CN116217341B - Photocatalytic preparation method of 1, 2-diphenyl-1, 2-ethylene glycol - Google Patents
Photocatalytic preparation method of 1, 2-diphenyl-1, 2-ethylene glycol Download PDFInfo
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- CN116217341B CN116217341B CN202310250400.7A CN202310250400A CN116217341B CN 116217341 B CN116217341 B CN 116217341B CN 202310250400 A CN202310250400 A CN 202310250400A CN 116217341 B CN116217341 B CN 116217341B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 title claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 97
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000007146 photocatalysis Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012456 homogeneous solution Substances 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000007193 benzoin condensation reaction Methods 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006046 pinacol coupling reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
-
- 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol, and relates to the technical field of fine chemical engineering. The method comprises the following steps: acetonitrile and benzyl alcohol are mixed and subjected to ultrasonic treatment, and then a P-doped g-C 3N4 catalyst modified by NiS nano particles is added to obtain a reaction solution; stirring, reacting under the condition of inert gas atmosphere, visible light and 10-20 ℃, centrifuging and collecting the solution to prepare the 1, 2-diphenyl-1, 2-glycol. The preparation method has mild reaction conditions, does not need harsh instruments and other conditions, and is a clean, environment-friendly, stable, efficient, environment-friendly and economical preparation process of the 1, 2-diphenyl-1, 2-glycol. The invention solves the problems that the existing preparation method is complex and needs toxic metal complex catalyst and a large amount of hydrogen-supplying reagent.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol.
Background
1, 2-Diphenyl-1, 2-glycol (hydrogenated benzoin) and its derivatives are a multifunctional structural unit in the synthesis of fine chemicals and pharmaceutical intermediates, and have wide application in chiral and synthetic chemistry. The traditional preparation methods of the 1, 2-diphenyl-1, 2-glycol comprise asymmetric hydroxylation of olefin, asymmetric pinacol coupling reaction of benzaldehyde, decomposition of racemic diol and the like, toxic metal complex catalysts and a large amount of hydrogen-supplying reagents (various alcohols: methanol, ethanol and the like) are needed, the process steps of the methods are complex, a large amount of industrial pollutants are generated in the intermediate treatment steps, and the method has serious corrosion to equipment and does not meet the requirements of green chemistry. At the same time, the yield of 1, 2-diphenyl-1, 2-glycol is low, and a large amount of byproducts are produced.
The photocatalysis technology takes solar energy as an energy source, has the advantages of environmental protection, low price and easy availability, and can effectively solve the defects of the traditional method by coupling benzyl alcohol C-C into 1, 2-diphenyl-1, 2-glycol through a photocatalysis means, in the light driving preparation of the hydrogenated benzoin reaction, the photo-generated holes can activate O-H bonds or sp 3 hybridized C-H bonds of a reaction substrate benzyl alcohol, however, the activation of the O-H bonds can lead to the generation of a plurality of benzyloxy free radicals (C 6H5-CH2 O) so as to generate benzaldehyde byproducts, so that the high selectivity control of the sp 3 hybridized C-H bonds of the activated benzyl alcohol is important to improve the yield of the 1, 2-diphenyl-1, 2-glycol.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol, which solves the problems that the existing preparation method is complex and needs toxic metal complex catalyst and a large amount of hydrogen-supplying reagent.
The technical scheme for solving the technical problems is as follows: the method for preparing the 1, 2-diphenyl-1, 2-glycol by photocatalysis comprises the following steps:
(1) Acetonitrile and benzyl alcohol are mixed and subjected to ultrasonic treatment, and then a P-doped g-C 3N4 catalyst modified by NiS nano particles is added to obtain a reaction solution;
(2) Stirring the reaction solution prepared in the step (1) for 25-35min, reacting for 5-7h under the conditions of inert gas atmosphere, visible light and 10-20 ℃, and centrifugally collecting the solution to prepare the 1, 2-diphenyl-1, 2-glycol.
Based on the technical scheme, the invention can also be improved as follows:
Further, in the step (1), the volume molar mass ratio of acetonitrile to benzyl alcohol is 8-12mL:0.2-1mmol of benzyl alcohol and NiS nano particle modified P doped g-C 3N4 catalyst, wherein the molar mass ratio is 0.2-1mmol:10-50mg.
Further, in the step (1), acetonitrile and benzyl alcohol are mixed before being mixed, acetonitrile and water are mixed to form a mixed solution, and then the mixed solution is mixed with benzyl alcohol; the volume fraction of water in the mixed solution is 8-12%.
The beneficial effects of adopting the further technical scheme are as follows: the addition of water can effectively regulate and control the activation path of substrate benzyl alcohol in the reaction, not only can precisely regulate and control the selectivity of the product 1, 2-diphenyl-1, 2-glycol, but also can realize the efficient preparation of another benzaldehyde product with high added value while preparing the 1, 2-diphenyl-1, 2-glycol.
Further, the volume fraction of water in the mixed solution was 10%.
In the step (1), the volume molar mass ratio of the mixed solution to the benzyl alcohol is 8-12mL:0.2-1mmol of benzyl alcohol and NiS nano particle modified P doped g-C 3N4 catalyst, wherein the molar mass ratio is 0.2-1mmol:10-50mg.
Further, in the step (1), the mass fraction of the P element in the NiS nanoparticle modified P-doped g-C 3N4 catalyst is 1-5%, and the mass fraction of the NiS is 1-3%.
Further, in the step (1), the mass fraction of the P element in the NiS nanoparticle modified P-doped g-C 3N4 catalyst is 1.25%, and the mass fraction of the NiS is 2%.
Further, in the step (1), the P-doped g-C 3N4 catalyst modified by the NiS nano-particles is prepared by the following method:
adding dicyandiamide and NH 4H2PO4 into water, stirring, evaporating the water, and roasting to obtain P-doped carbon nitride;
(1.2) dissolving Ni (CH 3COO)2·4H2 O) in water, adding the P-doped carbon nitride prepared in the step (1.1), carrying out ultrasonic treatment, adding thiourea and NaH 2PO2·H2 O under stirring, maintaining for 25-35min, carrying out hydrothermal reaction, washing, and drying to obtain the P-doped g-C 3N4 catalyst modified by the NiS nano particles.
Further, in the step (1.1), the mass-volume ratio of dicyandiamide, NH 4H2PO4 and water is 7-9g:0.7-0.9g:30mL.
Further, in the step (1.1), the mass-volume ratio of dicyandiamide, NH 4H2PO4 and water is 8g:0.8g:30mL.
Further, in the step (1.1), the water is evaporated to dryness under the water bath condition of 75-85 ℃.
Further, in the step (1.1), the firing is performed under an atmosphere of N 2.
Further, in the step (1.1), the mixture is baked for 3.5 to 4.5 hours at the temperature of 500 to 600 ℃.
Further, in the step (1.1), the roasting heating rate is 4.5-5.5 ℃/min.
Further, in the step (1.2), the molar volume ratio of Ni (CH 3COO)2·4H2 O, thiourea, naH 2PO2·H2 O and water is 0.1-0.4mmol:0.4-1.6mmol:0.1-0.4mmol:45-55mL.
Further, in step (1.2), ni (CH 3COO)2·4H2 O, thiourea, naH 2PO2·H2 O and water were in a molar volume ratio of 0.2mmol:0.8mmol:0.2mmol:50mL.
Further, in the step (1.2), the hydrothermal reaction is carried out for 3.5 to 4.5 hours at the temperature of 150 to 200 ℃.
Further, in step (1.2), washing with water and ethanol is performed sequentially.
Further, in the step (1.2), the mixture is dried at 55-65 ℃ for 10-15 hours.
Further, in the step (2), the inert gas is nitrogen or argon.
Further, in the step (2), the visible light wavelength is more than or equal to 420nm.
Further, in the step (2), the reaction is carried out under normal pressure.
The invention also provides the 1, 2-diphenyl-1, 2-ethylene glycol prepared by the method.
The invention has the following beneficial effects:
1. According to the invention, by using a photocatalysis means, P doped g-C 3N4 modified by NiS nano particles is selected as a photocatalyst, benzyl alcohol is used as a raw material, acetonitrile is used as a solvent under the condition of no need of an additional hydrogen supply reagent, and the benzyl alcohol is subjected to C-C coupling reaction under the irradiation of normal temperature, normal pressure and visible light to prepare the 1, 2-diphenyl-1, 2-ethylene glycol, so that the reaction rate and the product selectivity are high. The invention relates to a preparation method which has mild reaction conditions, does not need harsh instruments and other conditions, and is a clean, environment-friendly, stable, efficient, green and economical preparation process of 1, 2-diphenyl-1, 2-ethylene glycol.
2. The P-doped g-C 3N4 photocatalyst modified by the NiS nano particles does not contain toxic metal complex, does not need additional noble metal cocatalyst, shows high-efficiency photocatalytic activation benzyl alcohol performance, can precisely control the selectivity (more than 70%) of 1, 2-diphenyl-1, 2-glycol in the product, and shows high-efficiency stability in a cycle test.
Drawings
FIG. 1 is a TEM characterization of the catalyst of example 1;
FIG. 2 is an XRD characterization of the catalyst of example 1;
FIG. 3 is an XPS characterization of the catalyst of example 1;
FIG. 4 is a plot of product yield versus time for example 1;
FIG. 5 is a 5-cycle stability test of the catalyst of example 1;
FIG. 6 is a graph of the rate of product production and selectivity for examples 1, 8, 9 and comparative example 1;
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
(1) Preparation of the catalyst
(1.1) Adding 8g dicyandiamide and 0.8g NH 4H2PO4 into 30mL water, stirring for 1h to form a homogeneous solution, evaporating the water in a water bath at 80 ℃, and heating and roasting for 4h at 550 ℃ in an N 2 atmosphere at a heating rate of 5 ℃/min to obtain P-doped carbon nitride (PCN);
(1.2) dissolving 0.2mmol of Ni (CH 3COO)2·4H2 O) in 50mL of water, carrying out ultrasonic treatment to dissolve the Ni (CH 3COO)2·4H2 O), adding the P-doped carbon nitride prepared in the step (1.1), carrying out ultrasonic treatment for 30min, adding 0.8mmol of thiourea and 0.2mmol of NaH 2PO2·H2 O under stirring, keeping for 30min, transferring the stirred dispersion into a 50mL hydrothermal kettle, carrying out hydrothermal reaction for 4h at 180 ℃, cleaning with water and ethanol in sequence, and drying in a 60 ℃ oven for 12h to prepare a NiS nanoparticle modified P-doped g-C 3N4 catalyst (the mass fraction of P element in the catalyst is 1.25% and the mass fraction of NiS is 2%);
(2) 10mL of acetonitrile and 0.2mmol of benzyl alcohol are mixed, a homogeneous solution is formed by ultrasonic treatment, and then 20mg of NiS nano particle modified P-doped g-C 3N4 catalyst (the mass fraction of P element in the catalyst is 1.25 percent, and the mass fraction of NiS is 2 percent) is added to obtain a reaction solution;
(3) Placing the reaction solution prepared in the step (2) into a reactor, stirring for 30min, sealing the reactor, introducing inert gas N 2 min, discharging air in the reactor, injecting visible light into the reactor through top illumination by a 300W xenon lamp (the optical filter with the matching wavelength of more than or equal to 420 nm), controlling the temperature of the reactor to be 15 ℃ through water circulation condensation, reacting for 6h under normal pressure, centrifuging and collecting the solution, and preparing the 1, 2-diphenyl-1, 2-glycol.
Example 2:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
(1) Preparation of the catalyst
(1.1) Adding 8g dicyandiamide and 0.8gNH 4H2PO4 g dicyandiamide into 30mL water, stirring for 1h to form a homogeneous solution, evaporating the water in a water bath at 80 ℃, and heating and roasting for 4h at 550 ℃ in an N 2 atmosphere at a heating rate of 5 ℃/min to prepare P-doped carbon nitride (PCN);
(1.2) dissolving 0.1mmol of Ni (CH 3COO)2·4H2 O) in 50mL of water, carrying out ultrasonic treatment to dissolve the Ni (CH 3COO)2·4H2 O), adding the P-doped carbon nitride prepared in the step (1.1), carrying out ultrasonic treatment for 30min, adding 0.4mmol of thiourea and 0.1mmol of NaH 2PO2·H2 O under stirring, keeping for 25min, transferring the stirred dispersion into a 50mL hydrothermal kettle, carrying out hydrothermal reaction for 4h at 180 ℃, cleaning with water and ethanol in sequence, and drying in a 60 ℃ oven for 12h to prepare a NiS nanoparticle modified P-doped g-C 3N4 catalyst (the mass fraction of P element in the catalyst is 1.25% and the mass fraction of NiS is 1%);
(2) 8mL of acetonitrile and 0.5mmol of benzyl alcohol are mixed, a homogeneous solution is formed by ultrasonic treatment, and then 10mg of NiS nano particle modified P-doped g-C 3N4 catalyst (the mass fraction of P element in the catalyst is 1.25 percent, and the mass fraction of NiS is 1 percent) is added to obtain a reaction solution;
(3) Placing the reaction solution prepared in the step (2) into a reactor, stirring for 25min, sealing the reactor, introducing inert gas N 2 min, discharging air in the reactor, injecting visible light into the reactor through top illumination by a 300W xenon lamp (the optical filter with the matching wavelength of more than or equal to 420 nm), controlling the temperature of the reactor to be 10 ℃ through water circulation condensation, reacting for 7h under normal pressure, centrifuging and collecting the solution, and preparing the 1, 2-diphenyl-1, 2-glycol.
Example 3:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
(1) Preparation of the catalyst
(1.1) Adding 8g dicyandiamide and 0.8g NH 4H2PO4 into 30mL water, stirring for 1h to form a homogeneous solution, evaporating the water in a water bath at 80 ℃, and heating and roasting for 4h at 550 ℃ in an N 2 atmosphere at a heating rate of 5 ℃/min to obtain P-doped carbon nitride (PCN);
(1.2) dissolving 0.4mmol of Ni (CH 3COO)2·4H2 O) in 50mL of water, carrying out ultrasonic treatment to dissolve the Ni, adding the P-doped carbon nitride prepared in the step (1.1), carrying out ultrasonic treatment for 30min, adding 1.6mmol of thiourea and 0.4mmol of NaH 2PO2·H2 O under stirring, keeping for 35min, transferring the stirred dispersion into a 50mL hydrothermal kettle, carrying out hydrothermal reaction for 4h at 180 ℃, sequentially cleaning with water and ethanol, and drying in a 60 ℃ oven for 12h to prepare a P-doped g-C 3N4 catalyst modified by NiS nano particles (the mass fraction of P element in the catalyst is 1.25% and the mass fraction of NiS is 3%);
(2) Acetonitrile and water are mixed to form 12mL of mixed solution (the volume fraction of water in the mixed solution is 10%), 1mmol of benzyl alcohol is added, a homogeneous solution is formed by ultrasonic treatment, and then 50mg of NiS nanoparticle modified P-doped g-C 3N4 catalyst is added to obtain a reaction solution; the mass fraction of P element in the P-doped g-C 3N4 catalyst modified by the NiS nano particles is 1.25%, and the mass fraction of the NiS is 3%;
(3) Placing the reaction solution prepared in the step (2) into a reactor, stirring for 35min, sealing the reactor, introducing inert gas N 2 min, discharging air in the reactor, injecting visible light into the reactor through top illumination by a 300W xenon lamp (the optical filter with the matching wavelength of more than or equal to 420 nm), controlling the temperature of the reactor to be 20 ℃ through water circulation condensation, reacting for 5h under normal pressure, centrifuging and collecting the solution, and preparing the 1, 2-diphenyl-1, 2-glycol.
Examples 4-7:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In the step (2), the mass of the P-doped g-C 3N4 catalyst modified by the NiS nano particles is sequentially 10mg, 30mg, 40mg and 50mg. The procedure is as in example 1.
Examples 8 to 9:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In the step (2), the NiS nano particle modified P-doped g-C 3N4 catalyst is added, wherein the mass fraction of the NiS is sequentially 1% and 3%. The procedure is as in example 1.
Example 10:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In step (2), acetonitrile and water were mixed to form 10mL of a mixed solution (the volume fraction of water in the mixed solution was 10%), then 0.2mmol of benzyl alcohol was added, and a homogeneous solution was formed by ultrasonic wave, the remainder being the same as in example 1.
Examples 11 to 14:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
in the step (2), benzyl alcohol was added in an amount of 0.4mmol, 0.6mmol, 0.8mmol and 1mmol in this order, and the same procedure as in example 1 was followed.
Example 15:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
in the step (3), the inert gas was argon, and the rest was the same as in example 1.
Example 16:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In the step (2), 10mg of the NiS nanoparticle modified P-doped g-C 3N4 catalyst with a mass fraction of 2% was added, acetonitrile and water were mixed to form 10mL of a mixed solution (the volume fraction of water in the mixed solution was 10%), then 0.2mmol of benzyl alcohol was added, and a homogeneous solution was formed by ultrasonic treatment, and the rest was the same as in example 1.
Example 17:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
in the step (2), the mass fraction of NiS in the P-doped g-C 3N4 catalyst modified by NiS nano particles is 3%, the amount of benzyl alcohol is 0.6mmol, the inert gas is argon, and the rest is the same as in the example 1.
Example 18:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
in the step (2), 50mg of the P-doped g-C 3N4 catalyst modified by NiS nano particles is added, the mass fraction of the NiS is 1%, and the rest is the same as in the example 1.
Comparative example 1:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In the step (2), the mass fraction of NiS in the P-doped g-C 3N4 catalyst modified by the NiS nano particles is 0%, and the rest is the same as in the example 1.
Comparative examples 2 to 4:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
In step (2), acetonitrile and water were mixed to form 10mL of a mixed solution (the volume fraction of water in the mixed solution was 20%, 30% and 40% in this order), then 0.2mmol of benzyl alcohol was added, and a homogeneous solution was formed by ultrasonic wave, the remainder being the same as in example 1.
Comparative example 5:
A photocatalysis preparation method of 1, 2-diphenyl-1, 2-glycol comprises the following steps:
in the step (2), the inert gas is argon, and the rest is the same as in comparative example 3.
Test examples
1. The photocatalyst prepared in example 1 was subjected to TEM, XRD and XPS detection, and the results are shown in FIGS. 1 to 3.
As can be seen from fig. 1, the prepared NiS/PCN material shows a typical layered structure and pores exist in the layer, small nanoparticles are uniformly dispersed on the surface of PCN, and the size of the nanoparticles is 8nm, the lattice spacing is 0.27nm in HRTEM, and the nanoparticles are attributed to the (300) crystal plane of NiS; XRD in FIG. 2 shows that the samples have diffraction peaks at 12.8 and 27.4, which are attributed to the (100) and (002) planes of graphite-phase carbon nitride, and diffraction peaks at 18.46, 32.25, 35.77, 40.54 and 48.93 are attributed to NiS (PDF # 86-2280) particles; elements C, N, O, P, ni and S were detected in the XPS survey of fig. 3, where the O1S peak at 532eV was due to oxygen-containing functional groups (e.g., H 2 O or OH) adsorbed on the material surface, which together demonstrate that NiS was successfully dispersed as nanoparticles on the P-doped carbon nitride surface of the sheet.
2. The reaction times of step (3) of example 1 were set to 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and 10h, respectively, and the results of the statistics of the product were shown in FIG. 4.
As can be seen from FIG. 4, with 2.0% of NiS/PCN as a catalyst, the production content of 1, 2-diphenyl-1, 2-glycol showed a straight line rise in the first 6 hours along with the progress of the reaction time, and the rate was calculated to be 677.5. Mu. Mol.g -1·h-1, after the reaction for 6 hours, the content of 1, 2-diphenyl-1, 2-glycol did not rise any more, indicating that the reaction of benzyl alcohol was completed and the decomposition of the product 1, 2-diphenyl-1, 2-glycol did not occur.
3. The catalyst of example 1 was recycled 5 times and the results are shown in FIG. 5.
As can be seen from FIG. 5, good yields and selectivities remain after 5 cycles of reaction.
4. The product ingredients and amounts of examples 1, 4-18 and comparative examples 1-5 were determined by high performance liquid chromatography, and the production rates and product selectivities are shown in Table 1.
TABLE 1 product production Rate and Selectivity
As can be seen from Table 1, the production rate and the product selectivity of the photocatalytic preparation of 1, 2-diphenyl-1, 2-glycol are closely related to the quality of the catalyst, the kind of the solvent, and the benzyl alcohol content of the added reactant, in addition to the content of NiS in the NiS/PCN catalyst. Wherein, as the usage amount of the catalyst NiS/PCN increases, the production rate of the 1, 2-diphenyl-1, 2-glycol is obviously increased, and after 50mg of the catalyst is added, the highest production rate is up to 1331.9 mu mol.g -1·h-1; when water is added into acetonitrile, the water directly influences the activation path of benzyl alcohol as a reaction substrate, so that the production rate of 1, 2-diphenyl-1, 2-glycol is slightly reduced, the selectivity is reduced, and the content of the other benzaldehyde in the product is increased; when the reactant benzyl alcohol content is increased, the production rate of the 2-diphenyl-1, 2-glycol product is increased.
5. The product production rates and product selectivities of examples 1, 8, 9 and comparative example 1 are plotted, and the results are shown in fig. 6.
As can be seen from fig. 6, the introduction of NiS in the NiS/PCN catalyst has a significant effect on the efficiency of photocatalytic production of 1, 2-diphenyl-1, 2-ethylene glycol, and as the content of NiS increases, the production rate of 1, 2-diphenyl-1, 2-ethylene glycol increases and decreases, and when the mass fraction of NiS is 2.0%, the production rate of 1, 2-diphenyl-1, 2-ethylene glycol is as high as 677.5 μmol·g -1·h-1; the conversion rate of reactant benzyl alcohol also shows the same change trend, and the conversion rate of benzyl alcohol is more than 99% under the action of 2.0% of NiS/PCN catalyst.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The photocatalysis preparation method of the 1, 2-diphenyl-1, 2-glycol is characterized by comprising the following steps:
(1) Acetonitrile and benzyl alcohol are mixed and subjected to ultrasonic treatment, and then a P-doped g-C 3N4 catalyst modified by NiS nano particles is added to obtain a reaction solution;
(2) Stirring the reaction solution prepared in the step (1) for 25-35min, reacting for 5-7h under the conditions of inert gas atmosphere, visible light and 10-20 ℃ and centrifugally collecting the solution to prepare 1, 2-diphenyl-1, 2-ethylene glycol;
in the step (1), the mass fraction of P element in the P doped g-C 3N4 catalyst modified by the NiS nano particles is 1-5%, and the mass fraction of the NiS is 1-3%;
In the step (1), the P-doped g-C 3N4 catalyst modified by the NiS nano particles is prepared by the following method:
adding dicyandiamide and NH 4H2PO4 into water, stirring, evaporating the water, and roasting to obtain P-doped carbon nitride;
(1.2) dissolving Ni (CH 3COO)2·4H2 O) in water, adding the P-doped carbon nitride prepared in the step (1.1), carrying out ultrasonic treatment, adding thiourea and NaH 2PO2·H2 O under stirring, maintaining for 25-35min, carrying out hydrothermal reaction, washing, and drying to obtain the P-doped g-C 3N4 catalyst modified by the NiS nano particles.
2. The method for the photocatalytic preparation of 1, 2-diphenyl-1, 2-glycol according to claim 1, wherein in the step (1), the volume molar ratio of acetonitrile to benzyl alcohol is 8-12mL:0.2-1mmol of benzyl alcohol and NiS nano particle modified P doped g-C 3N4 catalyst, wherein the molar mass ratio is 0.2-1mmol:10-50mg.
3. The method for the photocatalytic production of 1, 2-diphenyl-1, 2-glycol according to claim 1, wherein in the step (1), acetonitrile and benzyl alcohol are mixed before being mixed, acetonitrile and water are mixed to form a mixed solution, and then mixed with benzyl alcohol; the volume fraction of water in the mixed solution is 8-12%.
4. The method for the photocatalytic production of 1, 2-diphenyl-1, 2-glycol according to claim 1, wherein in the step (2), the inert gas is nitrogen or argon.
5. The method for the photocatalytic production of 1, 2-diphenyl-1, 2-glycol according to claim 1, wherein in the step (2), the wavelength of visible light is not less than 420nm.
6. The method for the photocatalytic production of 1, 2-diphenyl-1, 2-glycol according to claim 1, wherein in the step (2), the reaction is carried out under normal pressure.
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| CN110813356A (en) * | 2019-11-15 | 2020-02-21 | 安徽科技学院 | CdIn2S4-C3N4Composite photocatalyst and preparation method and application thereof |
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| CN110813356A (en) * | 2019-11-15 | 2020-02-21 | 安徽科技学院 | CdIn2S4-C3N4Composite photocatalyst and preparation method and application thereof |
| CN114433048A (en) * | 2022-01-20 | 2022-05-06 | 内蒙古农业大学 | In-situ stripping preparation C3N4/TiO2(B) Method and application of micron flower composite catalyst |
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