CN113731503A - Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst - Google Patents
Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst Download PDFInfo
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- CN113731503A CN113731503A CN202111047260.0A CN202111047260A CN113731503A CN 113731503 A CN113731503 A CN 113731503A CN 202111047260 A CN202111047260 A CN 202111047260A CN 113731503 A CN113731503 A CN 113731503A
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- titanium dioxide
- metal phthalocyanine
- phthalocyanine complex
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- OFHQGJFSDJQXOB-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Cu+2] Chemical compound [O-2].[O-2].[Ti+4].C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Cu+2] OFHQGJFSDJQXOB-UHFFFAOYSA-N 0.000 description 1
- RDOUUDPRYOXGBF-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Ni+2] Chemical compound [O-2].[O-2].[Ti+4].[Ni+2] RDOUUDPRYOXGBF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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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
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
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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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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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
Abstract
The invention discloses a preparation method of a metal phthalocyanine complex-titanium dioxide composite photocatalyst, which comprises the steps of adding tetrabutyl titanate into hydrofluoric acid, uniformly stirring, and carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain TiO2Nanosheets, and precipitating TiO2Heating and refluxing the nano-sheet and metal phthalocyanine complex by using N, N-dimethylformamide as a solvent to obtain TiO of the composite metal phthalocyanine complex2. The method is universal, is suitable for various metal phthalocyanine complexes, is easy to regulate and control the composite proportion, and the prepared material has strong visible light response and photo-generated electron-spaceThe holes are separated more effectively, the photo-thermal stability of the material is improved, and the method for modifying the material as a titanium dioxide photocatalyst can effectively improve the effect of the semiconductor material on the photocatalytic reduction of CO2And the photocatalytic performance and the material stability of the organic pollutants in the water body are degraded.
Description
Technical Field
The invention belongs to the technical field of preparation of composite photocatalysts, and particularly relates to a preparation method of a metal phthalocyanine complex-titanium dioxide composite photocatalyst.
Background
With the development of science and technology, the environmental pollution is increasingly serious, wherein CO2And the discharge of organic pollutants is the primary treatment problem. The solar energy is utilized to carry out photocatalytic conversion to convert CO2Reduction to CO, CH3OH and CH4And the like, the reduction product with high added value can reduce CO in the process2The concentration of the organic fertilizer can further achieve the purposes of relieving greenhouse effect and protecting the environment, and can also provide important chemical raw materials and clean energy. Besides, the photocatalysis method can also degrade organic pollutants in water such as hormone, dye, medicine and the like, and is a very promising water pollution treatment technology.
The photocatalyst is an important factor for determining the photocatalytic effect, and the research of the photocatalyst is important in the field of photocatalysis. TiO 22Is widely noticed by researchers because of its stable physicochemical properties and its low price. But its wider forbidden band (3.2 ev) can only utilize lambda in sunlight>387.5nm UV completes the catalytic process, and the UV content is less than 5% in sunlight, resulting in CO under natural light conditions2The photocatalytic reduction efficiency is low. The improvement of TiO by modification2The performance of photocatalysts has become a hotspot in the field. The patent with publication number CN 111151246A discloses a gold atom/titanium dioxide compositeThe catalyst has the advantages of extremely low noble metal loading capacity, high visible light utilization rate and simple preparation process. The patent with publication number CN 110327926 a discloses a preparation method of iron ion doped titanium dioxide nano-material, which can realize specific site doping under the special molecular recognition and catalytic mineralization effects of zwitter ion short peptide self-assembly, thereby improving the responsiveness and photocatalytic activity of titanium dioxide in visible light region. The patent with the publication number of CN 108545773B discloses a preparation method of nano titanium dioxide/tungsten trioxide composite material powder, which has the advantages of simple steps, convenient operation, low raw material cost, controllable process, safety and environmental protection, and the prepared finished product of nano TiO is2/WO3The composite material powder has uniform granularity, good dispersibility, ideal mixed texture appearance and high purity, so that the product has excellent photocatalytic performance. The patent with publication number CN 1018794656A discloses a copper porphyrin titanium dioxide composite photocatalyst and a preparation method thereof, the spectral response range of the photocatalyst is widened, the utilization rate of sunlight is improved, and the synthesized composite photocatalyst has good degradation rate for nitrophenol wastewater and dye wastewater which are difficult to degrade. The dye compound has better absorption in the whole visible region and even near infrared region, which causes the dye sensitive modification to be widely concerned and also causes the titanium dioxide to be possible to utilize the sunlight in the visible region and the near infrared region. However, most phthalocyanine or porphyrin-sensitized titanium dioxide has the defects of low sensitization efficiency, easy degradation of the sensitizer by light or easy aggregation and inactivation of the sensitizer, and the like, so that the use of the prepared photocatalytic material is limited. Therefore, there is a need for an improvement of the existing synthesis method to enhance the recyclability of the material while effectively improving the photocatalytic performance of titanium dioxide.
Disclosure of Invention
The technical problem solved by the invention is to provide a preparation method of a metal phthalocyanine complex-titanium dioxide composite photocatalyst, the method has high repetition rate and forms a firmly combined titanium dioxide composite material, and a heterojunction can be constructed in the metal phthalocyanine complex and the nano titanium dioxide to enable the material to have stronger photon-generated carrier componentThe ion capacity, and electrons generated by exciting phthalocyanine molecules by visible light can be transported to a conduction band of a semiconductor by a sensitizer, so that the optical response range is wider, and the visible light is more fully utilized. In addition, the metal phthalocyanine complex-titanium dioxide composite photocatalyst prepared by the invention has the advantages of good photo-thermal stability, large specific surface area, high catalytic activity and the like, and can be used for designing efficient photocatalytic reduction of CO2And a photocatalyst for degrading organic contaminants.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the metal phthalocyanine complex-titanium dioxide composite photocatalyst is characterized by comprising the following specific steps of:
step S1: synthesizing flaky titanium dioxide by a hydrothermal method, adding hydrofluoric acid into tetrabutyl titanate, stirring for 20-60min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 12-24h, then respectively cleaning for 3 times by using ethanol and deionized water, drying and grinding to obtain TiO2Nanosheets, wherein the volume ratio of tetrabutyl titanate to hydrofluoric acid is 100: 6;
step S2: TiO prepared in the step S12Adding the nanosheet and the metal phthalocyanine complex into N, N-dimethylformamide, and heating and refluxing for 2-5h under the stirring condition to finally obtain the metal phthalocyanine complex-titanium dioxide composite photocatalyst, wherein the mass ratio of the metal phthalocyanine complex to the titanium dioxide nanosheet is 0.01-0.5: 100.
Further defined, the metal phthalocyanine complex is one or more of cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, copper phthalocyanine and zinc phthalocyanine.
Compared with the prior art, the invention has the following beneficial effects: the preparation method has high repetition rate and obvious effect, the operation is simple and easy to control, and the titanium dioxide nano composite material prepared by the composite metal phthalocyanine complex has strong visible light response, high photo-generated carrier separation efficiency and good photo-thermal stability, and has wide application prospect in the field of photocatalysis.
Drawings
FIG. 1 shows nickel phthalocyanine-titanium dioxide (CuPc-TiO) prepared in example 12) SEM images of the composite;
FIG. 2 shows nickel phthalocyanine-titanium dioxide (NiPc-TiO) prepared in example 22) TEM images of the composite;
FIG. 3 shows nickel phthalocyanine-titanium dioxide (NiPc-TiO) prepared in example 22) Reduction of CO by composite material under full light2Is a plot of the cyclic performance of CO.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Adding 3mL of hydrofluoric acid into 50mL of tetrabutyl titanate, stirring for 20min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 24h, cleaning with ethanol and deionized water for 3 times respectively, drying, and grinding to obtain TiO2Nanosheets; 0.6g of TiO to be obtained2Adding the nanosheet and 0.0221g of copper phthalocyanine into 50mL of N, N-dimethylformamide, heating and refluxing for 2h under the condition of magnetic stirring to obtain titanium dioxide CuPc-TiO of the composite metal phthalocyanine complex2。
Example 2
Adding 6mL of hydrofluoric acid into 100mL of tetrabutyl titanate, stirring for 20min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 24h, cleaning with ethanol and deionized water for 3 times respectively, drying, and grinding to obtain TiO2Nanosheets; 0.6g of TiO to be obtained2Adding the nanosheet and 0.0150g of nickel phthalocyanine into 50mL of N, N-dimethylformamide, heating and refluxing for 2h under the condition of magnetic stirring to obtain titanium dioxide NiPc-TiO of the composite metal phthalocyanine complex2。
Example 3
Adding 6mL of hydrofluoric acid into 100mL of tetrabutyl titanate, stirring for 30min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 24h, cleaning with ethanol and deionized water for 3 times respectively, drying, and grinding to obtain TiO2Nanosheets; 0.6g of TiO to be obtained2Adding the nanosheet and 0.0143g of zinc phthalocyanine into 50mL of N, N-dimethylformamide, heating and refluxing for 2h under the condition of magnetic stirring to obtain the titanium dioxide ZnPc-TiO of the composite metal phthalocyanine complex2。
Example 4
Adding 3mL of hydrofluoric acid into 50mL of tetrabutyl titanate, stirring for 30min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 22h, cleaning with ethanol and deionized water for 3 times respectively, drying, and grinding to obtain TiO2Nanosheets; 0.1g of TiO to be obtained2Adding the nanosheet and 0.0007g of iron phthalocyanine into 50mL of N, N-dimethylformamide, heating and refluxing for 2h under the condition of magnetic stirring to obtain titanium dioxide FePc-TiO of the composite metal phthalocyanine complex2。
Example 5
Adding 3mL of hydrofluoric acid into 50mL of tetrabutyl titanate, stirring for 40min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 22h, cleaning with ethanol and deionized water for 3 times respectively, drying, and grinding to obtain TiO2Nanosheets; 0.1g of TiO to be obtained2Adding the nanosheet and 0.0143g of cobalt phthalocyanine into 50mL of N, N-dimethylformamide, heating and refluxing for 2h under the condition of magnetic stirring to obtain the titanium dioxide CoPc-TiO of the composite metal phthalocyanine complex2。
FIG. 1 illustrates CuPc-TiO compounds obtained in example 1 of the present invention2SEM image of the composite material. The figure shows that the copper phthalocyanine-titanium dioxide composite photocatalyst NiPc-TiO prepared by the invention2The shape of the nano-film is an ultrathin nano-sheet with the length of 40nm to 60nm and the width of 60 nm.
FIG. 2 NiPc-TiO obtained in example 1 of the present invention2TEM images of the composite. It can be seen from the figure that the nickel phthalocyanine-titanium dioxide composite catalyst NiPc-TiO prepared by the invention2Is anatase with the (001) crystal face exposed.
FIG. 3 shows that the phthalocyanine nickel-titanium dioxide composite catalyst obtained in example 2 of the present invention photocatalytically reduces CO under the irradiation of a 300W xenon lamp2The figure shows that the nickel phthalocyanine-titanium dioxide composite catalyst NiPc-TiO prepared by the method of the invention is a CO cycle performance curve2And better photo-thermal stability is kept.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. A preparation method of a metal phthalocyanine complex-titanium dioxide composite photocatalyst is characterized by comprising the following specific steps:
step S1: synthesizing flaky titanium dioxide by a hydrothermal method, adding hydrofluoric acid into tetrabutyl titanate, stirring for 20-60min, carrying out hydrothermal reaction in a high-pressure reaction kettle at 180 ℃ for 12-24h, then respectively cleaning for 3 times by using ethanol and deionized water, drying and grinding to obtain TiO2Nanosheets, wherein the volume ratio of tetrabutyl titanate to hydrofluoric acid is 100: 6;
step S2: TiO prepared in the step S12Adding the nanosheet and the metal phthalocyanine complex into N, N-dimethylformamide, and heating and refluxing for 2-5h under the stirring condition to finally obtain the metal phthalocyanine complex-titanium dioxide composite photocatalyst, wherein the mass ratio of the metal phthalocyanine complex to the titanium dioxide nanosheet is 0.01-0.5: 100.
2. The method for preparing the metal phthalocyanine complex-titanium dioxide composite photocatalyst as claimed in claim 1, wherein: the metal phthalocyanine complex is one or more of cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, copper phthalocyanine and zinc phthalocyanine.
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