CN113385227B - Polyacid-based photocatalyst and preparation method and application thereof - Google Patents
Polyacid-based photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001450 anions Chemical class 0.000 claims abstract description 64
- 239000013460 polyoxometalate Substances 0.000 claims abstract description 60
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 37
- -1 quinolinium ion Chemical class 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 141
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000013067 intermediate product Substances 0.000 claims description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 34
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 31
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 15
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 13
- 238000005805 hydroxylation reaction Methods 0.000 claims description 13
- 230000033444 hydroxylation Effects 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 107
- 230000001699 photocatalysis Effects 0.000 description 27
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 239000012046 mixed solvent Substances 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- ODXRWDZWRBOJHZ-UHFFFAOYSA-M 1-butylquinolin-1-ium;bromide Chemical compound [Br-].C1=CC=C2[N+](CCCC)=CC=CC2=C1 ODXRWDZWRBOJHZ-UHFFFAOYSA-M 0.000 description 4
- MTAGVAABBYBXRA-UHFFFAOYSA-M 1-octylquinolin-1-ium;bromide Chemical compound [Br-].C1=CC=C2[N+](CCCCCCCC)=CC=CC2=C1 MTAGVAABBYBXRA-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 150000003248 quinolines Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KKRURATZPAVIHA-UHFFFAOYSA-M 1-hexadecylquinolin-1-ium;bromide Chemical compound [Br-].C1=CC=C2[N+](CCCCCCCCCCCCCCCC)=CC=CC2=C1 KKRURATZPAVIHA-UHFFFAOYSA-M 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 239000002265 redox agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of molecular oxygen
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
The application relates to a polyacid-based photocatalyst, a preparation method and application thereof, and polyacidBased on a photocatalyst having a molecular formula of
And has a structure shown in a formula I,
wherein, [ POM { (OCH)2)3CR1}2]m‑Represents a modified polyoxometalate anion, { POM } represents a polyoxometalate unit, R1At least one selected from hydroxyl, methyl, amino and nitro, and m is a positive integer; [ C ]9H7NR2]+Represents a quinolinium ion, R2At least one selected from linear or branched C1-C30 alkyl groups.
Description
Technical Field
The application relates to the technical field of photocatalytic chemistry, in particular to a polyacid-based photocatalyst, and a preparation method and application thereof.
Background
Phenol is an important and basic organic chemical raw material and has wide application in industry. Phenol has important applications in the industries of synthetic fibers, synthetic rubbers, plastics, pharmaceuticals, perfumes, paints, dyes, oil refining and the like.
With the development of industrial technology, the capacity and demand for phenol continues to increase. The industrial production method of phenol mainly comprises an iso-phenylpropyl method, a toluene-benzoic acid method, a benzene hydroxylation method and the like, wherein the iso-phenylpropyl method needs to produce phenol and acetone through multi-step reaction, and the method has the advantages of complex synthesis steps, low yield and high energy consumption. The catalyst of the toluene-benzoic acid method is easy to coke in the decarboxylation process, the yield of phenol and the service life of the catalyst are influenced, and carbon dioxide is released in the production process to cause waste of carbon resources. At present, a benzene hydroxylation method is commonly used, but has certain difficulty, and addition and oxidation are difficult to perform due to high thermodynamic stability of benzene; and due to the conjugation effect of benzene, electrophilic reaction is facilitated, and [ OH]Or [ O ]]Is nucleophilic, the product phenol is more active than benzene and can be further reacted to generate diphenol or quinone; to promote the reaction, H is often used2O2、O2When the oxidizing agent catalyzes the reaction, the oxidizing agent needs to be supplemented with additional redox agent to push the reaction to occur or realize catalysisCatalyst systems in which the recycling of the catalyst is not required to supplement additional redox agent are often completed under severe reaction conditions, and the catalytic efficiency is low.
Disclosure of Invention
The application provides a polyacid-based photocatalyst, a preparation method and application thereof, aiming at solving the problem of low catalytic efficiency.
In a first aspect, the present application provides a polyacid-based photocatalyst having the formula
And has a structure shown in a formula I,
wherein, [ POM { (OCH)2)3CR1}2]m-Represents a modified polyoxometalate anion, { POM } represents a polyoxometalate unit, R1At least one selected from hydroxyl, methyl, amino and nitro, and m is a positive integer;
[C9H7NR2]+represents a quinolinium ion, R2At least one selected from linear or branched C1-C30 alkyl groups.
According to one embodiment of the first aspect of the present application, the modified polyoxometalate anion comprises at least one of a modified Anderson-type, Keggin-type and Dawson-type polyoxometalate anion.
According to one embodiment of the first aspect of the present application, R2At least one selected from the group consisting of linear or branched butyl, octyl and hexadecyl.
In any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion is a modified Anderson polyoxometalate anion of the formula:
[Cr(OH)3Mo6O18{(OCH2)3CR1}2]3-。
in any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion is a modified Keggin-type polyoxometalate anion of formula:
[GeW9V3O37{(OCH2)3CR1}2]m-。
in any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion is a modified Dawson-type polyoxometalate anion of the formula:
[V3P2W15O59{(OCH2)3CR1}2]m-。
in any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Anderson polyoxometalate anion, the polyacid-based photocatalyst comprising at least one of a compound of the formula:
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]and
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]。
in any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Keggin-type polyoxometalate anion, the polyacid-based photocatalyst comprising at least one of a compound of the formula:
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3C NH2}]、
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3C CH3}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3C NH2}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3C CH3}]、
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3C NH2}]and
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3C CH3}]。
in any of the preceding embodiments according to the first aspect of the present application, the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Dawson-type polyoxometalate anion, the polyacid-based photocatalyst comprising at least one of a compound of the formula:
[C9H7N(C4H9)]m H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C NH2}]and
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C CH3}]。
in a second aspect, embodiments of the present application provide a method for preparing a polyacid-based photocatalyst, the method comprising the steps of: using compounds R containing trihydroxy groups1Tris-single or multi-side Tris covalent modification of polyoxometallate POM to prepare a first intermediate product R1Tris-POM, wherein R1At least one of hydroxyl, methyl, amino and nitro is selected, the reaction formula is shown as formula 1,
halogenated alkane R2-X and quinoline C9H7N is mixed and processed at 50-90 ℃ to synthesize a second intermediate product [ C ]9H7NR2]X, wherein R2At least one selected from linear or branched C1-C30 alkyl, X is at least one selected from bromine, iodine and chlorine, and the reaction formula is shown as formula 2,
the first intermediate product R1Tris-POM and a second intermediate [ C9H7NR2]X is respectively dissolved in the same or different first organic solvents, and the synthesis reaction is carried out at room temperature to obtain the polyacid-based photocatalyst
The reaction formula is shown as the formula (3),
according to one embodiment of the second aspect of the present application, a haloalkane R2-X and quinoline C9H7N is mixed at 50-90 deg.C to obtain halogenated alkane R2-X with quinoline C9H7The mol ratio of N is 4-6: 1; and/or
The first intermediate product R1Tris-POM and a second intermediate [ C ]9H7NR2]X are respectively dissolved in the same or different first organic solvents, and a first intermediate product R1-a solution of Tris-POM in a first organic solvent as a first intermediate, a second intermediate [ C9H7NR2]Dissolving X in a first organic solvent to serve as a solution of a second intermediate product, wherein the concentration of the solution of the first intermediate product is 0.04-0.05 mol/L, the concentration of the solution of the second intermediate product is 0.04-0.05 mol/L, and the first intermediate product R1Tris-POM with a second intermediate [ C9H7NR2]The molar ratio of X is 2-8: 1.
in any of the preceding embodiments according to the second aspect of the present application, the compound R containing a trihydroxy group1-Tris comprises dipentaerythritol C10H22O7And trimethylol R1Methyl hydride (CH)2OH)3-CH2-R1At leastOne kind of the medicine.
In any of the preceding embodiments according to the second aspect of the present application, the polyoxometalate POM comprises at least one of an Anderson-type, Keggin-type and Dawson-type polyoxometalate.
Embodiments of the third aspect of the present application provide an application of a polyacid-based photocatalyst in the field of a reaction for preparing phenol by hydroxylation of benzene using photocatalysis, where the polyacid-based photocatalyst is the polyacid-based photocatalyst provided in the embodiments of the first aspect of the present application or the polyacid-based photocatalyst prepared by the preparation method provided in the embodiments of the second aspect of the present application.
Polyacid-based photocatalysts according to embodiments of the present application include modified polyoxometalate anions and quinolinium ions, both of which have photocatalytic properties. Under the condition of illumination, the quinolinium ions or the derivatives thereof are converted into an excited state and then converted into a free radical form, and meanwhile, benzene is photo-catalyzed into benzene positive ions. The modified polyoxometalate anion-stabilized quinolinium ion abstracts a proton from a hydroxyl adduct generated by the reaction of a benzene cation and a water molecule and then is converted into a quinoline derivative, accompanied with the generation of phenol. Quinoline derivatives can be reoxidized to quinolinium ions by polyoxometalate anions, in which process the polyoxometalate anions are reduced and the reduced polyoxometalate anions can be reoxidized to polyoxometalate anions by oxygen. The modified polyoxometallate anions and the quinolinium ions are synergistic with each other, the benzene hydroxylation reaction is catalyzed under the condition of light irradiation, and the utilization rate of catalytic reaction atoms and the catalytic reaction efficiency can be effectively improved.
In an acidic environment, hydrogen peroxide is generated in the catalytic reaction process of the quinolinium ions or the derivatives thereof, and can be used as an oxidant of a modified polyoxometallate anion catalytic system to continuously catalyze and oxidize benzene, so that the utilization rate of catalytic reaction atoms and the catalytic reaction efficiency are further improved.
The preparation process of the embodiment of the application is simple, the reaction condition is mild, and the catalyst yield is high; the obtained catalyst is applied to the reaction of preparing phenol by photocatalysis and benzene hydroxylation, has high catalytic efficiency and high phenol selectivity, and has certain application potential in the industrial production of phenol.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
FIG. 1 is a nuclear magnetic spectrum of 1-butylquinolinium bromide disclosed in an example of the present application.
FIG. 2 is a nuclear magnetic spectrum of 1-octyl quinolinium bromide as disclosed in an example of the present application.
FIG. 3 is a nuclear magnetic spectrum of 1-hexadecylquinolinium bromide, disclosed in an example of the present application.
Fig. 4 is a catalytic mechanism diagram of a multi-acid based photocatalyst for photocatalytic benzene hydroxylation reaction in a water/acetonitrile system, which is disclosed in an embodiment of the present application.
Fig. 5 is a catalytic mechanism diagram of a multi-acid based photocatalyst for photocatalytic benzene hydroxylation reaction in a water/acetonitrile/sulfuric acid system, disclosed in an embodiment of the present application.
Detailed Description
Embodiments of the present application will be described in further detail below with reference to the drawings and examples. The following detailed description of the embodiments and the accompanying drawings are provided to illustrate the principles of the application, but are not intended to limit the scope of the application, i.e., the application is not limited to the described embodiments.
The inventors studied quinolinium ions and derivatives thereof and Polyoxometalates (POMs) in the development of a catalytic system for hydroxylation of benzene. The inventors have noted that quinolinium ions or derivatives thereof have photocatalytic activity for the oxidation of benzene to phenol and do not require the addition of an additional redox agent. The quinolinium ions or the derivatives thereof can generate hydrogen peroxide in the catalytic reaction process, but the function of the hydrogen peroxide is completely ignored, and the hydrogen peroxide can also be used as an oxidant for catalyzing the reaction of oxidizing benzene. POMs also have photocatalytic activity for oxidizing benzene to phenol, but the yield of phenol is low.
Based on the above problems discovered by the inventors, the inventors take the improvement of the atom utilization rate and reaction efficiency of the quinolinium ion photocatalytic benzene hydroxylation reaction system as the key point, and synthesize a series of polyacid-based photocatalysts by selecting a polyacid-based photocatalyst synthesis strategy of modified polyoxometallate anion cluster pairing quinolinium ions, and further describe the embodiments of the present application.
For a better understanding of the present application, embodiments of the present application are described below with reference to fig. 1 to 5.
Embodiments of the first aspect of the present application provide a polyacid-based photocatalyst comprising a modified multimetal oxolate anion and a quinolinium cation.
The modified polyoxometalate anion can be polyoxometalate ion modified by using a unilateral or multilateral Tris (hydroxymethyl) organic ligand, has photocatalytic properties, and can be represented by the following molecular formula: [ POM { (OCH)2)3CR1}2]m-Wherein { POM } represents a polyoxometalate unit, R1At least one selected from hydroxyl, methyl, amino and nitro, and m is a positive integer.
The quinolinium cation comprises a quinolinium ion skeleton structure, an alkyl group bonded to the quinolinium ion skeleton structure by a carbon-nitrogen single bond, and has photocatalytic properties, and the formula of the quinolinium cation can be represented by [ C [ ]9H7NR2]+Wherein R is2At least one selected from linear or branched C1-C30 alkyl groups.
The polyacid-based photocatalyst of the embodiment of the application has a structure shown in a formula I:
polyacid-based photocatalysts according to embodiments of the present application include modified polyoxometalate anions and quinolinium ions, both of which have photocatalytic properties. Under the condition of illumination, the quinolinium ions or the derivatives thereof are converted into an excited state and then converted into a free radical form, and meanwhile, benzene is photo-catalyzed into benzene positive ions. The modified polyoxometalate anion-stabilized quinolinium ion abstracts a proton from a hydroxyl adduct generated by the reaction of a benzene cation and a water molecule and then is converted into a quinoline derivative, accompanied with the generation of phenol. Quinoline derivatives can be reoxidized to quinolinium ions by polyoxometalate anions, in which process the polyoxometalate anions are reduced and the reduced polyoxometalate anions can be reoxidized to polyoxometalate anions by oxygen. The modified polyoxometallate anions and the quinolinium ions are synergistic with each other, the benzene hydroxylation reaction is catalyzed under the condition of light irradiation, and the utilization rate of catalytic reaction atoms and the catalytic reaction efficiency can be effectively improved.
In some possible embodiments, R2At least one selected from the group consisting of linear or branched butyl, octyl and hexadecyl.
According to embodiments of the present application, the modified polyoxometalate anion may include at least one of modified Anderson-type, Keggin-type and Dawson-type polyoxometalate anions. Polyoxometalate anions of different configurations have different lewis acidity and redox properties.
In some embodiments, the modified Anderson-type polyoxometalate anion has the formula: [ Cr (OH)3Mo6O18{(OCH2)3CR1}2]3-And has excellent photocatalytic characteristics.
As an example, in the case where the modified polyoxometalate anion of the polyacid-based photocatalyst is an Anderson-type polyoxometalate anion, the polyacid-based photocatalyst may include at least one of a compound of the following formula and derivatives thereof:
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]and
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]。
in some possible embodiments, the modified Keggin-type polyoxometalate anion has the formula: [ GeW ]9V3O37{(OCH2)3CR1}2]m-And has excellent photocatalytic characteristics.
As an example, in the case where the modified polyoxometalate anion of the polyacid-based photocatalyst is a Keggin-type polyoxometalate anion, the polyacid-based photocatalyst includes at least one of a compound of the following formula and a derivative thereof:
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3C NH2}]、
[C9H7N(C4H9)]4[GeW9V3 O37{(OCH2)3C CH3}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3C NH2}]、
[C9H7N(C8H17)]4[GeW9V3 O37{(OCH2)3C CH3}]、
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3C NH2}]and
[C9H7N(C16H33)]4[GeW9V3 O37{(OCH2)3C CH3}]。
in some embodiments, the modified Dawson-type polyoxometalate anion has the formula: [ V ]3P2W15O59{(OCH2)3CR1}2]m-And has excellent photocatalytic properties.
As an example, in the case where the modified polyoxometalate anion of the polyacid-based photocatalyst is a Dawson-type polyoxometalate anion, the polyacid-based photocatalyst includes at least one of a compound of the following formula and derivatives thereof:
[C9H7N(C4H9)]m H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C NH2}]and
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C CH3}]。
the polyacid-based photocatalyst of the embodiment of the application has a crystal structure and a stable structure, and modified polymetallic oxolate anions and quinolinium ions in the crystal structure can be cooperated with each other, so that the utilization rate of catalytic reaction atoms and the catalytic reaction efficiency are effectively improved.
In order to prepare the polyacid-based photocatalyst of an embodiment of the first aspect of the present application, an embodiment of the second aspect of the present application provides a method for preparing a polyacid-based photocatalyst, comprising the steps of: s100 preparation of a first intermediate product R1Tris-POM, S200 preparation of the second intermediate [ C9H7NR2]X, S300 first intermediate product R1Tris-POM and a second intermediate [ C ]9H7NR2]X is synthesized into polyacid-based photocatalyst.
Step S100, comprising: using compounds R containing trihydroxy groups1Tris-single or multi-side Tris covalent modification of polyoxometallate POM to prepare a first intermediate product R1Tris-POM, wherein R1May be selected from at least one of hydroxyl, methyl, amino and nitro. The reaction formula of step S100 is shown as formula 1;
note that the first intermediate product R is prepared1The reaction conditions and molar ratios of the Tris-POM can be chosen according to the prior art.
In some embodiments, compound R containing a trihydroxy group1Tris may comprise dipentaerythritol C10H22O7And trimethylol R1Methyl hydride (CH)2OH)3-CH2-R1At least one of (1) and (2) is used for single-sided or multi-sided modification of POM.
In some embodiments, the polyoxometalate POM may include at least one of an Anderson-type, Keggin-type, and Dawson-type polyoxometalate. The type of POM can be flexibly selected according to production needs.
Step S200, including: halogenated alkane R2-X and quinoline C9H7N is mixed and processed at 50-90 ℃ to synthesize a second intermediate product [ C ]9H7NR2]X，[C9H7NR2]X is a quinolinium salt type compound. The reaction condition is mild, and the product yield is high. Wherein R is2At least one selected from linear or branched C1-C30 alkyl groups, wherein X is a halogen element and is at least one selected from bromine, iodine and chlorine. The reaction formula of step S200 is shown as formula 2;
in some possible embodiments, R2-X and C9H7The mol ratio of N is 4-6: 1. control of R2-X and C9H7The molar ratio of N can be effectively increased9H7NR2]Yield of X.
Step S300, including: the first intermediate product R1Tris-POM and a second intermediate [ C9H7NR2]X is respectively dissolved in the same or different first organic solvents, and the synthesis reaction is carried out at room temperature to obtain the polyacid-based photocatalyst
The reaction can be completed at room temperature, the reaction condition is mild, and the yield of the polyacid-based photocatalyst is high.
The reaction formula of step S300 is shown in formula 3:
in some embodiments, the first organic solvent may be at least one of acetonitrile, acetone, and dichloromethane, and the first intermediate or the second intermediate has a higher solubility in the first organic solvent, so as to facilitate the subsequent reaction. The above examples are merely illustrations of the first organic solvent, and are not intended to limit the kind of the first organic solvent.
Note that the first intermediate product R1Tris-POM in a first organic solvent as a first intermediate, a second intermediate [ C9H7NR2]X dissolved in the first organic solvent may serve as a solution of the second intermediate. For example, the first intermediate product R1Tris-POM in acetonitrile as a first intermediate product R1Tris-POM in acetonitrile. Second intermediate product [ C9H7NR2]X dissolved in acetonitrile as a second intermediate product [ C9H7NR2]And (3) acetonitrile solution of X. Also for example, a second intermediate [ C9H7NR2]Dissolving X in mixed solvent of acetonitrile/acetone/dichloromethane to obtain second intermediate product [ C9H7NR2]Acetonitrile/acetone/dichloromethane solution of X.
As an example of step S300, R may be added under stirring at room temperature1Dropwise addition of an acetonitrile solution of Tris-POM to [ C9H7NR2]And (3) reacting in the acetonitrile solution of X to generate a large amount of precipitate, continuously stirring for 2 hours, centrifugally filtering, removing supernatant, and reserving the precipitate to obtain the crude product of the polyacid-based photocatalyst.
The crude product of the polyacid-based photocatalyst can be continuously cleaned by adopting acetonitrile for a plurality of times, so that the polyacid-based photocatalyst can be obtained, and the purity of the polyacid-based photocatalyst is higher. Wherein, the stirring condition can ensure the reaction uniformity and can improve the reaction rate; the reaction can be completed at room temperature, and the reaction condition is mild.
As yet another example of step S300, R may be set at room temperature1Acetonitrile solution of Tris-POM and [ C9H7NR2]And mixing the acetonitrile solution of the X to prepare a mixed solution, adding a second organic solvent such as diethyl ether into the mixed solution, and diffusing the diethyl ether into the mixed solution to obtain the polyacid-based photocatalyst. The first organic solvent and the second organic solvent are different in kind, and the first organic solvent and the second organic solvent with different solubility characteristics are utilized to improve the synthesisThe polyacid-based photocatalyst of (1) has a purity, and the polyacid-based photocatalyst obtained in this step is a yellow rod-like crystal.
In some embodiments, the concentration of the solution of the first intermediate product may be 0.04 to 0.05 mol/L. The concentration of the solution of the second intermediate product can be 0.04-0.05 mol/L. In step S300, a first intermediate product R1Concentration of Tris-POM solution and second intermediate [ C9H7NR2]The concentration of the solution of X may be the same or different. First intermediate product R1Tris-POM with a second intermediate [ C9H7NR2]The molar ratio of X can be 2-8: 1, the yield of the polyacid-based photocatalyst can be improved.
The preparation method disclosed by the embodiment of the application is simple in preparation process, mild in reaction condition and high in catalyst yield.
The polyacid-based photocatalyst of the first aspect of the application has photocatalysis, can be applied to the reaction of preparing phenol by hydroxylation of benzene through photocatalysis, has high catalysis efficiency and phenol selectivity, and has certain application potential in industrial production of phenol.
Therefore, the embodiment of the third aspect of the present application provides an application of a polyacid-based photocatalyst in the field of the reaction for preparing phenol by carrying out hydroxylation on benzene.
In some practical examples, benzene and polyacid-based photocatalyst are mixed in a mixed solvent of water/acetonitrile, and the benzene is hydroxylated into phenol by carrying out photocatalytic reaction under the conditions of room temperature, oxygen enrichment and illumination. The amount of the polyacid-based photocatalyst added can be 2.0-3.0 mol% of benzene, and 2.5 mol% can be selected. The addition amount of the polyacid-based photocatalyst is small, and the catalytic efficiency is high.
By way of example, benzene and a polyacid-based photocatalyst are mixed in a mixed solvent of water/acetonitrile, and the mixture reacts under the illumination conditions of room temperature and a wavelength of 200-520 nm, wherein the wavelength can be 365nm, so that phenol is obtained; wherein the adding amount of the polyacid-based photocatalyst is 2.5 mol% of benzene, and the volume ratio of water to acetonitrile in the water/acetonitrile mixed solvent can be (2-4): (18-16), optionally 3: 17; an oxygen enriched environment is provided in the form of an oxygen balloon.
In some practical examples, benzene and polyacid-based photocatalyst are mixed in a mixed solvent of water/acetonitrile/sulfuric acid, and the benzene is hydroxylated into phenol by performing a photocatalytic reaction under the conditions of room temperature, oxygen enrichment and illumination. In an acidic environment, hydrogen peroxide is generated in the catalytic reaction process of the quinolinium ions or the derivatives thereof, and can be used as an oxidant of a modified polyoxometallate anion catalytic system to continuously catalyze and oxidize benzene, so that the utilization rate of catalytic reaction atoms and the catalytic reaction efficiency are further improved. Wherein, the adding amount of the polyacid-based photocatalyst can be 2.0-3.0 mol% of benzene, and can be 2.5 mol%. The addition amount of the polyacid-based photocatalyst is small, and the catalytic efficiency is high.
As another example, benzene and a polyacid-based photocatalyst are mixed in a mixed solvent of water/acetonitrile/sulfuric acid, and react under the illumination conditions of room temperature and a wavelength of 200-520 nm, wherein the wavelength is 365nm optionally, so as to obtain phenol; wherein the dosage of the polyacid-based photocatalyst is 2.5mol percent of benzene, and the volume ratio of water to acetonitrile in the mixed solvent of water/acetonitrile/sulfuric acid is 3: 17, the sulfuric acid is concentrated sulfuric acid, and the adding amount of the concentrated sulfuric acid is 45-65 mol% of benzene, and can be 57 mol%; an oxygen-enriched environment is provided in the form of an oxygen balloon.
The following description will be given with reference to specific examples.
Example 1
Preparation of 1-butylquinolinium bromide, 1-octylquinolinium bromide and 1-hexadecylquinolinium bromide.
2mmol of quinoline (258mg) were reacted with 10mmol of 1-bromobutane (1.37g), 1-bromooctane (1.93g) and 1-bromohexadecane (3.05g), respectively, under heating at 80 ℃ for 24 hours (solvent-free reaction). The reacted solutions were added dropwise to 50mL of anhydrous ether, and centrifuged to obtain three kinds of oils. Respectively purifying the obtained oily substances by using a column chromatography method to sequentially obtain pure pink purple 1-butylquinolinium bromide (named as (C)4-Quin) Br of the formula: [ C ]9H7N(C4H9)]Br). 1-octyl quinolinium Bromide (named (C)8-Quin) Br of formula [ C9H7N(C8H17)]Br). 1-Hexadecyquinolinium Bromide (named (C)16-Quin) Br, molecular formula: [ C ]9H7N(C16H31)]Br)。
FIGS. 1 to 3 show nuclear magnetic spectra of 1-butylquinolinium bromide, 1-octylquinolinium bromide, and 1-hexadecylquinolinium bromide, respectively, and the specific data are as follows, as shown in FIGS. 1 to 3:
(C4of-Quin) Br1H NMR：(400MHz,DMSO-d6,TMS)，δ(ppm)＝0.93(t,3H,-CH3),1.41(t,2H,-CH2),1.95(t,2H,-CH2),5.10(t,2H,-CH2),8.06(t,1H,-CH),8.21(t,1H,-CH),8.28(t,1H,-CH),8.51(d,1H,-CH),8.64(d,1H,-CH),9.33(d,1H,-CH),9.64(d,1H,-CH)。
(C8of-Quin) Br1H NMR：(400MHz,DMSO-d6,TMS)，δ(ppm)＝0.83(t,3H,-CH3),1.22(m,8H,-CH2),1.39(t,2H,-CH2),1.96(t,2H,-CH2),5.09(t,2H,-CH2),8.06(t,1H,-CH),8.21(t,1H,-CH),8.28(t,1H,-CH),8.52(d,1H,-CH),8.64(d,1H,-CH),9.33(d,1H,-CH),9.64(d,1H,-CH)。
(C16of-Quin) Br1H NMR：(400MHz,DMSO-d6,TMS)，δ(ppm)＝0.85(t,3H,-CH3),1.22(m,24H,-CH2),1.39(t,2H,-CH2),1.96(t,2H,-CH2),5.06(t,2H,-CH2),8.06(t,1H,-CH),8.20(t,1H,-CH),8.28(t,1H,-CH),8.49(d,1H,-CH),8.63(d,1H,-CH),9.31(d,1H,-CH),9.57(d,1H,-CH)。
Example 2
Preparation of Anderson type polyacid-based photocatalyst
0.2mmol of [ (C)4H9)4N]3{Cr(OH)3Mo6O18[(OCH2)3CCH2OH]A solution of (365.4mg) in acetonitrile (5mL) was added dropwise to 0.8mmol of (C) respectively8After centrifugation, washing and drying in a solution of-Quin) Br (257.6mg) in acetonitrile (10mL), 539.8mg of a pink solid was obtained in 96% yield.
Example 3
Preparation of Keggin type polyacid-based photocatalyst
0.2mmol of [ (C)4H9)4N]4[GeW9V3((CH2O)3CNH2)O37](712.0mg) in acetonitrile (5mL) was added dropwise to each of the solutions0.8mmol of (C)8After centrifugation, washing and drying in a solution of-Quin) Br (257.6mg) in acetonitrile (10mL), 955.2mg of a solid was obtained in 98% yield.
Example 4
Preparation of Dawson type polyacid-based photocatalyst
0.2mmol of [ (C)4H9)4N]6[V3P2W15O59(OCH2)3CCH2OH](1100.9mg) in acetonitrile (5mL) was added dropwise to 0.8mmol of (C)8After centrifugation, washing and drying in a solution of-Quin) Br (257.6mg) in acetonitrile (10mL), 1459.5mg of a solid was obtained in 98.1% yield.
Photocatalytic test 1-1
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene and 0.044mmol (10. mu.L) of dodecane, and 12.5. mu. mol of the Anderson-type polyacid-based photocatalyst prepared in example 2 was further added, followed by addition of 2mL of a mixed solvent (water and acetonitrile in a volume ratio of 0.3 mL: 1.7mL) along the tube wall, capping of the tube with an oxygen balloon, and reaction at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, diluted and then quantitatively analyzed for phenol yield of 53% by GC-MS using dodecane as an internal standard.
Photocatalytic test 1-2
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene, 0.044mmol (10. mu.L) of dodecane and 0.288mmol (16. mu.L) of 98% concentrated sulfuric acid, and then 12.5. mu. mol of the Anderson type polyacid-based photocatalyst prepared in example 2 was added, followed by addition of 2mL of a mixed solvent (water and acetonitrile in a volume ratio of 0.3 mL: 1.7mL) along the tube wall, capping the vial with an oxygen balloon, and reacting at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, diluted and then quantitatively analyzed for phenol yield of 68% by GC-MS using dodecane as an internal standard.
Photocatalytic test 2-1
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene and 0.044mmol (10. mu.L) of dodecane, and 12.5. mu. mol of the Keggin-type polyacid-based photocatalyst prepared in example 3 was further added, followed by addition of 2mL of a mixed solvent (water and acetonitrile in a volume ratio of 0.3 mL: 1.7mL) along the tube wall, capping of the tube with an oxygen balloon, and reaction at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, diluted and then quantitatively analyzed by GC-MS with dodecane as an internal standard to yield 63% phenol.
Photocatalytic test 2-2
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene, 0.044mmol (10. mu.L) of dodecane and 0.288mmol (16. mu.L) of 98% concentrated sulfuric acid, and then 12.5. mu. mol of the Keggin-type polyacid-based photocatalyst prepared in example 3 was added, followed by addition of 2mL of a mixed solvent (water and acetonitrile in a volume ratio of 0.3 mL: 1.7mL) along the tube wall, capping of the bottle with an oxygen balloon, and reacting at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, diluted and then quantitatively analyzed for phenol yield of 60% by GC-MS using dodecane as an internal standard.
Photocatalytic test 3-1
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene and 0.044mmol (10. mu.L) of dodecane, and 12.5. mu. mol of the Dawson-type polyacid-based photocatalyst prepared in example 4 was further added, followed by addition of 2mL of a mixed solvent (water and acetonitrile in a volume ratio of 0.3 mL: 1.7mL) along the tube wall, capping of the vial with an oxygen balloon, and reaction at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, diluted and then quantitatively analyzed for phenol yield of 60% by GC-MS using dodecane as an internal standard.
Photocatalytic test 3-2
A clean quartz tube was charged with 0.5mmol (45. mu.L) of benzene, 0.044mmol (10. mu.L) of dodecane and 0.288mmol (16. mu.L) of 98% concentrated sulfuric acid, and then 12.5. mu. mol of the Dawson type polyacid-based photocatalyst prepared in example 4 was added, followed by addition of 2mL of a mixed solvent (volume ratio of water to acetonitrile: 0.3 mL: 1.7mL) along the tube wall, capping of the bottle with an oxygen balloon, and reaction at room temperature for 12 hours. After the reaction was completed, the reaction was filtered, and the reaction system was extracted 3 times with ethyl acetate, and after dilution, the yield of phenol was quantitatively analyzed by GC-MS using dodecane as an internal standard to be 67%.
As shown in FIG. 4, in the mixed solvent system of water/acetonitrile of the photocatalytic tests 1-1, 2-1, and 3-1, the quinoline ion (a) in the polyacid-based photocatalyst was irradiated on the light barUnder this condition, the material is first converted into an excited state (b) and then converted into a radical form (c), and the formation of benzene positive ions is accompanied. (c) stabilized by POM anion cluster, is converted to (d) by abstracting a proton from an OH-adduct formed by the reaction of benzene cation and water molecule, accompanied by the formation of phenol. (d) Can be reoxidized to a by POM (e), and reduced POM (f) is O2Reoxidizing to (e).
As shown in fig. 5, in the mixed solvent system of water/acetonitrile/sulfuric acid of the photocatalytic tests 1-2, 2-2, and 3-2, the whole photocatalytic process mainly comprises two parts: 1) the quinolinium ions of the polyacid-based photocatalyst catalyze benzene to be hydroxylated to generate phenol and hydrogen peroxide under the photocatalytic condition (figure 5 (a)); 2) h generated by POM anion cluster on quinolinium ion under acidic condition2O2Then, the benzene is continuously oxidized into phenol (figure 5 (b)); wherein, the POM anion cluster state is that POM (e) is reduced into POM (f) in a mixed solvent system, the reduced POM (f) is oxidized into POM (g) by H2O2, and the POM (g) is oxidized into POM (H) by H2O 2.
While the present application has been described with reference to preferred embodiments, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, features shown in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.
Claims (10)
1. A polyacid-based photocatalyst is characterized by that its molecular formula is
And has a structure shown in a formula (I),
wherein, [ POM { (OCH)2)3CR1}2]m-Represents a modified polyoxometalate anion including at least one of modified Anderson-, Keggin-and Dawson-type polyoxometalate anions, { POM } represents a polyoxometalate unit, R1At least one selected from hydroxyl, methyl, amino and nitro, and m is a positive integer;
[C9H7NR2]+represents a quinolinium ion, R2At least one selected from linear or branched C1-C30 alkyl groups.
2. The polyacid-based photocatalyst of claim 1,
R2at least one selected from the group consisting of linear or branched butyl, octyl and hexadecyl.
3. The polyacid-based photocatalyst of claim 1, wherein the modified polyoxometalate anion is a modified Anderson polyoxometalate anion of the formula:
[Cr(OH)3Mo6O18{(OCH2)3CR1}2]3-(ii) a Or
The modified polyoxometallate anions are modified Keggin type polyoxometallate anions, and the molecular formula is as follows:
[GeW9V3O37{(OCH2)3CR1}2]m-(ii) a Or
The modified polyoxometallate anion is a modified Dawson type polyoxometallate anion, and the molecular formula of the modified polyoxometallate anion is as follows:
[V3P2W15O59{(OCH2)3CR1}2]m-。
4. the polyacid-based photocatalyst of claim 1, wherein the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Anderson polyoxometalate anion, the polyacid-based photocatalyst comprising at least one of the compounds of the following formula and derivatives thereof:
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C4H9)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]、
[C9H7N(C8H17)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C NH2}]and
[C9H7N(C16H33)]3[Cr(OH)3Mo6O18{(OCH2)3C CH3}]。
5. the polyacid-based photocatalyst of claim 1, wherein the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Keggin-type polyoxometalate anion, and the polyacid-based photocatalyst comprises at least one of a compound of the following formula and derivatives thereof:
[C9H7N(C4H9)]4[GeW9V3O37{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]4[GeW9V3O37{(OCH2)3C NH2}]、
[C9H7N(C4H9)]4[GeW9V3O37{(OCH2)3C CH3}]、
[C9H7N(C8H17)]4[GeW9V3O37{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]4[GeW9V3O37{(OCH2)3C NH2}]、
[C9H7N(C8H17)]4[GeW9V3O37{(OCH2)3C CH3}]、
[C9H7N(C16H33)]4[GeW9V3O37{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]4[GeW9V3O37{(OCH2)3C NH2}]and
[C9H7N(C16H33)]4[GeW9V3O37{(OCH2)3C CH3}]。
6. the polyacid-based photocatalyst of claim 1, wherein the modified polyoxometalate anion of the polyacid-based photocatalyst is a modified Dawson-type polyoxometalate anion, and the polyacid-based photocatalyst comprises at least one of a compound of the following formula and derivatives thereof:
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C4H9)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C NH2}]、
[C9H7N(C8H17)]5H[V3P2W15O59{(OCH2)3C CH3}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3CCH2OH}]、
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C NH2}]and
[C9H7N(C16H33)]5H[V3P2W15O59{(OCH2)3C CH3}]。
7. a preparation method of a polyacid-based photocatalyst is characterized by comprising the following steps:
using compounds R containing trihydroxy groups1Tris-single or multi-side Tris covalent modification of polyoxometallate POM to prepare a first intermediate product R1Tris-POM, wherein R1At least one of hydroxyl, methyl, amino and nitro is selected, the reaction formula is shown as formula (1),
halogenated alkane R2-X and quinoline C9H7N is mixed and processed at 50-90 ℃ to synthesize a second intermediate product [ C ]9H7NR2]X, wherein R2At least one selected from linear or branched C1-C30 alkyl, X is at least one selected from bromine, iodine and chlorine, the reaction formula is shown as a formula (2),
the first intermediate product R is1-Tris-POM and said second intermediate [ C9H7NR2]X is respectively dissolved in the same or different first organic solvents, and the synthesis reaction is carried out at room temperature to obtain the polyacid-based photocatalyst
The reaction formula is shown as a formula (3),
8. the method of claim 7, wherein R is a halogenated alkane2-X and quinoline C9H7N is mixed and treated at 50-90 ℃, and the halogenated alkane R2-X and said quinoline C9H7The mol ratio of N is 4-6: 1; and/or
The first intermediate product R1-Tris-POM and said second intermediate [ C9H7NR2]X are respectively dissolved in the same or different first organic solvents, and the first intermediate product R1-a solution of Tris-POM in a first organic solvent as a first intermediate product, said second intermediate product [ C9H7NR2]Dissolving X in a first organic solvent to serve as a solution of a second intermediate product, wherein the concentration of the solution of the first intermediate product is 0.04-0.05 mol/L, the concentration of the solution of the second intermediate product is 0.04-0.05 mol/L, and the concentration of the first intermediate product R1-Tris-POM with said second intermediate [ C9H7NR2]The molar ratio of X is 2-8: 1.
9. the method according to claim 7, wherein the trihydroxy group-containing compound R1Tris comprising dipentaerythritol C10H22O7And trimethylol R1Methyl hydride (CH)2OH)3-CH2-R1At least one of; and/or
The polyoxometallate POM comprises at least one of an Anderson type, a Keggin type and a Dawson type polyoxometallate.
10. Use of a polyacid-based photocatalyst in the field of reactions for the preparation of phenol by the hydroxylation of benzene using photocatalysts, characterized in that the polyacid-based photocatalyst is a polyacid-based photocatalyst according to any one of claims 1 to 6 or a polyacid-based photocatalyst obtained by the preparation method according to any one of claims 7 to 9.
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