CN111841636A - Application of metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants - Google Patents
Application of metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants Download PDFInfo
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- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- WLOADVWGNGAZCW-UHFFFAOYSA-N 3-phenyl-23H-porphyrin-2,18,20,21-tetracarboxylic acid Chemical compound OC(=O)C=1C(N2C(O)=O)=C(C(O)=O)C(=N3)C(C(=O)O)=CC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C2C=1C1=CC=CC=C1 WLOADVWGNGAZCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007112 amidation reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000003223 protective agent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 7
- 229940012189 methyl orange Drugs 0.000 abstract description 7
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 5
- 150000001282 organosilanes Chemical class 0.000 abstract description 5
- 125000002252 acyl group Chemical group 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108060006006 Cytochrome-c peroxidase Proteins 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical class N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B01J35/39—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to application of a metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants, belonging to the technical field of photocatalysis and water treatment. The invention carries out directional hydrolytic polycondensation on organosilane molecules containing amino groups to form mesoporous organic silicon oxide containing amino groups. Meanwhile, tetracarboxyphenyl porphyrin is used as a basic photosensitive component, and thionyl chloride is adopted to perform acyl chlorination modification on carboxyl groups. The acyl-chlorinated metalloporphyrin can be subjected to amidation reaction with amino mesoporous organic silicon oxide, so that the metalloporphyrin is firmly loaded on the surface of the mesoporous organic silicon oxide by covalent bonds, the technical problem that the metalloporphyrin is easy to fall off is effectively solved, and the stability of the catalyst is improved. The photocatalytic material prepared by the method is applied to catalytic degradation of a simulated pollutant methyl orange, the initial degradation rate can reach 96.8%, and after 5 times of circulation, the photocatalytic material still can keep more than 90% of degradation rate, is obviously superior to a metalloporphyrin-silicon oxide composite material prepared by a traditional impregnation loading method, and has potential application value.
Description
Technical Field
The invention relates to an application of a metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants, belonging to the technical field of photocatalysis and water treatment.
Background
Porphyrin is a general name of homologues and derivatives of porphin with substituent at outer ring, and has functions of electron transfer, oxygen transfer, charge separation and the like in organisms. The metallized porphyrin can simulate important biological models of proteins such as catalase, peroxidase, cytochrome P450 and the like, and is also one of important biomimetic catalysts. Many researches on catalysis of metalloporphyrin are reported, including oxidation reaction, C-H bond activation, photocatalysis and the like. Although metalloporphyrin shows a good catalytic effect as a typical homogeneous catalyst, metalloporphyrin is unstable in the reaction solution. The metalloporphyrin is easy to be oxidized and degraded or irreversibly dimerized to inactivate, the catalytic activity of the metalloporphyrin can be reduced or even be ineffective due to the defects, and the porphyrin is difficult to separate from a reaction system after catalytic reaction and is difficult to recycle, so the practical application of the metalloporphyrin catalytic system is limited due to the defects.
Homogeneous metalloporphyrin is loaded on a solid insoluble carrier through a physical or chemical method to form a heterogeneous catalysis system, and the method is a method for solving the common problems of homogeneous catalysis of metalloporphyrin. Among them, the most commonly used and most effective is to dissolve the prepared homogeneous metalloporphyrin catalyst in a suitable organic solvent, such as dichloromethane (CH)2Cl2) N, N-Dimethylformamide (DMF), trichloromethane (CHCl)3) And adding inorganic carrier such as silicon oxide and aluminum oxide into the prepared solution to make the metalloporphyrin directly adsorbed on the carrier by physical adsorption or chemical adsorption, and then fully washing with corresponding solvent (multiple washing or Soxhlet extraction). The preparation process of the impregnation method is simple and convenient, but the obtained heterogeneous catalyst is unstable and is easy to lose active centers.
A Periodic Mesoporous organo-silicon oxide material (PMO) is a novel organic-inorganic composite Mesoporous material, which is a material with a specific micro-morphology formed by condensation polymerization of hydrolyzed organosilane molecules under the directional action of a surfactant. PMO has important roles in heterogeneous catalysis, substance adsorption, chromatographic phase, light absorption and emission, drug and biomolecule transfer and the like due to the regular pore channel structure, larger specific surface area, adjustable surface property and the self characteristics of different bridging functional groups. By modulating the organosilane raw material, more types of functional groups such as amino, aldehyde, sulfydryl and the like can be provided on the surface of the PMO, and the grafting of the functional groups enables the PMO to have better adjustable controllability and wider application range.
Based on the prior art, the invention firstly develops the metalloporphyrin-mesoporous organic silicon oxide material bridged by chemical covalent bonds and uses the metalloporphyrin-mesoporous organic silicon oxide material for photocatalytic degradation of organic pollutants. The invention carries out directional hydrolytic polycondensation on organosilane molecules containing amino groups to form mesoporous organic silicon oxide containing amino groups. Meanwhile, tetracarboxyphenyl porphyrin is used as a basic photosensitive component, and thionyl chloride is adopted to perform acyl chlorination modification on carboxyl groups. The acyl-chlorinated metalloporphyrin can be subjected to amidation reaction with amino mesoporous organic silicon oxide, so that the metalloporphyrin is firmly supported on the surface of the mesoporous organic silicon oxide through covalent bonds, when the acyl-chlorinated metalloporphyrin is applied to photocatalytic degradation of organic pollutants, the technical problem that the metalloporphyrin is easy to fall off is effectively solved, and the stability of a catalytic system is improved.
Disclosure of Invention
The invention aims to provide an application of a metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants, and specifically relates to a method for preparing the metalloporphyrin-mesoporous organic silicon oxide composite material, which comprises the steps of putting the metalloporphyrin-mesoporous organic silicon oxide composite material into wastewater containing the organic pollutants, keeping away from light to achieve adsorption balance, and irradiating the system by using a xenon lamp to perform photocatalytic degradation reaction; and after the reaction is finished, filtering and collecting the composite material, repeating the operation, and performing cyclic degradation reaction for 5-100 times.
Further, the metalloporphyrin-mesoporous organic silicon oxide composite material takes mesoporous organic silicon oxide as a carrier, metalloporphyrin is a photocatalytic active component, and the metalloporphyrin and the mesoporous organic silicon oxide are connected through an amide bond; the metalloporphyrin accounts for 10-20 wt% of the photocatalytic material.
Furthermore, the coordination metal in the metalloporphyrin is selected from Ti, Fe, Cu, Zn, Ni, Cr and Co.
Further, the preparation method of the metalloporphyrin-mesoporous organic silicon oxide composite material comprises the following preparation steps:
(1) dissolving 0.01-0.05 part by mass of metal coordinated tetracarboxyphenyl porphyrin (TCPP) in 500 parts by mass of DMF (dimethyl formamide), introducing nitrogen, adding 1-3 parts by mass of thionyl chloride, heating and refluxing for reaction at 40-80 ℃ for 3-8h, and evaporating to remove unreacted thionyl chloride and redundant solvent to obtain acylchlorinated metalloporphyrin;
(2) cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, polyvinylpyrrolidone (PVP) is used as a protective agent, 1-5 parts by mass of CTAB and 0.3-1 part by mass of PVP are respectively added into a mixed solution of water and ethanol of 200 parts by mass of 150-sodium chloride, and stirring and dissolving are carried out; slowly dripping 3-10 parts by mass of 3-aminopropyltriethoxysilane and 10-20 parts by mass of 1, 2-bis (trimethoxysilyl) ethane into the solution under continuous stirring, continuously stirring for 2-3h after dripping is finished, transferring the obtained homogeneous solution into a stainless steel reaction kettle with polytetrafluoroethylene, placing the stainless steel reaction kettle into a drying oven for reaction for 20-30h at 80-130 ℃, and fully washing reactants by adopting ethanol and hydrochloric acid to obtain PMO with amino;
(3) Dispersing 5-8 parts by mass of PMO with amino obtained in the step (2) in 150-300 parts by mass of dichloromethane, fully and uniformly stirring, adding 2-5 parts by mass of acylchlorinated metalloporphyrin obtained in the step (1), stirring until dissolving, dropwise adding 1-3 drops of DMF (dimethyl formamide) as a catalyst, introducing nitrogen, reacting for 20-40h at 80-160 ℃, filtering after the reaction is finished, and fully washing to obtain the metalloporphyrin-mesoporous organic silicon oxide photocatalytic material.
Further, in the step (2), the mass ratio of the 3-aminopropyltriethoxysilane to the 1, 2-bis (trimethoxysilyl) ethane is 0.3-0.5: 1.
Further, the temperature of the amidation reaction in the step (3) is preferably 100-.
Organic metalloporphyrin is loaded on an inorganic carrier by a traditional impregnation method, and the metalloporphyrin is difficult to be firmly loaded on the surface of the carrier through physical or chemical action due to the phase difference of organic matters and inorganic matters. Therefore, in the actual process of photocatalytic degradation of organic pollutants, metalloporphyrin is easy to fall off, and the stability of the catalyst is influenced. The periodic mesoporous organic silicon oxide is used as a carrier, and has an inorganic silicon oxide material framework and an organic group bridge, wherein the organic group bridge can be used for grafting and modifying different functional groups, so that the covalent loading of metalloporphyrin is possible.
The invention carries out directional hydrolytic polycondensation on organosilane molecules containing amino groups to form mesoporous organic silicon oxide containing amino groups. Meanwhile, tetracarboxyphenyl porphyrin is used as a basic photosensitive component, and thionyl chloride is adopted to perform acyl chlorination modification on carboxyl groups. The acyl-chlorinated metalloporphyrin can be subjected to amidation reaction with amino mesoporous organic silicon oxide, so that the metalloporphyrin is firmly loaded on the surface of the mesoporous organic silicon oxide by covalent bonds, the technical problem that the metalloporphyrin is easy to fall off is effectively solved, and the stability of the catalyst is improved.
The mesoporous organic silicon oxide has a hierarchical pore structure, and can improve the mass transfer diffusion efficiency of reactant molecules and further improve the photocatalytic degradation efficiency in the catalytic reaction process.
The initial degradation rate of the photocatalytic material prepared by the method for the simulated pollutant methyl orange can reach 96.8%, after 5 times of circulation, the photocatalytic material still can keep more than 90% of degradation rate, and is obviously superior to the metalloporphyrin-silicon oxide composite material prepared by the traditional impregnation loading method.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving 0.03 mass part of metal-coordinated tetracarboxyphenyl porphyrin (TCPP) in 300 mass parts of DMF (dimethyl formamide), introducing nitrogen, adding 3 mass parts of thionyl chloride, heating and refluxing for reaction at the reaction temperature of 70 ℃ for 5 hours, and evaporating to remove unreacted thionyl chloride and redundant solvent to obtain acyl-chlorinated metalloporphyrin;
(2) cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, polyvinylpyrrolidone (PVP) is used as a protective agent, 4 parts by mass of CTAB and 0.8 part by mass of PVP are respectively added into 200 parts by mass of a mixed solution of water and ethanol, and stirring and dissolving are carried out; slowly dripping 6 parts by mass of 3-aminopropyltriethoxysilane and 12 parts by mass of 1, 2-bis (trimethoxysilyl) ethane into the solution under continuous stirring, continuously stirring for 2 hours after dripping is finished, transferring the obtained homogeneous solution into a stainless steel reaction kettle with polytetrafluoroethylene, placing the stainless steel reaction kettle into a drying oven for reaction for 25 hours at 100 ℃, and fully washing reactants by adopting ethanol and hydrochloric acid to obtain PMO with amino;
(3) Dispersing 6 parts by mass of PMO with amino obtained in the step (2) in 200 parts by mass of dichloromethane, fully and uniformly stirring, adding 4 parts by mass of acylchlorinated metalloporphyrin obtained in the step (1), stirring until the acylchlorinated metalloporphyrin is dissolved, dropwise adding 2 drops of DMF (dimethyl formamide) as a catalyst, introducing nitrogen, reacting for 25 hours at 120 ℃, filtering after the reaction is finished, and fully washing to obtain the metalloporphyrin-mesoporous organic silicon oxide photocatalytic material; wherein the metalloporphyrin accounts for 18 wt% of the photocatalytic material.
Example 2
(1) Dissolving 0.04 part by mass of metal-coordinated tetracarboxyphenyl porphyrin (TCPP) in 400 parts by mass of DMF (dimethyl formamide), introducing nitrogen, adding 3 parts by mass of thionyl chloride, heating and refluxing for reaction at the reaction temperature of 60 ℃ for 8 hours, and evaporating to remove unreacted thionyl chloride and redundant solvent to obtain acyl-chlorinated metalloporphyrin;
(2) cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, polyvinylpyrrolidone (PVP) is used as a protective agent, 5 parts by mass of CTAB and 0.8 part by mass of PVP are respectively added into 200 parts by mass of a mixed solution of water and ethanol, and stirring and dissolving are carried out; slowly dripping 8 parts by mass of 3-aminopropyltriethoxysilane and 20 parts by mass of 1, 2-bis (trimethoxysilyl) ethane into the solution under continuous stirring, continuously stirring for 3 hours after dripping is finished, transferring the obtained homogeneous solution into a stainless steel reaction kettle with polytetrafluoroethylene, placing the stainless steel reaction kettle into a drying oven for reaction at 130 ℃ for 30 hours, and fully washing reactants by adopting ethanol and hydrochloric acid to obtain PMO with amino;
(3) Dispersing 8 parts by mass of PMO with amino obtained in the step (2) in 300 parts by mass of dichloromethane, fully and uniformly stirring, adding 4 parts by mass of acylchlorinated metalloporphyrin obtained in the step (1), stirring until the acylchlorinated metalloporphyrin is dissolved, dropwise adding 3 drops of DMF (dimethyl formamide) as a catalyst, introducing nitrogen, reacting at 130 ℃ for 30 hours, filtering after the reaction is finished, and fully washing to obtain the metalloporphyrin-mesoporous organic silicon oxide photocatalytic material; wherein the metalloporphyrin accounts for 15 wt% of the photocatalytic material.
Comparative example 1
The metalloporphyrin-silicon oxide composite material is prepared by adopting a traditional impregnation method, wherein the metalloporphyrin accounts for 18 wt% of the composite material.
Example 3
Carrying out a photocatalytic degradation test on the photocatalytic material prepared in the embodiment 1-2 and the composite material obtained in the comparative example 1 by using methyl orange as a test pollutant; firstly, preparing 150ml of 0.1mM methyl orange aqueous solution; 20mg of the photocatalytic material prepared in examples 1-2 and comparative example 1 was added to the prepared methyl orange aqueous solution and left to stand in the dark for 2 hours to reach adsorption equilibrium. The system was irradiated with 300W xenon for 3h photocatalytic degradation test. And filtering and collecting the degraded photocatalytic material, and repeating the steps to perform 5 times of cycle test. The test results are shown in table 1.
TABLE 1 degradation efficiency of methyl orange by different catalysts
As can be seen from table 1, the initial degradation rates of the photocatalytic materials prepared in examples 1 and 2 of the present invention to methyl orange are slightly better than those of the metalloporphyrin-silicon oxide composite materials prepared by the conventional impregnation loading method. However, after 5 cycles, the photocatalytic material prepared by the method can still maintain the degradation rate of more than 90%, and the degradation rate of the metalloporphyrin-silicon oxide composite material prepared by the traditional impregnation loading method is greatly reduced, which shows that the photocatalytic material prepared by the method has higher stability and can be recycled for multiple times.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. The application of the metalloporphyrin-mesoporous organic silicon oxide composite material in photocatalytic degradation of organic pollutants is characterized in that the metalloporphyrin-mesoporous organic silicon oxide composite material is put into wastewater containing the organic pollutants, is shaded to achieve adsorption balance, and is irradiated by a xenon lamp to perform photocatalytic degradation reaction; and after the reaction is finished, filtering and collecting the composite material, repeating the operation, and performing cyclic degradation reaction for 5-100 times.
2. The use according to claim 1, wherein the metalloporphyrin-mesoporous organic silicon oxide composite material uses mesoporous organic silicon oxide as a carrier, metalloporphyrin is a photocatalytic active component, and the metalloporphyrin and the mesoporous organic silicon oxide are connected through an amide bond; the metalloporphyrin accounts for 10-20wt% of the photocatalytic material.
3. Use according to claim 2, wherein the coordinating metal in the metalloporphyrin is selected from the group consisting of Ti, Fe, Cu, Zn, Ni, Cr, Co.
4. The use according to any one of claims 1 to 3, wherein the preparation method of the metalloporphyrin-mesoporous organic silica composite material comprises the following preparation steps:
(1) dissolving 0.01-0.05 part by mass of metal coordinated tetracarboxyphenyl porphyrin (TCPP) in 500 parts by mass of DMF (dimethyl formamide), introducing nitrogen, adding 1-3 parts by mass of thionyl chloride, heating and refluxing for reaction at 40-80 ℃ for 3-8h, and evaporating to remove unreacted thionyl chloride and redundant solvent to obtain acylchlorinated metalloporphyrin;
(2) cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, polyvinylpyrrolidone (PVP) is used as a protective agent, 1-5 parts by mass of CTAB and 0.3-1 part by mass of PVP are respectively added into a mixed solution of water and ethanol of 200 parts by mass of 150-sodium chloride, and stirring and dissolving are carried out; slowly dripping 3-10 parts by mass of 3-aminopropyltriethoxysilane and 10-20 parts by mass of 1, 2-bis (trimethoxysilyl) ethane into the solution under continuous stirring, continuously stirring for 2-3h after dripping is finished, transferring the obtained homogeneous solution into a stainless steel reaction kettle with polytetrafluoroethylene, placing the stainless steel reaction kettle into a drying oven for reaction for 20-30h at 80-130 ℃, and fully washing reactants by adopting ethanol and hydrochloric acid to obtain PMO with amino;
(3) Dispersing 5-8 parts by mass of PMO with amino obtained in the step (2) in 300 parts by mass of dichloromethane, fully and uniformly stirring, adding 2-5 parts by mass of acylchlorinated metalloporphyrin obtained in the step (1), stirring until dissolving, dropwise adding 1-3 drops of DMF (dimethyl formamide) as a catalyst, introducing nitrogen, reacting for 20-40h at 80-160 ℃, filtering after the reaction is finished, and fully washing to obtain the metalloporphyrin-mesoporous organic silicon oxide photocatalytic material.
5. The use according to claim 4, wherein in step (2), the mass ratio of 3-aminopropyltriethoxysilane to 1, 2-bis (trimethoxysilyl) ethane is 0.3-0.5: 1.
6. The use according to claim 4, wherein the temperature of the amidation reaction in step (3) is preferably 100 ℃ to 130 ℃, and the reaction time is preferably 20 to 30 hours.
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