CN116550385A - Titanium-porous organic cage photocatalyst and preparation method and application thereof - Google Patents
Titanium-porous organic cage photocatalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011941 photocatalyst Substances 0.000 title abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 29
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims 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 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical group [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 208000030452 Transient pseudohypoaldosteronism Diseases 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 6
- 238000001465 metallisation Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 22
- 239000000975 dye Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006263 metalation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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
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Abstract
The invention discloses a titanium-porous organic cage photocatalyst and a preparation method and application thereof, wherein resorcinol calix [4] arene-based porous organic cage HPOC-401 is used as a raw material, and a metal site highly-dispersed titanium-porous organic cage HPOC-401-Ti photocatalyst is obtained through post-modification metallization reaction (PSM), so that a novel method for preparing an inorganic-organic composite photocatalyst containing titanium is provided. The method has the advantages of low cost of materials, simple preparation process, simple and convenient operation, low reaction temperature, larger specific surface area of the prepared product, good stability and repeatability, strong operability and practicability, and potential application value and strong practicability in photocatalytic degradation of dye pollutants in water.
Description
Technical Field
The invention belongs to the field of material synthesis and catalysis, and particularly relates to a non-noble metal titanium (Ti) -Porous Organic Cage (POC) composite material, a preparation method and application thereof.
Background
In the last decades, with the continued development of the printing and dyeing industry, dye wastewater has become one of the important pollutants in environmental water bodies. Scientists have studied various methods for removing dye pollutants in water, such as chemical precipitation, electrolysis, evaporation, distillation, adsorption separation, ion exchange, solvent extraction, reverse osmosis, microfiltration, photocatalytic degradation, and the like. Among the above-mentioned methods, the photocatalytic degradation method for removing dye pollutants from dye wastewater is a green, environment-friendly, novel, efficient and energy-saving method, and can lead the dye remained in the water body to be finally converted into carbon dioxide, water or other nontoxic and harmless small molecular substances.
Titanium dioxide (TiO 2 ) Semiconductor materials are receiving great attention because of their wide range of applications, high catalytic efficiency, low toxicity, cleanliness, no pollution, and low cost. However, due to TiO 2 The band gap of the semiconductor is wider, and the absorbed light is mainly concentrated in the ultraviolet range<5% of the solar spectrum), so that the utilization rate of sunlight is very low, which greatly restricts the practical application of the solar energy-assisted solar energy system in photocatalysis. Therefore, the development and application of the simple, good repeatability and low cost synthesis method for preparing the titanium-based photocatalyst capable of efficiently utilizing sunlight are necessary.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a metal site high-dispersion titanium-porous organic cage photocatalyst by using a porous organic cage under simple and mild conditions. The method for preparing the titanium-porous organic cage photocatalyst by adopting the post-modification metallization synthesis method has the advantages of simple operation process, mild reaction and good repeatability and controllability.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
the invention provides a composite material (abbreviated as HPOC-401-Ti), which comprises a porous organic cage compound and metallic titanium loaded on the porous organic cage compound.
According to an embodiment of the present invention, in the composite material, a porous organic cage compound is used as a ligand, metallic titanium is used as an active component, and Ti is bonded through coordination bonds 4+ Chelate to the porous organic cage compound to form a complex. Preferably, ti is added by O/N/O sites 4+ Chelate to the porous organic cage compound to form a complex.
Preferably, the composite material has a molecular structure as shown in fig. 15.
According to an embodiment of the present invention, the composite material comprises 5 to 10% by mass of Ti, and exemplary amounts thereof are 5%, 8.63% and 10%.
According to an embodiment of the invention, the composite material has an ultraviolet-visible diffuse reflectance spectrum (UV-vis) substantially as shown in fig. 17, with the ultraviolet absorption edge at 872nm. According to an embodiment of the invention, the composite material is a red powdery sample, the surface of which is rough.
According to an embodiment of the invention, the BET surface area of the composite material is 976 to 977m 2 g -1 Exemplary is 976.5m 2 g -1 。
According to an embodiment of the present invention, the porous organic cage compound (abbreviated as HPOC-401), (C 384 H 408 N 48 O 72 ) Has a structure shown in a formula I:
according to an embodiment of the invention, the HPOC-401 is obtained from the reaction of tetra-aldehyde resorcinol calix [4] arene (C4 RACHO) and p-dibenzoic acid dihydrazide (TPHA).
Preferably, the molar ratio of tetra aldehyde resorcinol calix [4] arene (C4 RACHO) to p-dibenzoic acid dihydrazide (TPHA) is 1 (1-3), and exemplary is 1:1, 1:2, 1:3.
Preferably, the temperature of the reaction is 80 to 120 ℃, for example 100 ℃; the reaction time is 6 to 20 hours, for example 12 hours.
Preferably, the reaction is carried out in an organic solvent. For example, the solvent may be N, N-Dimethylformamide (DMF).
Preferably, the preparation method of the HPOC-401 further comprises the step of carrying out ultrasonic treatment on the reaction mixture to dissolve the solid raw materials before heating the reaction. Preferably, the time of the ultrasonic wave may be 10 to 30 minutes. An exemplary is about 20 minutes.
Preferably, the preparation method of the HPOC-401 further comprises the following steps: after the reaction, collecting HPOC-401 compound from the reaction liquid.
Preferably, the preparation method of the HPOC-401 further comprises the following steps: evaporating the reaction liquid obtained after the reaction is completed at a constant temperature to obtain the porous organic cage HPOC-401 crystal. For example, the temperature of the evaporation is room temperature; as another example, the evaporation time is 6-20 hours, for example 12 hours.
Preferably, the preparation method further comprises purifying the product obtained after evaporative crystallization. For example, by filtration, methanol washing, methanol exchange several times, drying, yellow powdery HPOC-401 crystals are obtained from which the guest solvent molecules are removed.
For example, the drying may be vacuum drying. Preferably, the temperature of the drying may be 60 to 100 ℃, and is exemplified by 100 ℃; the drying time is 6-20 hours, for example 12 hours.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystal has a symmetry center, a space group of Pnnn and a unit cell parameter ofα＝β＝γ＝90°。
According to the embodiment of the invention, the porous organic cage HPOC-401 crystal is an octahedral structure organic cage assembled by using 6 tetra-aldehyde resorcinol calix [4] arene ligands as vertexes and 12 p-dibenzoate dihydrazide ligands as edges. Preferably, the porous organic cage HPOC-401 crystals comprise oversized octahedral cavities and 8 triangular windows.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystals have a maximum cavity diameter and volume of about 3.25nm and
according to an embodiment of the invention, the porous organic cage HPOC-401 crystal has an intra-unit cell molecular number z=4.
According to an embodiment of the invention, the triangular window of the porous organic cage HPOC-401 crystals has an average length of about 2.0nm (which can pass through molecules having a diameter of about 0.95 nm).
According to the embodiment of the invention, the size of the HPOC-401 crystals of the porous organic cage is 1-3mm, and the surface is smoother.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystals are pale yellow tetrahedral crystals.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystals have a crystal structure as shown in FIG. 3.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystal has an X-ray powder diffraction pattern substantially as shown in FIG. 7.
According to an embodiment of the invention, the porous organic cage HPOC-401 crystals have a BET surface area of 3.5-3.6 m 2 g -1 Exemplary is 3.57m 2 g -1 。
The invention also provides a preparation method of the composite material, which comprises the following steps: comprises the steps of mixing the porous organic cage compound with a precursor containing Ti active metal components, and reacting to obtain the composite material.
According to an embodiment of the present invention, the precursor containing the Ti active metal component may be titanium acetylacetonate.
Preferably, the porous organic cage compound is reacted in a mass to volume ratio (mg: mL) of (1-5): 1, exemplary 1:1, 2:1, 3:1, 4:1, 5:1 with the Ti-active metal component containing precursor.
According to an embodiment of the invention, the temperature of the reaction is room temperature; as another example, the reaction time is 12-24 hours, for example 24 hours.
Preferably, the preparation method further comprises the process of carrying out solid-liquid separation on the reaction system after the reaction is finished to obtain a reaction product. For example, the solid-liquid separation may be by means known in the art, such as filtration.
According to an embodiment of the present invention, the preparation method further comprises washing the reaction product obtained by the solid-liquid separation. For example, the washing solvent may be methanol. As another example, the number of washes may be one, two or more.
According to an embodiment of the invention, the preparation method further comprises drying the washed reaction product. For example, the drying may be vacuum drying. Preferably, the temperature of the drying may be 60 to 100 ℃, and is exemplified by 100 ℃; the drying time is 6-20 hours, for example 12 hours.
According to an embodiment of the invention, the preparation method of the composite material comprises the steps of placing HPOC-401 in an titanyl acetylacetonate solution, soaking at room temperature, and then filtering, washing and drying to obtain the red powdery composite material HPOC-401-Ti.
The invention also provides application of the composite material as a photocatalytic material. Preferably in the photocatalytic degradation of dye contaminants.
According to embodiments of the present invention, the dye contaminants include, but are not limited to, methylene blue, rhodamine B, methyl orange.
The invention has the beneficial effects that:
porous organic cages (Porous organic cages, POCs) are a novel porous material which appears in recent years, comprise cavities with specific sizes, are stacked into an ordered structure by weak interaction by discrete building units, and have potential application prospects in the fields of gas storage and separation, sensing, catalysis, intelligent materials and the like, wherein the pores consist of cavities in the cages and stacked through holes. Since the structure contains rich nitrogen, oxygen and other sites, the original POC can be modified by Post-synthesis metallization (Post-synthetic metalation, PSM). Studies have shown that the performance can be modified by including various metals such as iron, cobalt, silver, gold, etc. on POC surfaces or cavities. The following are considered:
the invention provides a POC material functionalized by metal titanium, which combines the high specific surface area of the POC material through the titanium modified POC material, so that the material can efficiently enrich pollutants in water; meanwhile, POC can sensitize titanium metal sites, so that the absorption spectrum of the material to sunlight is enlarged, and the photocatalytic degradation performance of the metal sites to dye pollutants in water is promoted.
The invention uses resorcinol calix [4] arene-based porous organic cage HPOC-401 as a raw material, and obtains the titanium-porous organic cage HPOC-401-Ti photocatalyst with highly dispersed metal sites through post-modification metallization reaction (PSM), thereby providing a novel method for preparing the inorganic-organic composite photocatalyst containing titanium. The method has the advantages of low cost of materials, simple preparation process, simple and convenient operation, low reaction temperature, larger specific surface area of the prepared product, good stability and repeatability, strong operability and practicability, and potential application value and strong practicability in photocatalytic degradation of dye pollutants in water.
Drawings
FIG. 1 is a schematic diagram of the preparation of HPOC-401 in accordance with the present invention.
FIG. 2 is a diagram of a sample of powdered HPOC-401 after removal of solvent molecules.
FIG. 3 is a schematic diagram of a porous organic cage HPOC-401 synthesis.
FIG. 4 shows the nuclear magnetic hydrogen spectrum of HPOC-401 after immersion in water 1 H NMR)。
FIG. 5 is a high resolution mass spectrum (HR-MS) of HPOC-401.
FIG. 6 is an infrared spectrum (FT-IR) of HPOC-401.
FIG. 7 is a powder X-ray diffraction (PXRD) pattern of HPOC-401.
FIG. 8 is a thermogravimetric curve (TGA) of HPOC-401.
FIG. 9 is N of HPOC-401 2 Adsorption-desorption curves.
FIG. 10 is a diagram of a sample of powdered HPOC-401-Ti after removal of solvent molecules.
FIG. 11 is a schematic diagram of a polydisperse HPOC-401-Ti photocatalyst constructed using Post-modification metal synthesis (PSM, post-Synthetic Metalation).
FIG. 12 is a scanning electron microscope SEM-EDS spectrum of HPOC-401-Ti.
FIG. 13 is an infrared spectrum (FT-IR) of HPOC-401-Ti.
FIG. 14 is a powder X-ray diffraction (PXRD) pattern of HPOC-401-Ti.
FIG. 15 shows the molecular structure of HPOC-401-Ti.
FIG. 16 is a thermogravimetric analysis (TGA) of HPOC-401-Ti under nitrogen atmosphere.
FIG. 17N of HPOC-401-Ti 2 Adsorption-desorption curves.
FIG. 18 is a graph of HPOC-401-Ti ultraviolet-visible diffuse reflectance spectra (UV-vis).
FIG. 19 is a graph of the ultraviolet-visible absorption spectrum of HPOC-401-Ti for the photocatalytic degradation of methylene blue dye contaminants in water.
FIG. 20 is a graph of the ultraviolet-visible absorption spectrum of HPOC-401-Ti for the photocatalytic degradation of rhodamine B dye contaminants in water.
FIG. 21 is a graph of the ultraviolet-visible absorption spectrum of HPOC-401-Ti for the photocatalytic degradation of methyl orange dye contaminants in water.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The preparation method of HPOC-401-Ti comprises the following steps:
(1) Resorcinol calix [4] arene-based porous organic cage HPOC-401 crystals are synthesized in a pressure-resistant pipe by a conventional solvothermal method. Wherein C4RACHO (C4 racho=tetra aldehyde resorcinol calix [4] arene, 81mg,0.1 mmol) and TPHA (tpha=p-dibenzoic acid dihydrazide, 39mg,0.2 mmol) are dissolved in 12mL DMF (dmf=n, N-dimethylformamide). The solid sample was dissolved by sonication in an ultrasonic cleaner for about 20 minutes, and then the solution was heated in an oil bath at 100 ℃ for 12 hours. Then, the reaction solution was allowed to stand still and volatilize at room temperature for 12 hours to obtain pale yellow tetrahedral crystals having a grain size of 1 to 3mm (as shown in FIG. 1). Followed by filtration, methanol washing, methanol exchange several times. Finally, the mixture was dried in a vacuum oven (100 ℃) for 12 hours to give HPOC-401 (as shown in FIG. 2) as a yellow powder with the guest solvent molecules removed, in a yield of 70%.
HPOC-401 characterization means:
(1) The HPOC-401 structure was characterized by single crystal diffraction (SCXRD) and the results are shown in Table 1 below.
Table 1 shows the crystallographic data of HPOC-401
R 1 a ＝∑||F o |-|F c ||/∑|F o |. b wR 2 ＝{∑[w(F o 2 -F c 2 ) 2 ]/∑[w(F o 2 ) 2 ]} 1/2
The single crystal structure in table 1 shows that: HPOC-401 is crystallized in the space group of orthorhombic Pnnn and is composed of 6 tetra-aldehyde resorcinol cups [4]]The aromatic hydrocarbon ligand is an octahedral structure organic cage assembled by using vertexes and 12 p-dibenzoic dihydrazide ligands as edges. It contains an oversized octahedral cavity and 8 triangular windows. The maximum cavity diameter and volume is about 3.25nmIn addition, the triangular window has an average length of about 2.0nm, which can pass through molecules having a diameter of about 0.95nm (the isobutyl tail in HPOC-401 is not shown in the schematic structural diagram for the sake of simplicity, as shown in FIG. 3).
(2) Nuclear magnetic hydrogen spectrum of dried HPOC-401 sample 1 H NMR) and the results are shown in fig. 4. The appearance of characteristic peaks in NH and H-c=n in the figure represents an efficient synthesis of HPOC-401 organic cage. Subsequently, the HPOC-401 sample is soaked in water for one week and then is dried again for nuclear magnetic hydrogen spectrum test, and the spectrum is unchanged compared with the previous spectrum, so that the stability of the HPOC-401 in water environment is verified.
HPOC-401 was further characterized by high resolution mass spectrometry (HR-MS) and the results are shown in FIG. 5. From the high resolution mass spectrum, a peak near 2281.3015 was observed, which could be attributed to HPOC-401 after removal of three protons, confirming its water stability, and the unchanged signal indicated that HPOC-401 was stable in water, thus indicating that it was also stable in solution phase.
(3) FIG. 6 is an infrared spectrum (FT-IR) of HPOC-401, from which C-N (1274 cm) in the HPOC-401 cage was observed by Fourier infrared spectrum (FT-IR) testing -1 )、C＝N(1614cm -1 )、C＝O(1670cm -1 ) O-H and N-H (3270 cm) -1 ) The characteristic infrared vibration signal indicates that HPOC-401 is stably present in solid state conditions.
(4) FIG. 7 is an X-ray powder diffraction (PXRD) pattern of HPOC-401 with a large broad peak in the range of 4-40, indicating that the HPOC-401 sample is amorphous after activation.
(5) FIG. 8 is a thermogravimetric curve (TGA) of HPOC-401, from which it can be seen that HPOC-401 can be stabilized to 320 ℃.
(6) FIG. 9 is N of HPOC-401 2 adsorption-Desorption Curve, BET test, nitrogen adsorption at 77K, showed that HPOC-401 had a surface area of 3.57m 2 g -1 。
(2) Polydisperse HPOC-401-Ti was obtained using Post-modification metal synthesis (PSM, post-Synthetic Metalation) (see FIG. 10).
The above powdered HPOC-401 (100 mg) was placed in 50mL of saturated titanyl acetylacetonate solution and immersed for 24 hours at room temperature. Followed by filtration, methanol washing, methanol exchange several times. Finally, the mixture was dried in a vacuum oven (100 ℃) for 12 hours to obtain HPOC-401-Ti (as shown in FIG. 11) in the form of red powder from which the guest solvent molecules were removed. This shows that: the invention can obtain HPOC-401-Ti with 87 percent of yield by simply soaking HPOC-401 in saturated methanol solution of titanyl acetylacetonate.
HPOC-401-Ti characterization means:
(1) The composition of HPOC-401-Ti was confirmed by field emission scanning electron microscopy (FE-SEM) and EDS spectra showed that C, N, O, ti was uniformly distributed in HPOC-401-Ti and also showed successful chelation of Ti metal ions on HPOC-401 (as shown in FIG. 12).
(2) The content of Ti in the HPOC-401-Ti sample was determined to be 8.63% by plasma emission spectroscopy (ICP) characterization.
(3) FIG. 13 is an infrared spectrum (FT-IR) of HPOC-401-Ti, from which C-N (1290 cm) in the HPOC-401 cage was observed -1 )、C＝N(1614cm -1 )、C＝O(1670cm -1 ) O-H and N-H (3270 cm) -1 ) The characteristic infrared vibration signal is obviously changed. Wherein C-N, C = N, C =o has blue shifted to 1274cm, respectively -1 、1567cm -1 、1602cm -1 This further indicates that the Ti metal ions are successfully sequestered on HPOC-401.
(4) FIG. 14 is an X-ray powder diffraction (PXRD) pattern of HPOC-401-Ti with broad peaks in the range of 4-40, indicating that the HPOC-401-Ti sample is amorphous.
(5) HPOC-401-Ti was dried in a vacuum oven at 80℃for 5h and then subjected to thermogravimetric testing under nitrogen atmosphere, the results of which are shown in FIG. 16. As can be seen from Thermogravimetric (TGA) analysis, HPOC-401 can be stabilized to 300 ℃.
(6) N of HPOC-401-Ti 2 The adsorption-desorption curves are shown in FIG. 17, and the nitrogen adsorption result under 77K shows that the surface area of HPOC-401-Ti is as high as 976.5m 2 g -1 。
(7) HPOC-401-Ti ultraviolet-visible diffuse reflectance spectra (UV-vis) were tested by ultraviolet-visible diffuse reflectance (UV-vis) and the results are shown in FIG. 18. As can be seen from the figures: the ultraviolet absorption edge of HPOC-401-Ti is at 872nm, can effectively absorb visible light, and the corresponding energy band is 1.42eV, which indicates that the HPOC-401-Ti has semiconductor property.
(8) The degradation performance of HPOC-401-Ti on dye pollutants in water is determined by ultraviolet visible absorption spectroscopy (UV), and the specific method is as follows:
5mg of HPOC-401-Ti was added to 10mL of 50ppm methylene blue solution and subjected to 5h of sun light. The degradation efficiency of HPOC-401-Ti on methylene blue in water was measured by ultraviolet visible absorption spectroscopy (UV), and the results are shown in FIG. 19. The results in the figures show that: HPOC-401-Ti can degrade up to 99% methylene blue in water under solar conditions.
5mg of HPOC-401-Ti is added to 10mL of rhodamine B solution with the concentration of 50ppm, and 2 drops of hydrogen peroxide are added. The degradation efficiency of HPOC-401-Ti on rhodamine B in water was measured by ultraviolet visible absorption spectroscopy (UV), and the results are shown in FIG. 20. The results in the figures show that: after 5h of sun light, HPOC-401-Ti can be degraded into rhodamine B with the concentration of 99 percent in water.
5mg of HPOC-401-Ti was added to 10mL of 50ppm methyl orange solution, and 2 drops of hydrogen peroxide were added. The degradation efficiency of HPOC-401-Ti on methyl orange in water was measured by ultraviolet visible absorption spectroscopy (UV), and the results are shown in FIG. 21. The results in the figures show that: after 5h of sun light, HPOC-401-Ti can be degraded into methyl orange with the concentration of 95% in water.
Taken together, it is shown that: HPOC-401-Ti can efficiently degrade pollutants including methylene blue (> 99%), rhodamine B (> 99%), methyl orange (> 95%) under sunlight conditions.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A composite material comprising a porous organic cage compound and metallic titanium supported on the porous organic cage compound.
2. The composite material according to claim 1, wherein the composite material has a Ti content of 5 to 10% by mass.
3. The composite material of claim 1 or 2, wherein the composite material has a BET surface area of 976 to 977m 2 g -1 。
4. A composite material according to any one of claims 1 to 3, wherein the porous organic cage compound (abbreviated as HPOC-401) has the formula C 384 H 408 N 48 O 72 Has a structure shown in a formula I:
5. the composite material of claim 4, wherein the HPOC-401 is obtained from the reaction of tetra-aldehyde resorcinol calix [4] arene (C4 RACHO) and p-dibenzoate dihydrazide (TPHA).
Preferably, the HPOC-401 comprises tetra aldehyde resorcinol calix [4] arene (C4 RACHO) and paradibenzoic acid dihydrazide (TPHA) with a molar ratio of 1 (1-3).
Preferably, the temperature of the reaction is 80-120 ℃, and the time of the reaction is 6-20h.
6. The composite material of claim 5, wherein the method of preparing HPOC-401 further comprises: evaporating the reaction liquid obtained after the reaction is completed at a constant temperature to obtain the porous organic cage HPOC-401 crystal.
Preferably, the porous organic cage HPOC-401 crystal has a symmetry center, a space group of Pnnn and a unit cell parameter ofα＝β＝γ＝90°。
Preferably, the porous organic cage HPOC-401 crystal is an octahedral structure organic cage assembled by using 6 tetra-aldehyde resorcinol calix [4] arene ligands as vertexes and 12 p-dibenzoate dihydrazide ligands as edges.
Preferably, the porous organic cage HPOC-401 crystals comprise oversized octahedral cavities and 8 triangular windows.
Preferably, the porous organic cage HPOC-401 crystals have a maximum cavity diameter and volume of about 3.25nm and
preferably, the porous organic cage HPOC-401 crystal has an intra-unit cell molecular number z=4.
Preferably, the triangular window of the porous organic cage HPOC-401 crystals has an average length of about 2.0nm.
Preferably, the size of the porous organic cage HPOC-401 crystals is 1-3 mm.
Preferably, the porous organic cage HPOC-401 crystals are pale yellow tetrahedral crystals.
Preferably, the BET surface area of the porous organic cage HPOC-401 crystal is 3.5-3.6 m 2 g -1 Exemplary is 3.57m 2 g -1 。
7. A method of preparing a composite material according to any one of claims 1 to 6, comprising mixing the porous organic cage compound with a precursor comprising a Ti active metal component and reacting to obtain the composite material.
8. The method of preparing a composite material according to claim 7, wherein the precursor containing Ti active metal component is titanium acetylacetonate.
9. The method of producing a composite material according to claim 7 or 8, wherein the porous organic cage compound and the precursor containing Ti active metal component are reacted in a mass to volume ratio (mg: mL) of (1-5): 1.
Preferably, the temperature of the reaction is room temperature and the time of the reaction is 12-24 hours.
10. Use of a composite material according to any one of claims 1 to 6 and/or a composite material produced by a production process according to any one of claims 7 to 9 as a photocatalytic material.
Preferably in the photocatalytic degradation of dye contaminants.
Preferably, the dye contaminants include, but are not limited to, methylene blue, rhodamine B, methyl orange.
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