CN108722490B - Metal-bipyridinium photocatalyst, preparation method and application thereof - Google Patents
Metal-bipyridinium photocatalyst, preparation method and application thereof Download PDFInfo
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- CN108722490B CN108722490B CN201810495621.XA CN201810495621A CN108722490B CN 108722490 B CN108722490 B CN 108722490B CN 201810495621 A CN201810495621 A CN 201810495621A CN 108722490 B CN108722490 B CN 108722490B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229910052751 metal Chemical class 0.000 claims abstract description 28
- 239000002184 metal Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 8
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910009112 xH2O Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- -1 high-iodine salt Chemical compound 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009475 tablet pressing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
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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
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
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Abstract
The invention belongs to the field of photocatalysis, and particularly relates to a metal-bipyridinium photocatalyst, and a preparation method and application thereof. The catalyst is a compound consisting of bipyridinium salt and metal salt; the bipyridinium salt consists of a ligand and an anion. The method comprises the following steps: dissolving bipyridinium salt in a solvent to obtain a ligand solution; dissolving a metal salt in a solvent to obtain a metal salt solution; and mixing the ligand solution and the metal salt solution, stirring until a precipitate is generated, filtering, washing and drying the precipitate to obtain the ligand-metal complex. The photocatalyst can catalyze the oxidation of alcohol into aldehyde, and specifically comprises the following components: dissolving reactant alcohol in an organic solvent, adding a metal-bipyridinium photocatalyst, and irradiating and reacting for 0.5-30 h by using a light source under the stirring state. The photocatalyst is simple to prepare, does not use noble metal, and has good cyclability and mild reaction conditions. The catalyst is applied to alcohol oxidation reaction and has the characteristics of high activity, high selectivity and easy recovery.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a metal-bipyridinium photocatalyst, and a preparation method and application thereof.
Background
Aldehyde is an important fine chemical raw material and is widely applied to the fields of production, research and development of chemicals. Alcohol is a kind of organic matter with wide source and low price, so selective oxidation of alcohol to aldehyde is concerned by chemical researchers for many years. The traditional alcohol oxidation to aldehyde usually needs to use a large amount of oxidants, such as chromium oxide, manganese dioxide, high-iodine salt, hydrogen peroxide and the like, and the oxidants have the defects of environmental pollution, high danger, more activating components needed by a catalytic system, difficult recovery of the catalyst and the like. With the increasing attention on the environment and energy, researchers have begun to explore the selective oxidation of alcohols using noble metal complexes such as palladium (Pd), ruthenium (Ru), and copper (Cu) as catalysts. However, these catalysts have the disadvantages of high price, complicated preparation and the like. In view of the above problems, the development of a novel environmentally friendly, highly active and highly selective catalyst is of far-reaching importance.
In recent years, photocatalytic reactions have been used in the field of organic catalysis due to their particular advantages. The commonly used photocatalysts need to satisfy the following two conditions: 1. absorbing sunlight in an ultraviolet visible light region to generate electrons and holes and the catalyst can prevent recombination of the holes and the electrons; 2. has the oxidation capability to facilitate the catalytic oxidation reaction. At present, titanium dioxide and sulfide nanosheets are used as photocatalysts, but the catalysts are relatively complex to prepare, expensive metals are often used, and the cost is relatively high.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a metal-bipyridinium photocatalyst, which is simple to prepare, does not use noble metals, and has good recyclability and mild reaction conditions.
The second purpose of the invention is to provide a preparation method of the metal-bipyridinium photocatalyst, which is simple and easy to implement, and the metal salt and the bipyridinium salt are respectively dissolved in a solvent, mixed and heated to generate solid precipitates.
The invention also aims to provide application of the metal-bipyridinium photocatalyst, and the catalyst can efficiently catalyze alcohol to be oxidized into aldehyde.
In order to achieve the above object, the technical solution of the present invention is as follows.
A metal-bipyridinium photocatalyst, which is a compound consisting of a bipyridinium salt and a metal salt; the bipyridinium salt consists of a ligand and an anion;
the ligand in the bipyridinium salt is as follows:
R1is-H,
One or two of them;
R2is composed of
or/and-CH2COOH；
R3Is composed of
or/and-CH2CH2-；
The bipyridinium salt has Cl as the anion-、Br-、I-、BF4 -、ClO4 -Or PF6 -；
The metal salt is ZnCl2·xH2O、FeCl3·6H2O、MnCl2·4H2O、NiCl2·6H2O、CuCl、CdCl2·21/2H2O、Zn(NO3)2·6H2O、Cd(NO3)2·4H2O、Fe(NO3)3·9H2O、ZnSO4·7H2O or Fe2(SO4)3。
Preferably, the bipyridinium salt is:
preferably, the metal salt is ZnCl2·xH2O、Zn(NO3)2·6H2O、CdCl2·21/2H2O、Cd(NO3)2·4H2O or Fe (NO)3)3·9H2O。
The preparation method of the metal-bipyridinium photocatalyst comprises the following steps:
dissolving bipyridinium salt in a solvent to obtain a ligand solution; dissolving a metal salt in a solvent to obtain a metal salt solution; mixing the ligand solution and the metal salt solution, stirring until a precipitate is generated, filtering, washing and drying the precipitate to obtain a metal-bipyridinium photocatalyst;
wherein the molar ratio of the bipyridinium salt to the metal salt is 1: 2-3: 1;
the solvent is more than one of water, ethanol, tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide and methanol.
Preferably, the bipyridinium salt is dissolved in a solvent, and the pH is adjusted to be neutral to obtain a ligand solution; dissolving the auxiliary ligand in water, and adjusting the pH value to be neutral to obtain an auxiliary ligand solution; dripping the auxiliary ligand solution into the ligand solution to obtain a ligand mixed solution; dissolving a metal salt in a solvent to obtain a metal salt solution; mixing the ligand mixed solution and the metal salt solution, adding ethanol, stirring until a precipitate is generated, filtering, washing and drying the precipitate to obtain a metal-bipyridinium photocatalyst;
wherein the auxiliary ligand is trimesic acid, and the molar ratio of the trimesic acid to the bipyridinium salt is 1: 1-1: 2; the pH regulator is NaOH.
The application of the metal-bipyridinium photocatalyst as the photocatalyst for catalyzing alcohol oxidation to aldehyde specifically comprises the steps of dissolving reactant alcohol in an organic solvent, adding the metal-bipyridinium photocatalyst, and irradiating and reacting for 0.5-30 h by using a light source under the stirring state to obtain aldehyde, wherein the molar ratio of the amount of the reactant alcohol to the amount of the photocatalyst in the organic solvent is 1:1 × 10-5～1:1×10-1；
The reactant alcohol is aromatic alcohol;
the organic solvent is more than one of ethanol, tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, dimethyl sulfoxide and methanol.
Preferably, the organic solvent is acetonitrile or acetone.
Preferably, the light source wavelength is more than 200nm and less than 650 nm.
Preferably, the light source is sunlight, a xenon lamp, an L ED lamp or a high-pressure mercury lamp.
Preferably, the reactant alcohol has the following structure:
advantageous effects
The metal-bipyridinium photocatalyst is insoluble in common solvents, such as water, acetonitrile, acetone, ethanol, chloroform, N-dimethylformamide and the like, so that a heterogeneous system is formed in a reaction system, and the catalyst can be directly used for the next reaction by a centrifugation or filtration method.
The preparation method of the indissolvable metal-bipyridinium photocatalyst has a simple synthesis process.
The metal-bipyridinium photocatalyst is applied to alcohol oxidation reaction, and has the characteristics of high activity, high selectivity and easiness in recovery; no noble metal is used, so that the cost of industrial production is greatly reduced.
Drawings
FIG. 1 shows the catalyst Zn prepared in example 12C48N8Cl6H52O8FT-IR diagram of (1).
FIG. 2 shows the Zn catalyst prepared in example 12C48N8Cl6H52O8PXRD pattern of (a).
FIG. 3 shows Cd as catalyst prepared in example 24.5C66N3O37H55FT-IR diagram of (1).
FIG. 4 shows Cd as catalyst prepared in example 24.5C66N3O37H55PXRD pattern of (a).
Detailed Description
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples:
(1) fourier transform infrared spectroscopy (FT-IR) test: the KBr tablet pressing method is adopted to test on a NicoletiS10 type infrared spectrometer, and the test range is 400-4000cm-1。
(2) Powder X-ray diffraction (PXRD) test powder X-ray diffraction data were collected using a Bruker D8 Advance diffractometer with Cu-K α as the radiation source
Example 1:
preparation of metal-bipyridinium photocatalysts Zn2C48N8Cl6H52O8A mixed solvent of a ligand bipyridinium salt (0.05mmol) and 2m L was added to a 20m L glass vial, and dissolved by stirring to obtain an onium salt solution, and a ZnCl solution was added to a 20m L glass vial2·xH2Dripping the metal salt solution into the ligand solution to uniformly mix the metal salt solution and the ligand solution, stirring until precipitate is produced, filtering the precipitate, washing with acetone, and drying in a normal-pressure 70-DEG C oven for 1 hour to obtain a metal-bipyridinium photocatalyst;
wherein, the ligand onium salt has the structure:
wherein, the mixed solvent is: and (3) mixing the N, N-dimethylformamide and ethanol (the volume ratio is 1: 1).
IR (KBr, cm) of the final product–1) The characterization results are shown in FIG. 1, and the results show that the final product is Zn2C48N8Cl6H52O8：3429,3049,1637,1615,1593,1550，1472,1416,1245,1162, 1015,786,770,639。
PXRD characterization results of the final product are shown in FIG. 2, which shows Zn2C48N8Cl6H52O8Is a pure phase.
Example 2:
preparation of Cd from metal-bipyridinium photocatalyst4.5C66N3Cl11O37H55Adding bipyridinium salt (0.05mmol) and 2m L of water into a 20m L glass bottle, stirring for dissolution, adjusting pH to 7 with 2 mol/L of NaOH solution to obtain a ligand solution, weighing trimesic acid (0.05mmol) into a 10m L beaker, adding 1m L of water into the beaker, stirring for dissolution, adjusting pH to 7 with 2 mol/L of NaOH solution to obtain a trimesic acid solution, dripping the trimesic acid solution into the ligand solution, uniformly mixing the ligand solution and the ligand solution to obtain a mixed solution, adding 2m L0.01 mol/L of CdCl into the mixed solution, and stirring for dissolution2Adding 1m L ethanol into the water solution to adjust polarity, and stirring for 15min to obtain fructus Citri TangerinaeA colored columnar solid. And filtering the obtained solid, washing with acetone, and drying in an oven at 70 ℃ under normal pressure for 1 hour to obtain the metal-bipyridinium photocatalyst.
Wherein, the ligand onium salt has the structure:
IR (KBr, cm) of the final product–1) The characterization result is shown in FIG. 3, and the result shows that the final product is Cd4.5C66N3Cl11O37H55：3413,3121,3056,1637,1612,1558,1439,1404,1374,1206, 1188,1160,1105,1017,931,864,806,768,726,653,523。
PXRD characterization results of the final product are shown in FIG. 4, which shows that Cd4.5C66N3Cl11O37H55Is a pure phase.
Example 3:
preparation of aldehydes: the metal-bipyridinium photocatalyst Zn prepared in example 1 was added to a 10ml quartz centrifuge tube2C48N8Cl6H52O8(2mg) and 2m L acetone, then adding 0.2mmol of different aromatic alcohols, starting L ED light source, irradiating and reacting under the condition of uniform stirring, layering the photocatalyst and the solution after reaction, centrifuging, taking the upper layer solution, detecting the conversion rate of reactants by GC-2014C gas chromatography, and obtaining reaction products, illumination time, conversion rate and selectivity of different aromatic alcohols as shown in table 1.
TABLE 1 conversion and Selectivity of different aromatic alcohols in example 1
As can be seen from Table 1, the catalytic reaction system has a high selectivity. Wherein the aromatic alcohol of electron donating group has higher yield than that of the aromatic alcohol of electron withdrawing group, and the para-substituted aromatic alcohol has higher yield and selectivity than that of the meta-substituted aromatic alcohol.
Example 4:
preparation of aldehydesA10 m L quartz centrifuge tube was charged with the metal-bipyridinium photocatalyst Cd prepared in example 24.5C66N3Cl11O37H55(2mg) and 2m L acetone, then adding 0.2mm of L different aromatic alcohols, starting L ED light source, irradiating and reacting under the condition of uniform stirring, layering the photocatalyst and the solution after reaction, centrifuging, taking the upper layer solution, detecting the conversion rate of the reactant by GC-2014C gas chromatography, and obtaining the reaction products, the illumination time, the conversion rate and the selectivity of different aromatic alcohols are shown in table 2.
TABLE 2 conversion and Selectivity of different aromatic alcohols in example 2
As can be seen from Table 2, the catalytic reaction system has a high selectivity. Wherein the aromatic alcohol of electron donating group has higher yield than that of the aromatic alcohol of electron withdrawing group, and the para-substituted aromatic alcohol has higher yield and selectivity than that of the meta-substituted aromatic alcohol.
Example 5:
stability of Metal-bipyridinium photocatalyst the metal-bipyridinium photocatalyst Cd prepared in example 2 was added to a 10m L quartz centrifuge tube4.5C66N3Cl11O37H55(2mg) and 2m L acetone, then 0.2mmol of p-methoxybenzyl alcohol is added, L ED light source is started, the reaction is irradiated under the condition of uniform stirring, GC-2014C gas chromatography is used for detecting the conversion rate of the reactants, after the reaction is finished, centrifugal separation and standing are carried out, the upper solution is taken, and the product is obtained, and the stability results of the metal-bipyridinium photocatalyst after 4 times of circulation are shown in Table 3.
TABLE 3 catalyst stability in example 2
As can be seen from table 3, the metal-bipyridinium photocatalyst has high selectivity after 3 cycles, and similar yield can be achieved by prolonging the time when the catalyst is cycled for 4 cycles. The stability of the metal-bipyridinium photocatalyst is shown to be good.
The invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the spirit and principle of the invention are deemed to be within the scope of the invention.
Claims (10)
1. A metal-bipyridinium photocatalyst, characterized by: the catalyst is a compound consisting of bipyridinium salt and metal salt; the bipyridinium salt consists of a ligand and an anion;
the ligand in the bipyridinium salt is as follows:
R1is-H,
One or two of them;
R2is composed of
or/and-CH2COOH；
R3Is composed of
or/and-CH2CH2-；
The bipyridinium salt has Cl as the anion-、Br-、I-、BF4 -、ClO4 -Or PF6 -；
The metal salt is ZnCl2·xH2O、FeCl3·6H2O、MnCl2·4H2O、NiCl2·6H2O、CuCl、CdCl2·21/2H2O、Zn(NO3)2·6H2O、Cd(NO3)2·4H2O、Fe(NO3)3·9H2O、ZnSO4·7H2O or Fe2(SO4)3。
2. A metal-bipyridinium photocatalyst according to claim 1, wherein: the bipyridinium salt is:
3. a metal-bipyridinium photocatalyst according to claim 1, wherein: the metal salt is ZnCl2·xH2O、Zn(NO3)2·6H2O、CdCl2·21/2H2O、Cd(NO3)2·4H2O or Fe (NO)3)3·9H2O。
4. A method for preparing a metal-bipyridinium photocatalyst according to any one of claims 1 to 3, comprising: the method comprises the following steps:
dissolving bipyridinium salt in a solvent to obtain a ligand solution; dissolving a metal salt in a solvent to obtain a metal salt solution; mixing the ligand solution and the metal salt solution, stirring until a precipitate is generated, filtering, washing and drying the precipitate to obtain a metal-bipyridinium photocatalyst;
wherein the molar ratio of the bipyridinium salt to the metal salt is 1: 2-3: 1;
the solvent is more than one of water, ethanol, tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide and methanol.
5. The method of claim 4, wherein the metal-bipyridinium photocatalyst is prepared by: dissolving bipyridinium salt in a solvent, and adjusting the pH value to be neutral to obtain a ligand solution; dissolving the auxiliary ligand in water, and adjusting the pH value to be neutral to obtain an auxiliary ligand solution; dripping the auxiliary ligand solution into the ligand solution to obtain a ligand mixed solution; dissolving a metal salt in a solvent to obtain a metal salt solution; mixing the ligand mixed solution and the metal salt solution, adding ethanol, and stirring until a precipitate is generated; filtering, washing and drying the precipitate to obtain a metal-bipyridinium photocatalyst;
wherein the auxiliary ligand is trimesic acid, and the molar ratio of the trimesic acid to the bipyridinium salt is 1: 1-1: 2; the pH regulator is NaOH.
6. Use of a metal-bipyridinium photocatalyst according to any of claims 1 to 3, wherein: as a photocatalyst, catalyzing the oxidation of alcohol to aldehyde, specifically: dissolving reactant alcohol in an organic solvent, adding a metal-bipyridinium photocatalyst, and irradiating and reacting for 0.5-30 h by using a light source under the stirring state to obtain aldehyde;
wherein the molar ratio of the reactant alcohol in the organic solvent to the added photocatalyst is 1:1 × 10-5～1:1×10-1；
The reactant alcohol is aromatic alcohol;
the organic solvent is more than one of ethanol, tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, dimethyl sulfoxide and methanol.
7. Use of a metal-bipyridinium photocatalyst according to claim 6, wherein: the organic solvent is acetonitrile or acetone.
8. Use of a metal-bipyridinium photocatalyst according to claim 6, wherein: the wavelength of the light source is more than 200nm and less than 650 nm.
9. The use of a metal-bipyridinium photocatalyst as claimed in claim 6, wherein the light source is sunlight, xenon lamp, L ED lamp or high pressure mercury lamp.
10. Use of a metal-bipyridinium photocatalyst according to claim 6, wherein: the reactant alcohol has the following structure:
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