CN115400792A - Modified PDI photocatalyst and preparation method and application thereof - Google Patents
Modified PDI photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115400792A CN115400792A CN202211199470.6A CN202211199470A CN115400792A CN 115400792 A CN115400792 A CN 115400792A CN 202211199470 A CN202211199470 A CN 202211199470A CN 115400792 A CN115400792 A CN 115400792A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910021617 Indium monochloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion 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
- 239000004246 zinc acetate Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a modified PDI photocatalyst and a preparation method and application thereof, wherein Zn is attached to the surface of PDI 2 InS 4 Nanosheets forming a hierarchical direct Z-type heterojunction forming HC-PDI @ Zn 2 InS 4 The composite photocatalyst, wherein the PDI is high-crystallinity PDI and has a rod-like structure; the preparation method comprises the following steps: carrying out constant-temperature hydrothermal reaction on 3,4,9,10-tetracarboxylic anhydride, ammonium sulfate and imidazole in a nitrogen atmosphere, cooling after the reaction is finished, then adding hydrochloric acid to crystallize PDI, carrying out suction filtration, washing the obtained product, and carrying out freeze drying to obtain HC-PDI; dispersing HC-PDI in mixed solution of glycerin and water by ultrasonic wave, adding indium trichloride, zinc chloride and thioacetamide, and reactingMaking ZnIn 2 S 4 Growing on the surface of PDI, separating precipitate after the reaction is finished, washing and drying; the catalyst can efficiently catalyze the full hydrolysis of water by visible light and simultaneously generate H 2 And O 2 Has wide prospect in the field of actual application of photocatalysis.
Description
Technical Field
The invention relates to a photocatalyst, and in particular relates to a modified PDI photocatalyst as well as a preparation method and application thereof.
Background
Solar energy is inexhaustible green energy in nature, and hydrogen energy has the characteristic of no pollution of combustion products, and is clean energy with great development and utilization values. Water is decomposed through a photocatalytic technology, rich solar energy can be converted into hydrogen energy for utilization, and the development of a semiconductor photocatalyst for high-efficiency photocatalytic water decomposition is the key of the technology. The perylene bisimide supermolecule (PDI) photocatalyst has the advantages of cheap raw materials, high structural controllability, simple preparation and synthesis steps, wide spectral response, high efficiency, stability and the like, and is a research hotspot in the field of photocatalytic water decomposition in recent years. In practical application, the low-crystallinity PDI molecule still faces the problems of slow photoproduction electron-hole transfer, easy recombination and the like, so that the catalytic efficiency is low.
Disclosure of Invention
The invention aims to: the first purpose of the invention is to provide a modified PDI photocatalyst with high catalytic efficiency; a second object of the present invention is to provide a method for preparing the modified PDI photocatalyst; the third purpose of the invention is to provide the modified PDI photocatalyst for generating H while decomposing water by photocatalysis 2 And O 2 The use of (1).
The technical scheme is as follows: the modified PDI photocatalyst provided by the invention has Zn attached to the surface of PDI 2 InS 4 Nanosheets forming a hierarchical direct Z-type heterojunction forming HC-PDI @ Zn 2 InS 4 A composite photocatalyst; wherein the PDI is a high-crystallinity PDI and has a rod-like structure.
Preferably, the PDI is in combination with Zn 2 InS 4 The mass ratio of (A) to (B) is 1-4: 21.
The preparation method of the modified PDI photocatalyst comprises the following steps:
(1) Carrying out constant-temperature hydrothermal reaction on 3,4,9,10-tetracarboxylic anhydride, ammonium sulfate and imidazole in a nitrogen atmosphere, cooling after the reaction is finished, then adding hydrochloric acid to crystallize PDI, carrying out suction filtration, washing the obtained product, and carrying out freeze drying to obtain HC-PDI;
(2) Dispersing HC-PDI prepared in the step (1) in mixed solution of glycerol and water by ultrasonic, and then adding trichlorizationIndium, zinc chloride and thioacetamide, reacting to obtain ZnIn 2 S 4 Growing on the surface of PDI, separating precipitate, washing, drying to obtain HC-PDI @ Zn 2 InS 4 A composite photocatalyst is provided.
Preferably, in the step (1), the hydrothermal reaction temperature is 80-180 ℃, and the reaction time is 2-10 h;3,4,9,10-tetracarboxylic anhydride, ammonium sulfate and imidazole in a molar mass ratio of (0.1-10) mmol (1-200): (10-500) g.
Preferably, in the step (2), the reaction temperature is 40-130 ℃, and the reaction time is 0.5-8 h; PDI, glycerol and water in a mass-to-volume ratio of (0.01-10) g: (1-80) mL: (1-200) mL; the mass ratio of indium trichloride to zinc chloride to thioacetamide is (0.1-10) g: (0.01-10) g: (0.05-10) g.
The modified PDI photocatalyst can generate H while performing photocatalytic total hydrolysis 2 And O 2 The use of (1).
The invention mechanism is as follows: sulfur indium zinc (ZnIn) 2 S 4 ) Has a unique and adjustable electronic structure and has been applied to the aspect of photocatalytic hydrogen production. The invention mixes ZnIn 2 S 4 The direct Z-type heterostructure is constructed with PDI molecules, the difference of energy band positions is utilized to inhibit the rapid recombination of electron-hole pairs, and more active free radicals can be generated, so that the capability of visible light to catalytically decompose water is improved, and the high-crystallinity PDI (HC-PDI) is beneficial to enhancing a built-in electric field to drive photogenerated carriers, and the mechanism is as follows:
HC-PDI and Zn 2 InS 4 A Z-type heterojunction is constructed between the HC-PDI and the ZnIn, and in the photocatalytic reaction, the photo-excited electrons in the HC-PDI conduction band are spontaneously transferred to the ZnIn under the unique built-in electric field action 2 S 4 In the valence band of (C), znIn is consumed 2 S 4 The residual holes effectively realize the separation of photogenerated electron-hole pairs and keep the strongest redox capability of the system, therebyIs beneficial to high-efficiency photocatalytic full water decomposition and simultaneously generates hydrogen and oxygen.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) The catalyst is prepared by reacting HC-PDI with ZnIn 2 S 4 The Z-shaped direct heterojunction is constructed, so that the recombination of photoproduction electrons and holes can be effectively inhibited, the separation efficiency of the photoproduction electrons and the holes is improved, the transfer of photoproduction charges is promoted, and the efficient visible light catalytic decomposition of water can be realized; (2) The preparation method is simple, the raw materials are cheap and easy to obtain, the method is green and simple, the premise of being capable of being put into future large-scale production is provided, and the method has a good application prospect in the aspect of solving the problems of energy shortage and the like in the future; (3) The catalyst is applied to catalyzing full water decomposition, H 2 And O 2 The optimum precipitation rates of (a) are 275.4 mu mol g -1 h -1 And 138.4. Mu. Mol g -1 h -1 And has wide prospect in the field of actual application of photocatalysis.
Drawings
FIG. 1 shows HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 Scanning electron microscope images of the composite photocatalyst;
FIG. 2 shows HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 A transmission electron microscope image of the composite photocatalyst;
FIG. 3 shows HC-PDI @ Zn prepared by the present invention 2 InS 4 An X-ray diffraction pattern of the composite photocatalyst;
FIG. 4 is HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 Electron paramagnetic resonance superoxide radical (. O) of composite photocatalyst 2 - ) Detecting the map;
FIG. 5 shows HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 Electron paramagnetic resonance hydroxyl radical (. OH) detection graph of the composite photocatalyst;
FIG. 6 shows HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 Electron paramagnetic resonance hole (h) of composite photocatalyst + ) Detecting the map;
FIG. 7 shows HC-PDI @ Zn prepared in examples 1 to 4 of the present invention under irradiation of visible light 2 InS 4 Composite photocatalystThe effect graph of visible light catalytic water decomposition;
FIG. 8 is HC-PDI @ Zn prepared in example 4 of the present invention and comparative examples 1 to 3 under irradiation of visible light 2 InS 4 A visible light catalytic water decomposition effect diagram of the composite photocatalyst;
FIG. 9 shows HC-PDI @ Zn prepared in example 3 of the present invention 2 InS 4 X-ray diffraction patterns before and after direct Z-type heterojunction photocatalyst reaction.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The preparation method of the modified PDI photocatalyst comprises the following steps:
(1) And (2) carrying out constant-temperature thermal reaction on 0.5mmol of 3,4,9, 10-tetracarboxylic anhydride, 15mmol of ammonium sulfate and 20g of imidazole for 10h at the temperature of 80 ℃ in a nitrogen atmosphere, cooling, adding 5mL of 1M hydrochloric acid solution with the concentration, uniformly stirring, repeatedly washing the obtained product with ultrapure water, and carrying out freeze drying to obtain HC-PDI.
(2) 30mg of the prepared HC-PDI was added to a mixed solution of glycerol and water (10 mL of glycerol, 40mL of water) and ultrasonically dispersed for 1.8h, and 880mg of InCl was added 3 ·4H 2 O, 409mg of zinc chloride and 451mg of thioacetamide, and carrying out oil bath reaction at 130 ℃ for 0.5h, and naturally cooling to room temperature after the reaction is finished. Centrifuging the obtained precipitate, repeatedly washing with ultrapure water and anhydrous ethanol, and vacuum drying to obtain HC-PDI @ Zn 2 InS 4 A composite photocatalyst (HPZ-30).
Example 2
The preparation method of the modified PDI photocatalyst comprises the following steps:
(1) 2.8mmol 3,4,9, 10-tetracarboxylic anhydride, 50mmol ammonium sulfate and 100g imidazole are thermally reacted for 2h at the constant temperature of 180 ℃ in the nitrogen atmosphere, 8mL of hydrochloric acid solution with the concentration of 0.5M is added after cooling, the mixture is uniformly stirred, the obtained product is repeatedly washed by ultrapure water, and the HC-PDI is obtained after freeze drying.
(2) Taking 50mg of HC-PDI obtained by preparation, ultrasonically dispersing in a mixed solution of glycerol and water (60 mL of glycerol and 100mL of water) for 1.0h, and then adding880mg InCl 3 ·4H 2 O, 409mg of zinc chloride and 451mg of thioacetamide, and carrying out oil bath reaction at 40 ℃ for 8 hours, and naturally cooling to room temperature after the reaction is finished. Centrifuging the obtained precipitate, repeatedly washing with ultrapure water and anhydrous ethanol, and vacuum drying to obtain HC-PDI @ Zn 2 InS 4 A composite photocatalyst (HPZ-50).
Example 3
The preparation method of the modified PDI photocatalyst comprises the following steps:
(1) Carrying out a constant temperature thermal reaction on 8.0mmol of 3,4,9, 10-tetracarboxylic anhydride, 150mmol of ammonium sulfate and 80g of imidazole for 7h at 120 ℃ in a nitrogen atmosphere, cooling, adding 9mL of a 0.8M hydrochloric acid solution, uniformly stirring, washing the obtained product with ultrapure water in a reverse mode, and carrying out freeze drying to obtain HC-PDI.
(2) 80mg of HC-PDI obtained by preparation is taken, ultrasonically dispersed in a mixed solution of glycerol and water (55 mL of glycerol and 60mL of water) for 0.2h, and then 880mg of InCl is added 3 ·4H 2 O, 409mg of zinc chloride and 451mg of thioacetamide, carrying out oil bath reaction at 70 ℃ for 4h, and naturally cooling to room temperature after the reaction is finished. Centrifuging the obtained precipitate, repeatedly washing with ultrapure water and anhydrous ethanol, and vacuum drying to obtain HC-PDI @ Zn 2 InS 4 A composite photocatalyst (HPZ-80).
Example 4
The preparation method of the modified PDI photocatalyst comprises the following steps:
(1) 6.2mmol of 3,4,9, 10-tetracarboxylic anhydride, 80mmol of ammonium sulfate and 40g of imidazole are thermally reacted for 5 hours at a constant temperature of 150 ℃ in a nitrogen atmosphere, after cooling, 15mL of hydrochloric acid solution with the concentration of 0.3M is added and uniformly stirred, the obtained product is repeatedly washed by ultrapure water, and then freeze drying is carried out, thus obtaining HC-PDI.
(2) 120mg of HC-PDI obtained by preparation is taken, ultrasonic dispersion is carried out for 1.0h in a mixed solution of glycerol and water (30 mL of glycerol and 90mL of water), and 880mg of InCl is added 3 ·4H 2 O, 409mg of zinc chloride and 451mg of thioacetamide, performing oil bath reaction at 100 ℃ for 4 hours, and naturally cooling to room temperature after the reaction is finished. Centrifuging the obtained precipitate, repeatedly washing with ultrapure water and anhydrous ethanol, and vacuum drying to obtain HC-PDI@Zn 2 InS 4 A composite photocatalyst (HPZ-120).
Comparative example 1
HC-PDI was prepared by performing only the first step on the basis of example 3.
Comparative example 2
ZnIn was prepared by carrying out the reaction of only step (2) on the basis of example 3 without adding HC-PDI 2 S 4 。
Comparative example 3
80mg of HC-PDI and 634.53mg of ZnIn were added 2 S 4 And (4) mixing the monomers.
Comparative example 4
This comparative example provides a preparation method according to the prior art to obtain PDI/ZnIn 2 S 4 The specific operation method of the nanofiber heterojunction photocatalyst is as follows:
3.5mmol of 3,4,9,10-tetracarboxylic dianhydride, 28.1mmol of beta-alanine and 18g of imidazole were placed in a four-necked flask and heated at 110 ℃ for 4 hours under a nitrogen atmosphere. After the reaction mixture was cooled, 100mL ethanol and 300M L in 2M HCl were added and stirred overnight. And (3) carrying out vacuum drying on the red solid obtained by suction filtration and repeated washing to obtain the common low-crystallinity PDI photocatalyst.
Taking 1g of low-crystallinity PDI photocatalyst to be ultrasonically dispersed in 30mL of ultrapure water, then adding 0.5g of zinc acetate, 2g of indium trichloride and 1g of thioacetamide, stirring uniformly, transferring to a reaction kettle, and carrying out hydrothermal reaction for 8h at 150 ℃. The obtained precipitate is centrifugally separated, washed repeatedly by ultrapure water and absolute ethyl alcohol and dried in vacuum to obtain PDI/ZnIn 2 S 4 A heterojunction photocatalyst.
Structural characterization
FIGS. 1 and 2 are HC-PDI @ Zn prepared in example 3, respectively 2 InS 4 Scanning electron microscope images and transmission electron microscope images of the composite photocatalyst. ZnIn obtainable from FIG. 1 2 S 4 The nano-sheet is uniformly grown on the surface of HC-PDI. As can be seen from FIG. 2, HC-PDI molecules have a rod-like structure, znIn 2 S 4 The nano-sheet is attached to the rod-shaped HC-PDI, presents a hierarchical heterostructure and an intuitive appearance structure chartThe steps show that the two materials are compounded successfully.
FIG. 3 is HC-PDI @ Zn prepared in example 3 2 InS 4 The X-ray diffraction pattern of the composite photocatalyst shows that HC-PDI and ZnIn simultaneously appear in the composite photocatalyst 2 S 4 Further illustrating the intimate association of the two materials. And the crystal form of HC-PDI is good, which indicates high crystallinity.
FIGS. 4 to 6 show HC-PDI @ Zn prepared by the preparation method of example 3 2 InS 4 The electron paramagnetic resonance spectrogram of the composite photocatalyst is known as HC-PDI @ Zn 2 InS 4 The composite photocatalyst generates superoxide radical (O) in photocatalytic reaction 2 - ) Hydroxyl radical (. OH) and cavity (h) + ) Three active substances.
Characterization of Properties
The photocatalytic activity evaluation according to the present invention employed a top illumination (Perfect Light) system with a 300W xenon lamp as the Light source and a 400nm filter. Fully performing ultrasonic treatment and introducing N into the system before illumination 2 To remove air. In the reaction, 5mg of a photocatalyst was added to 50mL of an aqueous ascorbic acid solution (0.2M), and the water decomposition reaction was carried out by visible light irradiation without a sacrifice agent.
The effect of the photocatalysts prepared in examples 1 to 4 on water decomposition is shown in fig. 7, and the effect of the photocatalysts prepared in comparative examples 1 to 3 on water decomposition is shown in fig. 8. As can be seen from FIGS. 7-8, the photocatalyst HPZ-80 prepared in the optimal composite proportion shows excellent visible light catalytic total hydrolysis efficiency without sacrifice agent, H 2 And O 2 The precipitation rates of (a) and (b) are 275.4. Mu. Mol g -1 h -1 And 138.4. Mu. Mol g -1 h -1 Efficiency compared to HC-PDI and ZnIn 2 S 4 The monomer and the physical mixture of the monomer and the monomer are obviously improved.
FIG. 9 is HC-PDI @ Zn prepared in example 3 2 InS 4 The X-ray diffraction patterns of the composite photocatalyst before and after reaction show that the original crystal structure of the catalyst is still maintained before and after reaction, which indicates that the catalyst has excellent stability.
PDI/ZnIn obtained in comparative example 4 2 S 4 Heterojunction catalyst under the same experimental conditions as in example 3 and without sacrificial agent, H 2 And O 2 The precipitation rate of (2) is only 48.9. Mu. Mol g -1 h -1 And 6.32. Mu. Mol g -1 h -1 . HC-PDI has a highly ordered self-assembled structure and a suitable energy band, and compared with PDI with low crystallinity, HC-PDI can be compared with ZnIn 2 S 4 A tighter heterojunction is formed, so that efficient and stable visible light-driven full-water decomposition is realized.
Claims (7)
1. A modified PDI photocatalyst is characterized in that Zn is attached to the surface of PDI 2 InS 4 Nanosheets forming a hierarchical direct Z-type heterojunction forming HC-PDI @ Zn 2 InS 4 A composite photocatalyst; wherein the PDI is a high-crystallinity PDI and has a rod-like structure.
2. The modified PDI photocatalyst according to claim 1, wherein the PDI is in combination with Zn 2 InS 4 The mass ratio of (A) to (B) is 1-4: 21.
3. A method for preparing the modified PDI photocatalyst of claim 1, comprising the steps of:
(1) Carrying out constant-temperature hydrothermal reaction on 3,4,9,10-tetracarboxylic anhydride, ammonium sulfate and imidazole in a nitrogen atmosphere, cooling after the reaction is finished, then adding hydrochloric acid to crystallize PDI, carrying out suction filtration, washing the obtained product, and carrying out freeze drying to obtain HC-PDI;
(2) Dispersing HC-PDI prepared in the step (1) in a mixed solution of glycerol and water by ultrasonic, adding indium trichloride, zinc chloride and thioacetamide, and reacting to obtain ZnIn 2 S 4 Growing on the surface of PDI, separating precipitate, washing, drying to obtain HC-PDI @ Zn 2 InS 4 A composite photocatalyst.
4. The method for preparing a modified PDI photocatalyst according to claim 3, wherein in the step (1), the hydrothermal reaction temperature is 80-180 ℃ and the reaction time is 2-10 h.
5. The method of preparing a modified PDI photocatalyst as claimed in claim 3, wherein in step (2), the reaction temperature is 40-130 ℃ and the reaction time is 0.5-8 h.
6. The method of preparing a modified PDI photocatalyst according to claim 3, wherein in step (2), the mass-to-volume ratio of PDI, glycerol and water is (0.01 to 10) g: (1-80) mL: (1-200) mL.
7. The modified PDI photocatalyst of claim 1 for producing H simultaneously through photocatalytic total hydrolysis 2 And O 2 The use of (1).
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| CN111389458A (en) * | 2020-01-16 | 2020-07-10 | 江南大学 | Carboxyl-containing perylene bisimide/oxygen-doped carbon nitride nanosheet heterojunction photocatalyst and preparation method and application thereof |
| CN112871186A (en) * | 2021-03-11 | 2021-06-01 | 福州大学 | Nickel diselenide/sulfur indium zinc composite photocatalyst and preparation method and application thereof |
| CN113769762A (en) * | 2021-10-09 | 2021-12-10 | 上海市普陀区人民医院(上海纺织第一医院) | Ultrathin ZnIn2S4Nano-sheet photocatalyst material and preparation method and application thereof |
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