CN112221541B - Polyacid-porphyrin hybrid material and preparation method and application thereof - Google Patents
Polyacid-porphyrin hybrid material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 25
- 229910020881 PMo12O40 Inorganic materials 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 235000013824 polyphenols Nutrition 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000126 substance Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000011071 total organic carbon measurement Methods 0.000 description 2
- 238000010396 two-hybrid screening Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/39—
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of hybrid materials, in particular to a polyacid-porphyrin hybrid material and a preparation method and application thereof. The polyacid-porphyrin hybrid material is composed of FeTCPP cations and polyacid anions, wherein the FeTCPP cations and the polyacid anions are combined through electrostatic attraction, and the polyacid anions are PW12O40 3‑Or PMo12O40 3‑. The invention uses polyacid anions PW12O40 3‑Or PMo12O40 3‑The polyacid anions have excellent charge transmission performance by being introduced into FeTCPP cations and combined with the FeTCPP cations through electrostatic attraction, so that the transmission and separation of photogenerated carriers in the FeTCPP cations are effectively improved, the charge transfer impedance is reduced, and the obtained polyacid-porphyrin hybrid material has higher photocatalytic efficiency.
Description
Technical Field
The invention relates to the technical field of hybrid materials, in particular to a polyacid-porphyrin hybrid material and a preparation method and application thereof.
Background
The concept of green chemistry and low pollution environments is gradually moving into our lives. However, how to effectively reduce the toxicity of various pollution systems in life still remains a great problem to researchers. Phenolic compounds are important chemical raw materials and can be used for producing dyes, medicines, phenolic resins, adhesives, preservatives and the like. Phenolic substances are in a wide variety and include phenol, cresol, aminophenol, nitrophenol, naphthol, chlorophenol, etc., with phenol being the most predominant contaminant. Phenol can cause harm to human body through skin contact, and further cause symptoms such as endocrine dyscrasia and the like. Whether from environmental or human health considerations, it is crucial to find materials that are effective in removing phenolics.
Metalloporphyrin materials are widely researched in recent years, and the complex electronic structure of the metalloporphyrin materials endows the metalloporphyrin materials with unique chemical properties, so that the metalloporphyrin materials have potential application prospects in the fields of solar cells, photoelectric materials and photocatalysis. Iron (III) chloride (FeTCPPCl) 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin is a synthetic precursor for a variety of hybrid materials, which inherit the ligand tetra (4-carboxyphenyl) porphyrin (H) in simulating the absorption of light in sunlight4TCPP). However, FeTCPPCl alone was used forThe photo-generated carriers of the degraded phenolic substances are easy to compound, and the charge transfer resistance is high, so that the photocatalytic performance of the degraded phenolic substances is poor.
Disclosure of Invention
The polyacid-porphyrin hybrid material provided by the invention has good catalytic performance and higher degradation rate on phenolic substances.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyacid-porphyrin hybrid material, which consists of FeTCPP cations and polyacid anions, wherein the FeTCPP cations and the polyacid anions are combined by electrostatic attraction, and the polyacid anions are PW12O40 3-Or PMo12O40 3-。
Preferably, the polyacid-porphyrin hybrid material has a spherical structure.
Preferably, the particle size of the polyacid-porphyrin hybrid material is more than 200nm
The invention provides a preparation method of the polyacid-porphyrin hybrid material, which comprises the following steps: mixing a water-soluble salt solution of FeTCPP with a polyacid solution, adjusting the pH value of the obtained mixed solution to be below 2 to form a precipitate, and carrying out solid-liquid separation to obtain a polyacid-porphyrin hybrid material; the polyacid is H3PW12O40Or H3PMo12O40。
Preferably, the water-soluble salt solution of FeTCPP is a potassium salt solution of FeTCPP or a sodium salt solution of FeTCPP.
Preferably, the molar ratio of the polyacid in the polyacid solution to the FeTCPP in the water-soluble salt solution of FeTCPP is 1: (1-6).
Preferably, the reagent used to adjust the pH of the resulting mixture to 2 or less is dilute hydrochloric acid.
Preferably, the solid-liquid separation further comprises washing and drying the obtained solid product.
The invention provides application of the polyacid-porphyrin hybrid material prepared by the preparation method in the scheme or the polyacid-porphyrin hybrid material prepared by the preparation method in the scheme as a photocatalyst.
Preferably, the application is the degradation of phenolics which include phenol.
The invention provides a polyacid-porphyrin hybrid material, which consists of FeTCPP cations and polyacid anions, wherein the FeTCPP cations and the polyacid anions are combined by electrostatic attraction, and the polyacid anions are PW12O40 3-Or PMo12O40 3-. The invention uses polyacid anions PW12O40 3-(hereinafter abbreviated as PW)12) Or PMo12O40 3-(PMo for short hereinafter)12) The polyacid anions have excellent charge transmission performance by being introduced into FeTCPP and combined with FeTCPP cations through electrostatic attraction, so that the transmission and separation of photogenerated carriers in the FeTCPP cations are effectively improved, the charge transfer impedance is reduced, and the obtained polyacid-porphyrin hybrid material has higher photocatalytic efficiency.
The results of the examples show that when the polyacid-porphyrin hybrid material is used for degrading phenol, the degradation rate of phenol is obviously higher than that of FeTCPPCl.
Drawings
FIG. 1 is an electron micrograph of the polyacid-porphyrin hybrid materials prepared in examples 1 to 5;
FIG. 2 shows FeTCPP-PW prepared in example 112EDX element map of (a);
FIG. 3 shows FeTCPP-PMo prepared in example 412EDX element map of (a);
FIG. 4 is a graph of UV-Vis spectra and Mottky plots for various materials;
FIG. 5 shows FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412And photocurrent and impedance curves for FeTCPPCl;
FIG. 6 shows FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412And the degradation curve of FeTCPPCl for phenol;
FIG. 7 shows FeTCPP-PW prepared in example 112Heshi (Chinese character of' HeshiFeTCPP-PMo prepared in example 412Total organic carbon measurement curve after photocatalysis of phenol.
Detailed Description
The invention provides a polyacid-porphyrin hybrid material, which consists of FeTCPP cations and polyacid anions, wherein the FeTCPP cations and the polyacid anions are combined by electrostatic attraction, and the polyacid anions are PW12O40 3-Or PMo12O40 3-。
In the invention, the FeTCPP cation is a cation of FeTCPPCl and is in positive trivalent; PW (pseudo wire)12O40 3-And PMo12O40 3-Are respectively H3PW12O40And H3PMo12O40Anion of (2), PW12O40 3-Abbreviated as PW12，PMo12O40 3-Short for PMo12(ii) a The polyacid-porphyrin hybrid material is neutral in electricity.
In the present invention, the polyacid-porphyrin hybrid material is preferably a spherical structure. In the invention, the particle size of the polyacid-porphyrin hybrid material is preferably more than 200nm, and more preferably 200-500 nm. In the invention, when the polyacid-porphyrin hybrid material is FeTCPP-PW12When the particle size of the polyacid-porphyrin hybrid material is 200nm, the polyacid-porphyrin hybrid material has the best catalytic performance; when the polyacid-porphyrin hybrid material is FeTCPP-PMo12When the particle size of the polyacid-porphyrin hybrid material is 250nm, the polyacid-porphyrin hybrid material has the best catalytic performance.
In the embodiment of the invention, the particle size of the polyacid-porphyrin hybrid material is 200nm, 250nm, 350nm or 500 nm.
The invention utilizes polyacid anions PW12O40 3-And PMo12O40 3-Good charge transport property, and the polyacid anion PW12Or PMo12Introduced into FeTCPP cation, and combined with the FeTCPP cation through electrostatic attraction, thereby effectively improving the transmission and separation of FeTCPP photon-generated carriers and reducing the number of the photon-generated carriersThe charge transfer resistance is low, and the obtained polyacid-porphyrin hybrid material has good photocatalytic efficiency.
The invention provides a preparation method of the polyacid-porphyrin hybrid material, which comprises the following steps: mixing a water-soluble salt solution of FeTCPP with a polyacid solution, adjusting the pH value of the obtained mixed solution to be below 2 to form a precipitate, and carrying out solid-liquid separation to obtain a polyacid-porphyrin hybrid material; the polyacid is H3PW12O40Or H3PMo12O40。
In the present invention, the water-soluble salt solution of FeTCPP is preferably a potassium salt solution of FeTCPP or a sodium salt solution of FeTCPP. In the invention, the potassium salt solution of the FeTCPP is preferably obtained by mixing FeTCPPCl and KOH solution for reaction, and the sodium salt solution of the FeTCPP is preferably obtained by mixing FeTCPPCl and NaOH solution for reaction. In the present invention, the concentration of the KOH solution or NaOH solution is preferably 0.1 to 0.5 mmol/mL-1More preferably 0.2 to 0.4 mmol/mL-1(ii) a The molar ratio of KOH in the KOH solution or NaOH in the NaOH solution to FeTCPPCl is preferably more than 4, and more preferably 4-5. In the invention, FeTCPPCl is insoluble in water and shows acidity, and the ligand of the FeTCPPCl has 4 carboxyl groups and can react with KOH or NaOH to generate potassium salt or sodium salt which is dissolved in water.
The source of the FeTCPPCl is not particularly required in the invention, and the FeTCPPCl can be prepared by adopting commercial FeTCPPCl or a well-known preparation method which is well known to a person skilled in the art.
In the embodiment of the invention, the FeTCPPCl is prepared by adopting the following method:
refluxing 100mL of propionic acid, 3.0g of pyrrole and 6.9g of methyl p-formylbenzoate in the dark for 12 hours to obtain purple crystals;
0.8g of the violet crystals, 2.5g of FeCl3·4H2Refluxing O in 100mL of DMF for 6h, cooling to room temperature, and adding 150mL of deionized water to obtain a dark brown precipitate;
and dissolving the dark brown precipitate in chloroform, washing with a potassium hydroxide solution and water, and drying to obtain a dark brown crystal, namely FeTCPPCl.
In the present invention, the polyacid solution is preferably obtained by dissolving a polyacid in water. The method has no special requirement on the dosage of the water, and can completely dissolve the polyacid. In the present invention, the polyacid is H3PW12O40Or H3PMo12O40. The source of the polyacid in the present invention is not particularly limited, and commercially available products known in the art can be used.
In the present invention, the molar ratio of polyacid in the polyacid solution to the FeTCPP in the water-soluble salt solution of FeTCPP is preferably 1: (1-6), in the embodiment of the invention, the ratio is 1:1, 1:3 or 1: 6. The invention controls the particle size of the polyacid-porphyrin hybrid material by controlling the molar ratio of the polyacid in the polyacid solution and the FeTCPP in the water-soluble salt solution of the FeTCPP. When the relative concentration of FeTCPP is increased, the increase in concentration during particle binding causes the particle size to become larger.
In the embodiment of the invention, when PW is used12When the molar ratio of the polyacid to the FeTCPP positive ions is 1:1, the particle size of the polyacid-porphyrin hybrid material is 200 nm; when PW is generated12When the molar ratio of the polyacid to the FeTCPP cation is 1:3, the particle size of the polyacid-porphyrin hybrid material is 350 nm; when PW is generated12When the molar ratio of the polyacid to the FeTCPP cation is 1:6, the particle size of the polyacid-porphyrin hybrid material is 500 nm; when PMo is in12When the molar ratio of the polyacid to the FeTCPP cation is 1:1, the particle size of the polyacid-porphyrin hybrid material is 250 nm; when PMo is in12And when the molar ratio of the polyacid to the FeTCPP cation is 1:3, the particle size of the polyacid-porphyrin hybrid material is 500 nm.
In the present invention, the process of mixing the water-soluble salt solution of FeTCPP and the polyacid solution is preferably: the aqueous salt solution of FeTCPP was added dropwise to the polyacid solution. The present invention has no particular requirement on the rate of the dropping, and for example, the dropping may be performed dropwise (about 1 drop per second). The invention adopts a dripping mode to ensure that the hybrid material particles are uniformly distributed.
After the mixing is finished, the pH value of the obtained mixed solution is adjusted to be below 2, precipitate is formed, and the polyacid-porphyrin hybrid material is obtained after solid-liquid separation.
In the present invention, the reagent used for adjusting the pH of the mixed solution to 2 or less is preferably dilute hydrochloric acid, and the mass fraction of the dilute hydrochloric acid is not particularly limited in the present invention, and may be any of those known in the art having a mass fraction of less than 20%.
In the present invention, the process of adjusting the pH is preferably carried out under stirring. The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art.
The pH value of the mixed solution is adjusted to be below 2, so that anions of the polyacid and FeTCPP cations are combined more easily to form precipitates, and when the precipitates are not increased any more, the solid-liquid separation is carried out to obtain the polyacid-porphyrin hybrid material.
The invention has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode which is well known in the field, such as filtration, can be adopted.
After solid-liquid separation, the invention preferably also comprises washing and drying the obtained solid to obtain the polyacid-porphyrin hybrid material. The invention has no special requirements on the washing process, and preferably adopts distilled water to repeatedly wash the materials.
The present invention has no special requirement for the drying process, and the drying process well known in the art can be adopted.
The invention provides application of the polyacid-porphyrin hybrid material prepared by the preparation method in the scheme or the polyacid-porphyrin hybrid material prepared by the preparation method in the scheme as a photocatalyst.
In the present invention, the application is preferably the degradation of a phenolic substance, preferably comprising phenol. The concentration of the phenolic substances is not particularly required, and any concentration can be adopted, and in the embodiment of the invention, the concentration is 400 mg/L. In the case of phenol, the degradation products are carbon dioxide and water.
The invention has no special requirements on the application process, and the application process well known in the field can be adopted. In the embodiment of the invention, the polyacid-porphyrin hybrid material is added into a solution containing the phenolic substance, the adsorption equilibrium is stirred under the dark condition, and then the photocatalytic reaction is carried out under the irradiation of visible light. In the embodiment of the present inventionThe optical power density of the visible light is 100mW/cm2. In one embodiment, the time for the adsorption equilibrium is 10 min.
The polyacid-porphyrin hybrid materials provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
The FeTCPPCl used in the following examples was prepared by the following method:
refluxing 100mL of propionic acid, 3.0g of pyrrole and 6.9g of methyl p-formylbenzoate in the dark for 12 hours to obtain purple crystals;
0.8g of the violet crystals, 2.5g of FeCl3·4H2Refluxing O in 100mL of DMF for 6h, cooling to room temperature, and adding 150mL of deionized water to obtain a dark brown precipitate;
and dissolving the dark brown precipitate in chloroform, washing with a potassium hydroxide solution and water, and drying to obtain a dark brown crystal, namely FeTCPPCl.
Examples 1 to 3 are FeTCPP-PW12The preparation of (1):
example 1
Dissolving 0.1mmol phosphotungstic acid in 5mL water to obtain H3PW12O40A solution; 0.1mmol of FeTCPPCl and 5mL of KOH (0.1 mmol. multidot.mL)-1) Mixing the solutions to obtain a potassium salt solution of FeTCPP; slowly dropping FeTCPP potassium salt solution into (1 drop per second) H3PW12O40In the solution, the pH value is adjusted to 2 by using dilute hydrochloric acid under the stirring condition, and the filtered reddish brown precipitate is repeatedly washed by using distilled water and dried to obtain the polyacid-porphyrin hybrid material with the particle size of 200 nm.
Example 2
Dissolving 0.1mmol phosphotungstic acid in 5mL water to obtain H3PW12O40A solution; 0.3mmol of FeTCPPCl and 5mL of KOH (0.25 mmol. multidot.mL)-1) Mixing the solutions to obtain a potassium salt solution of FeTCPP; slowly dropping (1 drop per second) FeTCPP potassium salt solution into H3PW12O40Adjusting pH to 2 with dilute hydrochloric acid under stirring, filtering, and repeatedly washing the red brown precipitate with distilled waterAnd drying to obtain the polyacid-porphyrin hybrid material with the particle size of 350 nm.
Example 3
Dissolving 0.1mmol phosphotungstic acid in 5mL water to obtain H3PW12O40A solution; 0.6mmol of FeTCPPCl and 5mL of KOH (0.5 mmol. multidot.mL)-1) Mixing the solutions to obtain a potassium salt solution of FeTCPP; slowly dropping FeTCPP potassium salt solution into (1 drop per second) H3PW12O40In the solution, the pH value is adjusted to 2 by using dilute hydrochloric acid under the stirring condition, and the filtered reddish brown precipitate is repeatedly washed by using distilled water and dried to obtain the polyacid-porphyrin hybrid material with the particle size of 500 nm.
Examples 4 to 5 are FeTCPP-PMo12The preparation of (1):
example 4
Dissolving 0.1mmol of phosphomolybdic acid in 5mL of water to obtain H3PMo12O40A solution; 0.1mmol of FeTCPPCl and 5mL of KOH (0.1 mmol. multidot.mL)-1) Mixing the solutions to obtain a potassium salt solution of FeTCPP; slowly dropping FeTCPP potassium salt solution into (1 drop per second) H3PMo12O40In the solution, the pH value is adjusted to 2 by using dilute hydrochloric acid under the stirring condition, and the filtered reddish brown precipitate is repeatedly washed by using distilled water and dried to obtain the polyacid-porphyrin hybrid material with the particle size of 250 nm.
Example 5
Dissolving 0.1mmol of phosphomolybdic acid in 5mL of water to obtain H3PMo12O40A solution; 0.3mmol of FeTCPPCl and 5mL of KOH (0.25 mmol. multidot.mL)-1) Mixing the solutions to obtain a potassium salt solution of FeTCPP; slowly dropping FeTCPP potassium salt solution into (1 drop per second) H3PMo12O40In the solution, the pH value is adjusted to 2 by using dilute hydrochloric acid under the stirring condition, and the filtered reddish brown precipitate is repeatedly washed by using distilled water and dried to obtain the polyacid-porphyrin hybrid material with the particle size of 500 nm.
Structural and performance characterization
The products prepared in examples 1 to 5 were observed by an electron microscope, and the results are shown in FIG. 1. In FIG. 1, a to c are PW in the order of12Scanning electron micrographs of FeTCPP and FeTCPP in molar ratios of 1:1, 1:3 and 1:6, respectively(ii) a d and e are PMo respectively12A scanning electron microscope picture with the molar ratio of FeTCPP being 1:3 and 1: 1; f is PW12And a transmission electron micrograph of FeTCPP at a molar ratio of 1: 1. As can be seen from FIG. 1, the particles of the two hybrid materials are both spherical structures, the particle sizes synthesized from different raw material ratios are different from 200nm to 500nm, and the specific sizes are controllable by controlling the raw material dosage.
FIG. 2 shows FeTCPP-PW prepared in example 112EDX element map of (a). As can be seen from FIG. 2, in FeTCPP-PW12In the hybrid material, six elements of C, N, O, P, Fe and W exist in different contents.
FIG. 3 shows FeTCPP-PMo prepared in example 412EDX element map of (a). As can be seen from FIG. 3, in FeTCPP-PMo12In the hybrid material, six elements of C, N, O, P, Fe and Mo exist in different contents.
XPS tests are carried out on the products prepared in the embodiments 1-5, and the XPS tests show that elements in the combined particles have no valence change, which indicates that the polyacid-porphyrin hybrid material is formed by electrostatic combination of anions and cations.
FIG. 4 is a graph of UV-visible spectrum and Mottky curves for different materials, where (a) is FeTCPPCl, H3PMo12O40、H3PW12O40FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412The (b) is FeTCPPCl or H3PMo12O40、H3PW12O40FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412Band gap spectrum of (c) FeTCPP-PW prepared in example 112The Mott Schottky curve of (d) is FeTCPP-PMo prepared in example 412Mott schottky curve of (a). As can be seen from FIG. 4, pure FeTCPPCl has strong absorption almost in the whole light region, and the hybrid material FeTCPP-PW12And FeTCPP-PMo12This property is well inherited. H3PMo12O40And a small amount of absorption is also generated in the visible light wavelength range of 420nm to 500 nm. FeTCPP-PW12And FeTCPP-PMo12The band gap energies of the two hybrid materials are 1.25eV and 1.06eV respectively.
FIG. 5 shows FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412And photocurrent and impedance curves (EIS) for FeTCPPCl. The photocurrent response and EIS results further confirm the excellent performance of the hybrid materials. After FeTCPP cation is combined with polyacid anion, the resistance is obviously reduced, and the charge transfer efficiency is improved; the empty orbit of the polyacid accelerates the transfer of interface electrons and enhances the separation of electron hole pairs; transient photocurrent response also indicates that the lifetime of photogenerated carriers in the hybrid material is extended.
Application example
To the reaction vessel were added 10mL of a phenol solution (400mg/L) and 20mg of a catalyst. The mixture was stirred in the dark for 10 minutes, after equilibration of the adsorption under visible light (100 mW/cm)2) Irradiating the reaction container to circulate condensed water, keeping room temperature, sampling periodically, filtering the catalyst, and detecting the sample.
The catalyst adopts FeTCPPCl and FeTCPP-PW prepared in example 1 respectively12FeTCPP-PMo prepared in example 412。
FIG. 6 shows FeTCPPCl, FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412Degradation curve for phenol. As can be seen from the graph, phenol was almost completely degraded within 15 minutes, and FeTCPP-PMo12The degradation effect is better than that of FeTCPP-PW12. Specific degradation rate: FeTCPP-PW1298.10% FeTCPP-PMo1299.13% and 16.80% of FeTCPPCl. Meanwhile, the degradation test is also carried out on the polyacid-hybrid materials prepared in other examples, the degradation rate of the product in example 2 is 96.4%, the degradation rate of the product in example 3 is 95.2%, and the degradation rate of the product in example 5 is 98.9% within 15 minutes.
FIG. 7 shows FeTCPP-PW prepared in example 112FeTCPP-PMo prepared in example 412Total organic carbon measurement curve after photocatalysis of phenol. As can be seen from the figure, the two materials have good degradation effect on phenol, the mineralization rate can reach 93.5 percent, and FeTCPP-PMo12The mineralization efficiency of the phenol is better than that of FeTCPP-PW12。
Note: mineralization rate means complete conversion to CO2And H2The degree of O.
The figures 4-7 show that the polyacid anions introduced into FeTCPP can enable the hybrid material to absorb more visible light photons, and the photocatalytic activity is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The polyacid-porphyrin hybrid material consists of FeTCPP cations and polyacid anions, wherein the FeTCPP cations and the polyacid anions are combined through electrostatic attraction, and the polyacid anions are PW12O40 3-Or PMo12O40 3-(ii) a The particle size of the polyacid-porphyrin hybrid material is 200-250 nm; the polyacid-porphyrin hybrid material is used for degrading phenols.
2. The polyacid-porphyrin hybrid material according to claim 1, wherein said polyacid-porphyrin hybrid material has a spherical structure.
3. A method for preparing polyacid-porphyrin hybrid material according to any one of claims 1 to 2, comprising the following steps: mixing a water-soluble salt solution of FeTCPP with a polyacid solution, adjusting the pH value of the obtained mixed solution to be below 2 to form a precipitate, and carrying out solid-liquid separation to obtain a polyacid-porphyrin hybrid material; the polyacid is H3PW12O40Or H3PMo12O40(ii) a The molar ratio of the polyacid in the polyacid solution to the FeTCPP in the water-soluble salt solution of the FeTCPP is 1: 1.
4. the method according to claim 3, wherein the water-soluble salt solution of FeTCPP is a potassium salt solution of FeTCPP or a sodium salt solution of FeTCPP.
5. The method according to claim 3, wherein the reagent used for adjusting the pH of the mixed solution to 2 or less is diluted hydrochloric acid.
6. The method according to claim 3, wherein the solid-liquid separation further comprises washing and drying the obtained solid product.
7. The polyacid-porphyrin hybrid material of any one of claims 1 to 2 or the polyacid-porphyrin hybrid material prepared by the preparation method of any one of claims 3 to 6 is used as a photocatalyst; the application is the degradation of phenolics, which include phenol.
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