CN115870000A - Porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, preparation method and application - Google Patents
Porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, preparation method and application Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 71
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 69
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 35
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 35
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 claims description 60
- 239000002057 nanoflower Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 230000001699 photocatalysis Effects 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 15
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- TUQTZPCIOZGMCW-UHFFFAOYSA-N C1=CC(N)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(N)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 TUQTZPCIOZGMCW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SUHPVIWAYJQMBD-UHFFFAOYSA-N [C].N1C=CC=C1 Chemical compound [C].N1C=CC=C1 SUHPVIWAYJQMBD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- -1 phenyl carbon Chemical compound 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 230000000452 restraining effect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to a porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, a preparation method and application thereof.
Description
Technical Field
The invention relates to a photocatalytic hydrogen production catalyst, in particular to a nano flower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, a preparation method and application thereof, belonging to the technical field of photocatalytic materials.
Background
The increasingly serious global energy crisis and environmental pollution cause the conversion of green energy, especially the conversion of solar energy into hydrogen energy, to be more widely concerned, and the realization of water decomposition and hydrogen production by utilizing the photocatalysis technology becomes an effective strategy for utilizing solar energy, thereby realizing energy conversion and storage and restraining environmental pollution. How to improve the efficiency of the photocatalyst has been a hot issue in the field of photocatalytic research. In the research process of the photocatalysis technology, the separation of a photon-generated carrier is the most important step in the photocatalysis process, and the charge separation efficiency directly influences the final efficiency of the photocatalyst, so that the effective design of the photocatalyst with different structures is an important means for realizing the high-efficiency separation of the carrier.
Researchers have constructed heterostructures of type i, type ii, p-n, and Z-scheme, and in recent years, direct Z-scheme heterostructures have become one of the most effective strategies for preparing efficient photocatalysts as a structure simulating the natural photosynthesis process. The prerequisite for the production of Z-scheme heterostructures is a band-structure matching, in which the conduction band of one semiconductor should be as close as possible to the valence band of the other semiconductor. The Z-scheme heterostructure inherits the higher redox capability of two semiconductors, namely a photoproduced hole with low oxidation potential in one semiconductor is compounded with a photoproduced electron with low reduction potential in the other semiconductor, so that the separation of electron-hole pairs is effectively enhanced, the high oxidation potential and reduction potential of the two semiconductors are respectively maintained, and the redox capability of the photocatalyst is improved to participate in surface redox reaction.
Covalent Organic Polymers (COP) are a novel multi-dimensional functional material and have been widely studied in artificial photosynthetic systems. They have many inherent advantages, such as strong visible light absorption, tunable energy bands and chemical structures, and unique electronic properties. Although great efforts have been made to promote the development of COP photocatalysis, the energy band is above 0, and the water cannot be decomposed to produce hydrogen by photocatalysis.
How to reasonably design a Z-scheme heterostructure formed between a COP and an inorganic semiconductor so as to fully utilize a covalent organic polymer to transfer electrons to the inorganic semiconductor and consume photogenerated holes on a valence band of the semiconductor, thereby improving the photocatalytic hydrogen production activity of the semiconductor is still a great challenge.
The forbidden band width of indium zinc sulfide is 2.6eV, the conduction band position and the valence band position of the indium zinc sulfide are-0.60V (vs. NHE) and 1.93V (vs. NHE) respectively, the material has stronger reduction potential for photocatalytic decomposition of water to produce hydrogen, but the oxidation capability of the material is insufficient, so that the material has different consumption rates of photogenerated electrons and holes, the concentration of the photogenerated electrons can be obviously inhibited, and the efficiency of photocatalytic hydrogen production is further reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nano floriform porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a direct Z-scheme photocatalyst of nanometer flower-shaped porphyrin-based porous organic polymer/indium zinc sulfide is characterized in that porphyrin-based porous organic polymer nanoparticles are loaded on indium zinc sulfide nanometer flowers in situ, and energy bands of the porphyrin-based porous organic polymer nanoparticles and the indium zinc sulfide nanometer flowers are matched to form a direct Z-scheme heterojunction catalyst.
Preferably, according to the present invention, the indium zinc sulfide nanosheets have a thickness of 20-40nm, a length of 700-1000nm, and the porphyrin-based porous organic polymer nanoparticles have a diameter of 40-60nm.
Preferably, according to the present invention, the loading of the porphyrin-based porous organic polymer nanoparticles is 1wt% to 6wt%.
The invention also aims to provide a preparation method of the nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst.
A preparation method of a nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst comprises the following steps:
(1) Uniformly dispersing indium zinc sulfide nanoflowers into a mixed solution of 1,3,5-trimethylbenzene, acetic acid and 1,4-dioxane to obtain indium zinc sulfide nanoflower dispersion liquid;
(2) Adding 5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin and 4,4', 4' - (1,3,5-triazine ring-2,4,6-tribenzyl) to the indium zinc sulfide nanoflower dispersion, ultrasonically stirring for reaction for 30-35min, and then placing at 115-125 ℃ for heat preservation and reaction for 70-75h;
(3) Filtering the reaction solution obtained in the step (2), and repeatedly washing the reaction solution with acetone, tetrahydrofuran, trichloromethane and methanol in sequence; and drying the separated product to obtain the nano floriform porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst.
Preferably, in step (1), the mass-to-volume ratio of the indium-zinc sulfide nanoflowers to 1,3,5-trimethylbenzene is as follows: (0.1-0.5): (10-20), unit: g/mL.
Further preferably, in the step (1), the mass-to-volume ratio of the indium zinc sulfide nanoflower to 1,3,5-trimethylbenzene is as follows: (0.1-0.2): (10-20), unit: g/mL.
Preferably, in step (1), the mass-to-volume ratio of the indium-zinc sulfide nanoflowers to the acetic acid is as follows: (0.1-0.5): (1-5), unit: g/mL.
Further preferably, in the step (1), the mass-to-volume ratio of the indium zinc sulfide nanoflowers to the acetic acid is as follows: (0.1-0.2): (1-5), unit: g/mL.
Preferably, in step (1), the mass-to-volume ratio of the indium-zinc sulfide nanoflowers to 1,4-dioxane is as follows: (0.1-0.5): (10-20), unit: g/mL.
Further preferably, in the step (1), the mass-to-volume ratio of the indium zinc sulfide nanoflower to 1,4-dioxane is as follows: (0.1-0.2): (10-20), unit: g/mL.
Preferably, in step (1), the indium-zinc sulfide nanoflower is prepared by the following method:
dissolving zinc acetate dihydrate, thioacetamide and indium trichloride tetrahydrate in a mixed solution of water and ethanol, then placing the mixture at 180 ℃ for heat preservation reaction for 24 hours, washing the mixture with ethanol, then washing the mixture with deionized water after the reaction is finished, and drying the mixture at 60 ℃ for 12 hours to obtain the three-dimensional indium zinc sulfide nanoflower structure.
More preferably, the volume ratio of water to ethanol in the mixed solution of water and ethanol is 1:1.
More preferably, the molar ratio of zinc acetate dihydrate, thioacetamide and indium trichloride tetrahydrate is (0.2-0.6): (3-3.5): (0.6-1.0).
More preferably, the ratio of the number of moles of zinc acetate dihydrate to the volume of the mixed solution is (0.2-0.6): 30, units, mmol/mL.
Preferably, in the step (2), the mass ratio of the addition amount of 5,10,15,20-tetra (4-aminophenyl) -21h, 23h-porphyrin to the indium zinc sulfide nanoflower is: 0.008-0.06:1.
Further preferably, in the step (2), the mass ratio of the added amount of 5,10,15,20-tetra (4-aminophenyl) -21h, 23h-porphyrin to the indium zinc sulfide nanoflower is: 0.015-0.037:1.
Preferably, in step (2), the mass ratio of the added amount of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde to indium zinc sulfide nanoflower is: 0.006-0.06:1.
Further preferably, in the step (2), the mass ratio of the addition amount of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde to the indium zinc sulfide nanoflower is: 0.015-0.03:1.
According to the invention, in the step (2), the reaction temperature is kept at 120 ℃ and the reaction time is 72h.
Preferably, in step (3), the product is dried, and the obtained product is kept at 55-65 ℃ for 12h.
The application of the direct Z-scheme photocatalyst of the nano floriform porphyrin-based porous organic polymer/indium zinc sulfide is used for photocatalytic decomposition of water to produce hydrogen; the dosage is 0.5-1 g/L.
The invention has the technical characteristics and excellent effects that:
1. the invention utilizes indium zinc sulfide and a porphyrin-based porous organic polymer to construct a heterostructure, the forbidden bandwidth of the indium zinc sulfide is 2.6eV, the positions of the conduction band and the valence band are-0.60V (vs. NHE) and 1.93V (vs. NHE), respectively, the forbidden bandwidth of the porphyrin-based porous organic polymer is 1.61eV, the positions of the conduction band and the valence band are 1.34V (vs. NHE) and 2.95V (vs. NHE), respectively, and the energy bands of the conduction band and the valence band are matched to form a direct Z-scheme heterojunction catalyst; the recombination of the photoproduction holes of the indium zinc sulfide and the photoproduction electrons of the porphyrin-based porous organic polymer is realized, the remaining photoproduction electrons on the indium zinc sulfide can fully decompose water to produce hydrogen, the remaining photoproduction holes on the porphyrin-based porous organic polymer can fully perform oxidation reaction, the reaction in two directions in the whole photocatalytic reaction is realized to be synchronously performed, and the photocatalytic efficiency is improved.
2. The method utilizes a hydrothermal method to prepare the nano flower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, is beneficial to carrying out surface oxidation-reduction reaction, promoting efficient separation of photon-generated carriers, maintaining strong oxidation-reduction potential and realizing efficient hydrogen production through photocatalytic water decomposition.
3. According to the invention, a hydrothermal method is utilized to load the porphyrin-based porous organic polymer nanoparticles on the surface of the indium zinc sulfide nanoflower in situ, the preparation cost is low, the equipment requirement is low, the method is simple, and the prepared porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalyst can effectively promote photo-generated charge separation, so that photocatalytic water decomposition and high-efficiency hydrogen production are realized.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalyst prepared in example 3 of the present invention.
FIG. 2 is an infrared spectrum of a porphyrin-based covalent organic polymer of comparative example 1;
FIG. 3 is a nuclear magnetic carbon spectrum of a porphyrin-based covalent organic polymer of comparative example 1;
FIG. 4 is an IR spectrum of indium zinc sulfide of comparative example 2;
FIG. 5 is an XRD pattern of the product of example 3, comparative example 1, comparative example 2;
FIG. 6 is a graph of the UV absorption diffuse reflectance of the products of example 3, comparative example 1, and comparative example 2;
FIG. 7 is a band gap diagram of porphyrin-based covalent organic polymers of comparative example 1;
FIG. 8 is a band gap diagram of indium zinc sulfide of comparative example 2;
FIG. 9 is an energy band diagram of a porphyrin-based covalent organic polymer of comparative example 1;
FIG. 10 is a band diagram of indium zinc sulfide of comparative example 2;
FIG. 11 is a schematic energy band diagram of a porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalyst;
FIG. 12 is a graph showing the change of photocatalytic hydrogen production rate-time of porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalyst with different loading amounts and indium zinc sulfide with a single structure.
FIG. 13 is a graph showing the rate of hydrogen production by direct Z-scheme photocatalyst in the presence of porphyrin-based porous organic polymer/indium zinc sulfide nanoflower with different loading amounts.
Detailed Description
The present invention will be more fully described in the following examples, which are not intended to limit the scope of the invention.
5,10,15,20-tetrakis (4-aminophenyl) -21H, 23H-porphyrin, 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) triphenylformaldehyde are all commercially available products, 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) triphenylformaldehyde, commercially available from Shanghai Micheln Biochemical technology Ltd.
Example 1:
the preparation method of the nanometer flower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst comprises the following steps:
(1) Dissolving 0.4mmol of zinc acetate dihydrate, 3.2mmol of thioacetamide and 0.8mmol of indium trichloride tetrahydrate in 15mL of deionized water and 15mL of ethanol, then placing the mixture at 180 ℃ for heat preservation reaction for 24 hours, after the reaction is finished, washing the mixture with ethanol, then washing the mixture with deionized water, and drying the mixture at 60 ℃ for 12 hours to obtain a three-dimensional indium zinc sulfide nanoflower structure;
(2) Weighing 0.11g of indium zinc sulfide nanoflower, placing the indium zinc sulfide nanoflower in a mixed solution consisting of 15mL of 1,3,5-trimethylbenzene, 3mL of acetic acid and 15mL of 1,4-dioxane, ultrasonically stirring to uniformly disperse the indium zinc sulfide nanoflower, then adding 0.001g of 5,10,15,20-tetrakis (4-aminophenyl) -21H, 23H-porphyrin and 0.0008g of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) triphenylformaldehyde, ultrasonically stirring for 30min, then placing the ultrasonically treated solution in a 50mL hydrothermal reaction kettle, preserving the temperature for 72h at 120 ℃, filtering the reacted solution, sequentially and repeatedly washing with acetone, tetrahydrofuran, trichloromethane and methanol, and then placing the separated product in a 60 ℃ for 12h, thus obtaining the porphyrin-based porous organic polymer/zinc sulfide indium nanoflower direct Z-scheme photocatalysis; 1% of COP-ZIS; the yield of the porphyrin-based porous organic polymer was 61%.
1% COP-ZIS calculation method: (0.001 g of 5,10,15,20-tetrakis (4-aminophenyl) -21h, 23h-porphyrin +0.0008g of 4,4',4"- (1,3,5-triazine ring-2,4,6-triyl) triphenylformaldehyde) 61% yield/0.11 g indium zinc sulfide nanoflower =1%.
The thickness of indium zinc sulfide nanosheets in the catalyst is 20-40nm, the length of the indium zinc sulfide nanosheets is 700-1000nm, and the diameter of the porphyrin-based porous organic polymer nanoparticles is 40-60nm.
Example 2:
the preparation method of the nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst is the same as that of example 1, except that:
5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin with the dosage of 0.002g, 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde with the dosage of 0.0016g, obtaining the porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalysis; 2% of COP-ZIS; the yield of the porphyrin-based porous organic polymer was 61%.
Example 3:
the preparation method of the nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst is the same as that of example 1, except that:
5,10,15,20-tetrakis (4-aminophenyl) -21H, 23H-porphyrin in an amount of 0.004g, 4',4"- (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde in an amount of 0.0032g, obtaining porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalysis; 4% of COP-ZIS; the yield of the porphyrin-based porous organic polymer was 61%.
Example 4:
the preparation method of the nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst is the same as that of example 1, except that:
5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin with the dosage of 0.006g, 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde with the dosage of 0.0048g, and obtaining the porphyrin-based porous organic polymer/indium zinc sulfide nanoflower direct Z-scheme photocatalysis; score 6% COP-ZIS; the yield of the porphyrin-based porous organic polymer was 61%.
Comparative example 1
Preparation of porphyrin-based covalent organic polymers by the following steps:
taking 15mL of 1,3,5-trimethylbenzene, 3mL of acetic acid and 15mL of 1,4-dioxane, ultrasonically stirring to uniformly disperse the mixture, then adding 0.004g of 5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin and 0.0032g of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) triphenylformaldehyde, ultrasonically stirring for 30min, then placing the ultrasonically-treated solution in a 50mL hydrothermal reaction kettle, preserving heat for 72h at 120 ℃, filtering the reacted solution, repeatedly washing the reacted solution with acetone, tetrahydrofuran, trichloromethane and methanol sequentially, and preserving heat for 12h at 60 ℃ to obtain the porphyrin-based covalent organic polymer, wherein the yield is 61%.
Comparative example 2
The preparation method of the indium zinc sulfide comprises the following steps:
dissolving 0.4mmol of zinc acetate dihydrate, 3.2mmol of thioacetamide and 0.8mmol of indium trichloride tetrahydrate in 15mL of deionized water and 15mL of ethanol, then placing the mixture at 180 ℃ for heat preservation reaction for 24 hours, after the reaction is finished, washing the mixture with ethanol, then washing the mixture with deionized water, and drying the mixture at 60 ℃ for 12 hours to obtain the three-dimensional indium zinc sulfide nanoflower structure.
Test example 1
1. Fig. 1 shows Scanning Electron Microscope (SEM) photographs of the nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst and indium zinc sulfide prepared in example 3, and it can be seen from fig. 1 that porphyrin-based porous organic polymer nanoparticles are supported on the surface of indium zinc sulfide nanoflowers, thus proving the formation of a heterostructure of porphyrin-based porous organic polymer/indium zinc sulfide nanoflowers.
2. Comparative example 1 the infrared spectrum and nuclear magnetic carbon spectrum of the porphyrin-based covalent organic polymer are shown in FIG. 2 and 1694cm, respectively, in FIG. 3 and FIG. 2 -1 And 3352cm -1 The vibration bands are 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde (TATTBD), C = O and 5,10,15,20-tetrakis (4-aminophenyl) -21H, and N-H in 23H-porphyrin (TAPPP), respectively, and are obviously weakened in the obtained COP. At the same time, 1605cm -1 A new vibration band was detected, corresponding to the C = N bond in COP. This result indicates that COP can be successfully synthesized using TAPPP and TATTBD precursors;
as can be seen from fig. 3, the low-field signals observed at 163 (a) and 154ppm (C) are assigned to the C atom in the C = N bond, the strong peaks at 129 (b) and 137ppm (d) are assigned to the phenyl carbon and the C-N bond, respectively, the peaks at 113 (e) and 147 (f) ppm correspond to the pyrrole carbon, and the peak at 122ppm (g) is assigned to the C = C bond.
3. The infrared spectrum of the nano flower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst prepared in example 3 is shown in FIG. 4, and it can be seen from FIG. 4 that the wavelength is 1605cm -1 The peak observed here belongs to the C = N bond, which is a unique chemical bond in COP, demonstrating successful synthesis of a COP-ZIS heterojunction.
4. The XRD of the products of example 3, comparative example 1, and comparative example 2 are shown in fig. 5, and as can be seen from fig. 5, the XRD spectrum of the COP of comparative example 1 shows low crystallinity, having a weak peak at 2 θ =8.0 °, belonging to the (100) plane of COP. The strong peak observed at 2 θ =21.4 ° lies at the (001) plane of the COP, indicating that there is strong pi-pi stacking between adjacent layers. The XRD spectrum peaks for both ZIS of comparative example 2 and COP-ZIS heterostructure of example 1 are clearly pointed towards the hexagonal phase of ZIS (JCPDS nos. 65-2023,
) Due to the low COP signal content, the crystallinity is negligible.
5. The ultraviolet absorption diffuse reflection of the products of example 3, comparative example 1 and comparative example 2 is shown in figure 6, and as can be seen from figure 6, the heterostructure of COP, ZIS and COP-ZIS has visible light absorption, but the heterostructure of COP-ZIS of example 1 has better visible light absorption effect, which shows that the introduction of COP is beneficial to forming wider visible light absorption of COP-ZIS.
6. The band gap diagrams of the products of comparative example 1 and comparative example 2 are shown in FIGS. 7 and 8, and are derived from the Tauc diagram (ah v) of FIG. 7 2 ＝A(hν-E g ) Determination of the band gap (E) of the COP g ) Is 1.63eV; from FIG. 8Tauc picture (ah ν) 2 ＝A(hν-E g ) Determination of the band gap (E) of ZIS g ) It was 2.53eV.
7. Determination of the lowest occupied molecular orbital level (E) of COP based on UPS Spectroscopy LUMO ) The minimum occupied molecular orbital level (E) of COP was calculated from 2.95eV HOMO ) 1.34eV, FIG. 9; the valence band energy level (E) of ZIS was determined based on UPS spectroscopy VB ) The conduction band energy level (E) of ZIS was calculated to be 1.93eV CB ) Is-0.60 eV; see fig. 10.
8. The band gap energy band positions of COP and ZIS are taken to give a band diagram, see FIG. 11, illustrating E for COP HOMO E with ZIS VB Similarly, it is shown that porphyrin-based porous organic polymers with indium zinc sulfide can construct direct Z-scheme.
Test example 2:
the change curve of the photocatalytic hydrogen production rate-time of the porphyrin-based porous organic polymer/indium zinc sulfide nanoflower photocatalyst with different loading amounts is shown in fig. 12, and as can be seen from fig. 12, the photocatalytic hydrogen production performance of the porphyrin-based porous organic polymer/indium zinc sulfide nanoflower photocatalyst is greatly improved compared with that of the indium zinc sulfide alone under ultraviolet-visible light.
The graph of the change of the direct Z-scheme photocatalyst hydrogen production rate of the porphyrin-based porous organic polymer loading of the porphyrin-based porous organic polymer/indium zinc sulfide nanoflowers with different loadings is shown in FIG. 13, and the optimal loading of the porphyrin-based porous organic polymer is 4wt% as can be seen from FIG. 13; the reason is as follows: the content of the porphyrin-based porous organic polymer is too low, which is not beneficial to the sufficient combination of the photoproduction holes of the indium zinc sulfide and the photoproduction electrons of the porphyrin-based porous organic polymer; the content of the porphyrin-based porous organic polymer is too high, and the charge transfer distance between the porphyrin-based porous organic polymer and the indium zinc sulfide nanoflowers is long, so that the photoproduction electrons and holes cannot be effectively separated and transferred.
Therefore, the Z-scheme photocatalyst formed by the porphyrin-based porous organic polymer and indium zinc sulfide is beneficial to separation of photo-generated charges, so that the performance of hydrogen production through photocatalytic water decomposition is remarkably improved.
Claims (10)
1. A direct Z-scheme photocatalyst of nanometer flower-shaped porphyrin-based porous organic polymer/indium zinc sulfide is characterized in that porphyrin-based porous organic polymer nanoparticles are loaded on indium zinc sulfide nanometer flowers in situ, and energy bands of the porphyrin-based porous organic polymer nanoparticles and the indium zinc sulfide nanometer flowers are matched to form a direct Z-scheme heterojunction catalyst.
2. The nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst as claimed in claim 1, wherein the thickness of indium zinc sulfide nanosheets is 20-40nm, the length is 700-1000nm, the diameter of the porphyrin-based porous organic polymer nanoparticles is 40-60nm, and the loading of the porphyrin-based porous organic polymer nanoparticles is 1-6 wt%.
3. The method for preparing nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst as claimed in claim 1, comprising the following steps:
(1) Uniformly dispersing indium zinc sulfide nanoflowers into a mixed solution of 1,3,5-trimethylbenzene, acetic acid and 1,4-dioxane to obtain indium zinc sulfide nanoflower dispersion liquid;
(2) Adding 5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin and 4,4', 4' - (1,3,5-triazine ring-2,4,6-tribenzyl) to the indium zinc sulfide nanoflower dispersion, ultrasonically stirring for reaction for 30-35min, and then placing at 115-125 ℃ for heat preservation and reaction for 70-75h;
(3) Filtering the reaction solution obtained in the step (2), and repeatedly washing the reaction solution with acetone, tetrahydrofuran, trichloromethane and methanol in sequence; and drying the separated product to obtain the nano floriform porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst.
4. The preparation method according to claim 3, wherein in the step (1), the mass-to-volume ratio of the indium zinc sulfide nanoflowers to 1,3,5-trimethylbenzene is as follows: (0.1-0.5): (10-20), unit: g/mL, the mass-volume ratio of the indium zinc sulfide nanoflower to the acetic acid is as follows: (0.1-0.5): (1-5), unit: g/mL, the mass-volume ratio of the indium zinc sulfide nanoflower to 1,4-dioxane is as follows: (0.1-0.5): (10-20), unit: g/mL.
5. The method of claim 3, wherein in step (1), the indium-zinc sulfide nanoflowers are prepared by:
dissolving zinc acetate dihydrate, thioacetamide and indium trichloride tetrahydrate in a mixed solution of water and ethanol, then placing the mixture at 180 ℃ for heat preservation reaction for 24 hours, washing the mixture with ethanol after the reaction is finished, then washing the mixture with deionized water, and drying the mixture at 60 ℃ for 12 hours to obtain the three-dimensional indium zinc sulfide nanoflower structure.
6. The method according to claim 5, wherein the volume ratio of water to ethanol in the mixture of water and ethanol is 1:1, and the molar ratio of zinc acetate dihydrate, thioacetamide, and indium trichloride tetrahydrate is (0.2-0.6): (3-3.5): (0.6-1.0), wherein the molar ratio of the zinc acetate dihydrate to the volume of the mixed solution is (0.2-0.6): 30, units, mmol/mL.
7. The preparation method according to claim 3, wherein in the step (2), the mass ratio of the addition amount of 5,10,15,20-tetra (4-aminophenyl) -21H, 23H-porphyrin to the indium zinc sulfide nanoflower is: 0.008-0.06;
preferably, in the step (2), the mass ratio of the addition amount of 5,10,15,20-tetra (4-aminophenyl) -21H and 23H-porphyrin to the indium zinc sulfide nanoflower is as follows: 0.015-0.037:1.
8. The preparation method according to claim 3, wherein in the step (2), the mass ratio of the addition amount of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde to the indium zinc sulfide nanoflower is: 0.006-0.06;
preferably, in the step (2), the mass ratio of the addition amount of 4,4', 4' - (1,3,5-triazine ring-2,4,6-triyl) tribenzaldehyde to the indium zinc sulfide nanoflower is: 0.015-0.03:1.
9. The preparation method according to claim 3, wherein in the step (2), the reaction temperature is kept at 120 ℃ and the reaction time is 72 hours, and in the step (3), the product is dried, and the obtained product is kept at 55-65 ℃ for 12 hours.
10. The use of nanoflower-like porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst as claimed in claim 1 for photocatalytic decomposition of water to produce hydrogen; the dosage is 0.5-1 g/L.
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