functional molecules on TiO2And obtaining a visible light catalyst capable of catalyzing the trichlorotoluene to be converted into ester on the surface of the nanospheres. The material has better application prospect in the field of organic synthesis.
In order to achieve the purpose, the invention adopts the technical scheme that: a visible light catalyst for catalyzing the conversion of trichlorotoluene into ester is prepared from the carboxy-contained VB12The derivative and photosensitizer ruthenium complex N3 are adsorbed together on TiO2N3-TiO obtained from the surface of nano-spheres2-B12And (c) a complex.
A preparation method of a visible light catalyst for catalyzing the conversion of trichlorotoluene into ester comprises the following steps: adding appropriate amount of vitamin B containing carboxyl12Dissolving the derivative and photosensitizer ruthenium complex N3 in absolute ethyl alcohol, adding proper amount of TiO2And (3) carrying out ultrasonic dispersion on the nanospheres, stirring for 20-24 hours at normal temperature, centrifuging, washing precipitates by absolute ethyl alcohol, and drying in vacuum to obtain a target product.
Further, vitamin B containing carboxyl groups in mass ratio12Derivative of ruthenium complex as photosensitizer N3 TiO2＝1:0.5～1.0:5～7。
Further, vitamin B having carboxyl group in mass ratio12Derivative of ruthenium complex as photosensitizer N3 TiO2＝1:0.68:6。
Further, the vitamin B having a carboxyl group12The derivative is [ (CN) (H)2O)Cob(III)7COOH]Cl, structural formula shown below:
[(CN)(H2O)Cob(III)7COOH]Cl
further, the photosensitizer ruthenium complex N3 is Ru (dcbpy)2(SCN)2The structural formula is as follows:
Ru(dcbpy)2(SCN)2
further, the TiO2The nanosphere is P25 type TiO2Nanospheres.
The application of the visible light catalyst in catalyzing the conversion of trichlorotoluene into ester. The method comprises the following steps: taking a proper amount of the visible light catalyst, ultrasonically dispersing the visible light catalyst in a methanol solution of trichlorotoluene, adding triethanolamine, and carrying out photocatalysis by using visible light as a light source.
The beneficial effects of the invention are: the invention relates to vitamin B containing carboxyl12Derivative and photosensitizer ruthenium complex N3 and P25 type TiO2The visible light catalyst N3-TiO for catalyzing the conversion of the trichlorotoluene into ester is prepared2-B12. The catalyst has better light responsiveness in a visible light region due to the existence of the photosensitizer, realizes the co-immobilization of the catalyst and the photosensitizer, promotes the efficient recycling of the catalyst, and has good application prospect in the field of organic synthesis.
The invention is prepared by mixing vitamin B12Derivative and photosensitizer ruthenium complex are simultaneously immobilized on TiO with ultraviolet response2The composite photocatalyst with wide spectral response is obtained on the surface of the nanosphere, so that the trichlorotoluene is efficiently catalyzed to be completely dechlorinated and converted into an environment-friendly ester compound methyl benzoate under visible light, and the composite photocatalyst can be used for organic synthesis.
Drawings
FIG. 1 is a composite N3-TiO2-B12Schematic synthesis of (a).
FIG. 2 is a diagram of the complex N3-TiO2-B12Photo of the product of (1).
FIG. 3 is P25TiO2(a) And the complex N3-TiO2-B12(b) Dispersion in methanol.
FIG. 4 is a diagram of the complex N3-TiO2-B12Ultraviolet-visible diffuse reflectance spectrum of (a).
FIG. 5 is a diagram of the complex N3-TiO2-B12Schematic diagram of photocatalytic trichlorotoluene conversion reaction.
FIG. 6 is a composite of N3-TiO2-B12Gas chromatography comparison before and after catalytic trichlorotoluene conversion reaction.
Fig. 7 is a mass spectrum of the product methyl benzoate (M ═ 136.05).
Detailed Description
EXAMPLE 1A visible light catalyst, N3-TiO, for the conversion of trichlorotoluene to esters2-B12
The preparation method comprises the following steps:
1. vitamin B containing carboxyl group12Preparation of the derivatives:
30ml of 98 percent concentrated sulfuric acid is slowly dripped into 100ml of methanol, and the temperature is controlled between 0 ℃ and 5 ℃. Then slowly dripping vitamin B 12(commercially available, 2.0g, 1.5mmol) in methanol (200 ml). And concentrating the solution to 100ml after refluxing for 72 hours, dropwise adding a saturated sodium carbonate solution to adjust the pH value to 7-8, and removing methanol under reduced pressure. Extracting the rest water solution with carbon tetrachloride for three times (3 × 100ml), mixing extractive solutions, and removing solvent to obtain estervitamin B12Derivative [ (CN) (H)2O)Cob(III)7Cester]Cl, yield 1.1g, 65% yield.
Ester-substituted vitamin B12Derivative [ (CN) (H)2O)Cob(III)7Cester]Cl (1.0g, 0.90mmol) was dissolved in 20ml methanol and mixed with 50ml 0.26mol/L aqueous NaOH and reacted for 12 h. After the completion of the reaction, the reaction solution was adjusted to pH 5 with 5mol/L hydrochloric acid. Extracting with phenol three times (3 × 50ml), mixing phenol phases, adding 300ml diethyl ether, back-extracting with distilled water three times (3 × 100ml), collecting water phase, and spin drying to obtain vitamin B containing carboxyl12Derivative ([ (CN) (H)2O)Cob(III)7COOH]Cl), yield 0.45g, 49% yield. The reaction formula is as follows:
the obtained vitamin B containing carboxyl12The derivative is [ (CN) (H)2O)Cob(III)7COOH]Cl, structural formula shown below:
[(CN)(H2O)Cob(III)7COOH]Cl
2. photosensitizer ruthenium complex N3:
the commercially available photosensitizer ruthenium complex N3 is Ru (dcbpy)2(SCN)2The structural formula is as follows:
Ru(dcbpy)2(SCN)2
3. visible light photocatalyst N3-TiO2-B12Preparation of
FIG. 1 shows a visible light catalyst N3-TiO2-B12The synthetic route of (1).
2mL of the solution was taken at a concentration of 2.4X 10 -3mol/L of vitamin B containing carboxyl12Ethanol solution of the derivative and 2mL of 2.4X 10-3mixing the ethanol solution of photosensitizer ruthenium complex N3 in mol/L, and adding P25 type TiO2Dispersing nanosphere powder (30mg) with ultrasound, stirring at room temperature for 24h, centrifuging, washing with ethanol until the supernatant is colorless, centrifuging to obtain precipitate, and vacuum drying to obtain purple powder (32 mg), which is the target product visible light catalyst N3-TiO2-B12。
(II) the result of the detection
FIG. 2 shows the visible light catalyst N3-TiO2-B12The product photo of (1) is a purple powder.
FIG. 3 is TiO form P252(a in FIG. 3) and N3-TiO2-B12(b in FIG. 3) drawing of a dispersion in methanol.As can be seen from FIG. 3, the composite catalyst N3-TiO2-B12Has good dispersity in methanol, and the good dispersity is beneficial to improving the catalytic efficiency.
FIG. 4 shows [ (CN) (H)2O)Cob(III)7COOH]Cl and Ru (dcbpy)2(SCN)2Ultraviolet-visible absorption spectrum of (A) and N3-TiO2-B12And TiO2Ultraviolet-visible diffuse reflectance spectrum of (a). By comparison, it can be confirmed that the molecular structure is in the N3-TiO range2-B12The ultraviolet-visible diffuse reflectance spectrum of (A) shows the appearance at 458nm and at 507nm, respectively, of a complex [ (CN) (H)2O)Cob(III)7COOH]Cl and Ru (dcbpy)2(SCN)2Thereby proving that vitamin B contains carboxyl groups12Derivatives and photosensitizer ruthenium complexes N3 have been successfully immobilized on TiO 2And (4) the surface of the nanosphere. In addition, according to B in the ultraviolet-visible absorption spectrum of the immobilized ethanol solution before and after immobilization12And the change of the characteristic absorption peak in N3, and determining the composite N3-TiO2-B12In (B)12Is 4.9X 10- 5mol/g, N3 content 1.1X 10-5mol/g。
Example 2A visible light catalyst, N3-TiO, for the conversion of trichlorotoluene to esters2-B12Application of (2)
FIG. 5 shows a composite of N3-TiO2-B12Schematic representation of the photocatalytic conversion of trichlorotoluene to esters.
The method comprises the following steps: the N3-TiO prepared in example 1 was added2-B12(10mg) was ultrasonically dispersed in 6ml of trichlorotoluene (3X 10)-3mol/L) in methanol, and triethanolamine (0.2mol/L) was added thereto. Using xenon lamp with lambda greater than or equal to 420nm filter as light source and 100mW/cm2Distance: irradiating for 20-60 min at the wavelength of 10 cm. After the reaction is finished, the catalyst is centrifugally separated, the internal standard substance biphenyl is added into the reaction liquid after centrifugation, the product and the yield are respectively determined by GC-MS and GC, and a GC-MS spectrogram (figure 7) proves that the product is methyl benzoate. The relevant catalytic data are listed in table 1.
TABLE 1 visible light driven N3-TiO2-B12Catalytic conversion of trichlorotoluene to esters
As can be seen from table 1, by comparison, the yield of methyl benzoate was 46% by irradiation with visible light for 20min, and 83% by irradiation for 40min, and when the irradiation time was increased to 60min, the trichlorotoluene was almost completely converted into methyl benzoate. When the substrate concentration is increased to 10 times, the yield can reach 75% after illumination for 60 min. This reaction did not proceed in the absence of light, indicating that the complex N3-TiO 2-B12Has catalytic activity under irradiation of visible light. Thus, the composite catalyst N3-TiO2-B12Can efficiently catalyze the conversion of the trichlorotoluene into ester under the irradiation of visible light. As a novel green photocatalyst, the photocatalyst has good application prospect in the aspect of photocatalytic organic synthesis.
Claims (1)
1. A method for catalyzing the conversion of trichlorotoluene into ester is characterized by comprising the following steps: 10 mg of visible-light-driven photocatalyst N3-TiO2-B12 Ultrasonic dispersing in 6 mL of 3X 10-3Adding 0.2 mol/L triethanolamine into mol/L trichlorotoluene methanol solution, using xenon lamp equipped with lambda not less than 420 nm filter as light source, and using 100 mW/cm2Distance: irradiating for 40-60 min at the wavelength of 10 cm;
the preparation method of the visible light photocatalyst comprises the following steps: 2 mL of the solution was taken at a concentration of 2.4X 10-3mol/L of vitamin B containing carboxyl12Ethanol solution of the derivative and 2 mL of 2.4X 10-3mixing uniformly with ethanol solution of photosensitizer ruthenium complex N3 mol/L, and adding 30 mg of P25 type TiO2Dispersing nanosphere powder with ultrasound, stirring at room temperature for 24 hr, centrifuging, washing with ethanol until the supernatant is colorless, centrifuging, and collecting precipitateVacuum drying to obtain visible light catalyst N3-TiO2-B12；
The vitamin B containing carboxyl 12The derivative is [ (CN) (H)2O)Cob(III)7COOH]Cl, formula (I):
the photosensitizer ruthenium complex N3 is Ru (dcbpy)2(SCN)2The structural formula is shown as (II):
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910061963.5A CN109622040B (en) | 2019-01-23 | 2019-01-23 | Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910061963.5A CN109622040B (en) | 2019-01-23 | 2019-01-23 | Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109622040A CN109622040A (en) | 2019-04-16 |
| CN109622040B true CN109622040B (en) | 2022-06-14 |
Family
ID=66063187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910061963.5A Active CN109622040B (en) | 2019-01-23 | 2019-01-23 | Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109622040B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185238B (en) * | 2020-02-20 | 2022-07-19 | 辽宁大学 | Copper doped ultra-thin TiO2Nanosheet-loaded cobalt oxime complex composite photocatalyst and preparation method and application thereof |
| CN111229328A (en) * | 2020-03-25 | 2020-06-05 | 辽宁大学 | Coenzyme B12Modified Ti3C2(OH)XNanosheet composite photocatalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006191947A (en) * | 2005-01-11 | 2006-07-27 | Sumitomo Chemical Co Ltd | Dehalogenation method of organic halide |
| CN105669435A (en) * | 2015-02-15 | 2016-06-15 | 浙江永太科技股份有限公司 | Method used for preparing 2,4-dichloro-5-fluorobenzoyl chloride |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN108579813A (en) * | 2018-04-19 | 2018-09-28 | 辽宁大学 | A kind of composite photo-catalyst and its preparation method and application with catalytic activity under visible optical drive |
-
2019
- 2019-01-23 CN CN201910061963.5A patent/CN109622040B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006191947A (en) * | 2005-01-11 | 2006-07-27 | Sumitomo Chemical Co Ltd | Dehalogenation method of organic halide |
| CN105669435A (en) * | 2015-02-15 | 2016-06-15 | 浙江永太科技股份有限公司 | Method used for preparing 2,4-dichloro-5-fluorobenzoyl chloride |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN108579813A (en) * | 2018-04-19 | 2018-09-28 | 辽宁大学 | A kind of composite photo-catalyst and its preparation method and application with catalytic activity under visible optical drive |
Non-Patent Citations (2)
| Title |
|---|
| Oxygen-Controlled Catalysis by Vitamin B12-TiO2:Formation of Esters and Amides from Trichlorinated Organic Compounds by Photoirradiation;Hisashi Shimakoshi et al.;《Angew. Chem. Int. Ed.》;20151103;第54卷;第15440页左栏第2段、Scheme 1 * |
| 维生素B12衍生物的固载及其可见光诱导体系的光催化活性;孙颖;《中国博士学位论文全文数据库 工程科技I辑》;20180215(第2期);摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109622040A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110773213B (en) | One-dimensional cadmium sulfide/two-dimensional titanium carbide composite photocatalyst and preparation method and application thereof | |
| Deng et al. | Visible-light-driven selective cleavage of CC bonds in lignin model substrates using carbon nitride-supported ruthenium single-atom catalyst | |
| CN109622040B (en) | Visible light catalyst for catalyzing trichlorotoluene to be converted into ester and preparation method and application thereof | |
| CN110272402B (en) | Method for producing 2, 5-furandicarboxylic acid by coupling chemical reaction and biological reaction | |
| CN113663731B (en) | Preparation method and application of FL @ MOF composite photocatalyst | |
| CN106732774B (en) | A kind of vitamin B12Functionalization graphene composite material and preparation method and application | |
| CN112110420B (en) | Method for catalytically synthesizing hydrogen peroxide by using visible light to drive aminophenol formaldehyde resin | |
| CN112592361A (en) | Fluoroboropyrrole functionalized metal organic framework material and preparation method and application thereof | |
| CN104844423A (en) | Application of MIL-100 (Fe) in preparation of phenol through photocatalytic hydroxylation of benzene | |
| CN113976148B (en) | Z-shaped C 60 Bi/BiOBr composite photocatalyst and preparation method and application thereof | |
| CN107744814A (en) | A kind of preparation method and application of composite photo-catalyst | |
| CN111185238B (en) | Copper doped ultra-thin TiO2Nanosheet-loaded cobalt oxime complex composite photocatalyst and preparation method and application thereof | |
| CN107362792A (en) | A kind of preparation method of strontium titanates/niobic acid tin composite nano materials | |
| CN111229328A (en) | Coenzyme B12Modified Ti3C2(OH)XNanosheet composite photocatalyst and preparation method and application thereof | |
| CN111978164B (en) | Method for preparing aromatic aldehyde by visible light catalytic oxidation of lignin | |
| CN106146277B (en) | A method of naphthoquinone compound is synthesized using photochemical catalytic oxidation naphthol compound | |
| CN104773807B (en) | Application of Co(salen) catalytic paper in lignin oxidation | |
| CN101362680B (en) | Hypnone preparation method | |
| CN114908127B (en) | enzyme-TiO (TiO) utilization method 2 Method for catalyzing and synthesizing nanotube-quantum dot co-assembly | |
| CN107115893B (en) | Preparation method of indium tin sulfide/squarylium cyanine composite visible-light-driven photocatalyst | |
| CN114100692B (en) | Porphyrin-based multifunctional photocatalytic MOFs material | |
| CN116120505A (en) | Halogen-containing pyrenyl covalent organic framework polymer photocatalyst, and preparation method and application thereof | |
| CN113275038B (en) | Method for photocatalytic oxidative cracking of lignin C-O bond and benzene ring | |
| CN104496945B (en) | A kind of preparation method of gamma-valerolactone | |
| CN108794432B (en) | Method for preparing gamma lactone by photosensitization catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |