CN111841637A - Metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and preparation method thereof - Google Patents

Metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and preparation method thereof Download PDF

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CN111841637A
CN111841637A CN202010585085.XA CN202010585085A CN111841637A CN 111841637 A CN111841637 A CN 111841637A CN 202010585085 A CN202010585085 A CN 202010585085A CN 111841637 A CN111841637 A CN 111841637A
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metalloporphyrin
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silicon oxide
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CN111841637B (en
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朱轶宁
仲超
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Taizhou Jiurun Environmental Protection Technology Co ltd
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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
    • B01J31/16—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
    • B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
    • B01J35/39—
    • B01J35/60—
    • 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
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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    • 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
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    • C02F2305/10—Photocatalysts

Abstract

The invention relates to a metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and a preparation method thereof, belonging to the technical field of 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 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 initial degradation rate of the photocatalytic material prepared by the method for the simulated pollutant methyl orange can reach 96.8%, the degradation rate can still be maintained to be more than 90% after 5 times of circulation, the photocatalytic material is obviously superior to the metalloporphyrin-silicon oxide composite material prepared by the traditional impregnation loading method, and the photocatalytic material has potential application value.

Description

Metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and preparation method thereof
Technical Field
The invention relates to a metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and a preparation method thereof, belonging to the technical field of photocatalytic degradation of organic pollutants.
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.
On the basis of the prior art, the invention firstly develops the metalloporphyrin-mesoporous organic silicon oxide material bridged by chemical covalent bonds. 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.
Disclosure of Invention
One of the purposes of the invention is to provide a metalloporphyrin-mesoporous organic silicon oxide photocatalytic material, wherein the photocatalytic material takes mesoporous organic silicon oxide as a carrier, metalloporphyrin as 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.
The second purpose of the invention is to provide a preparation method of the metalloporphyrin-mesoporous organic silicon oxide photocatalytic material, which 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
Figure BDA0002552602070000051
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 (5)

1. A metalloporphyrin-mesoporous organic silicon oxide photocatalytic material is characterized in that the photocatalytic material takes mesoporous organic silicon oxide as a carrier, metalloporphyrin as 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.
2. The photocatalytic material of claim 1, wherein the coordination metal in the metalloporphyrin is selected from the group consisting of Ti, Fe, Cu, Zn, Ni, Cr, and Co.
3. The preparation method of metalloporphyrin-mesoporous organic silicon oxide photocatalytic material according to claim 1, characterized by comprising 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.
4. The production method according to claim 3, wherein in the step (2), the mass ratio of 3-aminopropyltriethoxysilane to 1, 2-bis (trimethoxysilyl) ethane is 0.3-0.5: 1.
5. The process according to claim 3, wherein the temperature of the amidation reaction in the step (3) is preferably 100 ℃ to 130 ℃ and the reaction time is preferably 20 to 30 hours.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033097A (en) * 2007-02-12 2007-09-12 杭州师范学院 Method of preparing metalloporphyrin/silicon dioxide degradation agent
CN102941122A (en) * 2012-10-23 2013-02-27 中北大学 Immobilization cationic metal porphyrin/heteropolyanion composite catalyst, preparation method and application method thereof
CN103554302A (en) * 2013-10-29 2014-02-05 广西大学 Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin
CN103657726A (en) * 2013-12-23 2014-03-26 湖南大学 Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst
CN105289734A (en) * 2015-10-28 2016-02-03 湖南大学 Method for degrading organic dye through metal organic framework film based on metalloporphyrin
CN109569721A (en) * 2018-12-27 2019-04-05 南京医科大学 A kind of preparation method and application of PORPHYRIN IRON modification mesopore silicon oxide composite material
CN109926096A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 One-step method prepares the meso pore silicon oxide material of metalloporphyrin functional and its application in heterogeneous catalysis

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033097A (en) * 2007-02-12 2007-09-12 杭州师范学院 Method of preparing metalloporphyrin/silicon dioxide degradation agent
CN102941122A (en) * 2012-10-23 2013-02-27 中北大学 Immobilization cationic metal porphyrin/heteropolyanion composite catalyst, preparation method and application method thereof
CN103554302A (en) * 2013-10-29 2014-02-05 广西大学 Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin
CN103657726A (en) * 2013-12-23 2014-03-26 湖南大学 Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst
CN105289734A (en) * 2015-10-28 2016-02-03 湖南大学 Method for degrading organic dye through metal organic framework film based on metalloporphyrin
CN109926096A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 One-step method prepares the meso pore silicon oxide material of metalloporphyrin functional and its application in heterogeneous catalysis
CN109569721A (en) * 2018-12-27 2019-04-05 南京医科大学 A kind of preparation method and application of PORPHYRIN IRON modification mesopore silicon oxide composite material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHIARA MAURIELLO-JIMENEZ: "Porphyrin-functionalized mesoporous organosilica nanoparticles for two-photon imaging of cancer cells and drug delivery", 《J. MATER. CHEM. B》 *
EUN-YOUNG JEONG: "Synthesis of porphyrin-bridged periodic mesoporous organosilica and their catalytic applications", 《RES CHEM INTERMED》 *
王琪莹: "氧化硅基固载金属卟啉多相仿生催化剂研究进展", 《功能材料》 *
黄萍: "空心介孔有机硅的可控制备与肿瘤诊疗应用研究", 《中国优秀硕士学位论文全文数据库医药卫生科技辑》 *

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