CN116440955A - Porphyrin-based MOF/sulfur indium zinc heterojunction composite photocatalyst and preparation and application thereof - Google Patents
Porphyrin-based MOF/sulfur indium zinc heterojunction composite photocatalyst and preparation and application thereof Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 title claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052717 sulfur Inorganic materials 0.000 title claims description 18
- 239000011593 sulfur Substances 0.000 title claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000005083 Zinc sulfide Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 9
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002135 nanosheet Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002071 nanotube Substances 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 52
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 229910052763 palladium Inorganic materials 0.000 description 30
- -1 palladium porphyrin Chemical class 0.000 description 29
- 239000000843 powder Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 3
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- 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
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Abstract
The invention discloses a porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst, and preparation and application thereof, and relates to the technical field of photocatalysts, wherein a sulfur-indium-zinc nano sheet is directionally induced to grow on a frame of the porphyrin-based MOF by a solvothermal method to construct a nano tube with a binary shell heterostructure, and the nano tube has rich active sites, good band gap matching, strong visible light capturing capability and excellent charge migration efficiency, shows remarkable photocatalytic hydrogen production activity, and has a hydrogen evolution rate of up to 8000 mu mol g under visible light irradiation –1 h –1 The hydrogen evolution rate of the pure sulfur indium zinc is more than 20 times of that of the pure sulfur indium zinc.
Description
Technical field:
the invention relates to the technical field of photocatalysts, in particular to a porphyrin-based MOF/indium zinc sulfide heterojunction composite photocatalyst, and preparation and application thereof.
The background technology is as follows:
porphyrin-based MOFs due to their conjugated macrocyclesStructure and adjustable active sites show remarkable potential in the catalytic field. Porphyrin-based MOFs are typically synthesized by selecting appropriate metal salts and porphyrin ligands, and building up a network by precisely controlling their synthesis conditions, involving individual metal clusters/nodes and secondary building blocks. Many porphyrin-based MOFs have been widely used as photocatalysts for photocatalytic reactions, including nitrogen fixation reactions, CO 2 Reduction, moisture desorption hydrogen/oxygen evolution, organic compound degradation or conversion.
However, the performance of single metal coordination porphyrin-based MOF photocatalysts is still limited by the rapid recombination of photoexcited electrons and holes, so the preparation of composite materials and the construction of multi-metal active sites have proven to be important strategies for improving photocatalytic activity. It is emphasized that to address the energy crisis, various photocatalysts have been developed for use in the field of high efficiency photocatalytic hydrogen production, including titanium dioxide, carbon nitride, indium zinc sulfide, and the like. The zinc indium sulfide is used as a ternary sulfide with a layered structure and stable chemical properties, and is a very promising visible light response type photocatalyst. However, the photocatalytic activity of the single-component catalyst is still limited by the rapid recombination of light-induced electrons and holes, so that the development of the multi-component composite photocatalyst has important significance for improving the mobility of carriers.
The invention comprises the following steps:
the technical problem to be solved by the invention is to provide a preparation method of a porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst, wherein the porphyrin-based MOF/sulfur-indium-zinc heterojunction is successfully constructed by a solvothermal method, so that the visible light response range of pure sulfur-indium-zinc is widened, the defect of high recombination rate of photogenerated electrons and holes of single-metal porphyrin-based MOF and pure sulfur-indium-zinc is successfully solved, the efficient transfer of electrons is realized, the photocatalytic performance is further improved, and the preparation method has very important practical application prospect.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the invention aims at providing a preparation method of a porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst, which comprises the following steps:
s1, reacting metal salt with 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin to obtain porphyrin-based MOF;
s2, reacting the porphyrin-based MOF with a zinc source, an indium source and a sulfur source to obtain the porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst.
Preferably, the metal salt in step S1 is Cu 2+ 、Co 2+ 、Ni 2+ 、Fe 3+ 、Ru 3+ 、Pt 2+ 、Pd 2+ At least one of the hydrochloride or nitrate salts of (a).
Preferably, the mass ratio of the metal salt to the 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin in the step S1 is 1 (2-6).
Preferably, the reaction temperature of the metal salt and the 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin in the step S1 is 110-140 ℃ and the reaction time is 3-6 h.
Preferably, the zinc source in the step S2 is at least one of zinc acetate and zinc chloride; the indium source is at least one of indium nitrate and indium chloride; the sulfur source is at least one of thioacetamide and thiourea.
Preferably, in the step S2, the mass ratio of the porphyrin-based MOF to the zinc source, the indium source and the sulfur source is 1 (1-1.5): 2-3): 5-10. The dispersion degree of the sulfur indium zinc nano-sheets is controlled by regulating and controlling the porphyrin-based MOF with different contents, and the absorption intensity of visible light is regulated.
Preferably, the reaction temperature of the porphyrin-based MOF and the zinc source, the indium source and the sulfur source in the step S2 is 120-160 ℃ and the reaction time is 4-10 h.
The second purpose of the invention is to provide a porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst obtained by the preparation method. According to the invention, porphyrin-based MOF is used as a carrier, and the peripheral carboxyl active site of porphyrin is utilized to directionally induce the package of the sulfur indium zinc nano-sheet so as to form a compact heterostructure. Density Functional Theory (DFT) calculations indicate that the construction of the heterojunction establishes a strongly covalent electron transport channel and that electrons are accumulated and consumed at the interface between the porphyrin-based MOF and the sulfur-indium-zinc, the electron transfer pathway being from the porphyrin-based MOF to the sulfur-indium-zinc.
The invention further aims to provide application of the porphyrin-based MOF/indium zinc sulfide heterojunction composite photocatalyst in photocatalytic hydrogen production. The composite photocatalyst is used for photocatalytic hydrogen production under visible light irradiation, and electrons are enabled to transition from a porphyrin-based MOF conduction band to a sulfur-indium-zinc conduction band through heterojunction formation, so that charge separation is greatly accelerated, and further the photocatalytic hydrogen production activity is improved.
The beneficial effects of the invention are as follows:
1. the invention directionally induces the sulfur-indium-zinc nano-sheet to grow on the framework of the porphyrin-based MOF by a solvothermal method to construct the nano-tube with a binary shell heterostructure, and the nano-tube has rich active sites, good band gap matching, strong visible light capturing capability and excellent charge migration efficiency, shows remarkable photocatalytic hydrogen production activity, and has a hydrogen evolution rate of up to 8000 mu mol g under the irradiation of visible light –1 h –1 The hydrogen evolution rate of the pure sulfur indium zinc is more than 20 times of that of the pure sulfur indium zinc.
2. The invention provides a convenient and advanced prototype for synthesizing the binary heterojunction photocatalyst with excellent charge separation and transfer efficiency, and is expected to be widely applied to actual production.
Description of the drawings:
FIG. 1 is a three-dimensional simulation block diagram of palladium porphyrin-based MOF (a), indium zinc sulfide (b) and palladium porphyrin-based MOF/indium zinc sulfide (c) prepared in example 1 of the present invention;
FIG. 2 is a graph of N1s spectra of XPS for raw material 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin and palladium porphyrin MOF prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the sulfur indium zinc (a), palladium porphyrin based MOF (b) and palladium porphyrin based MOF/sulfur indium zinc (c) prepared in example 1 of the present invention;
FIG. 4 is a graph showing the solid absorbance curves of the zinc indium sulfide, the palladium porphyrin based MOF, and the palladium porphyrin based MOF/zinc indium sulfide prepared in example 1 of the present invention;
FIG. 5 shows Photoluminescence (PL) spectra of the indium zinc sulfide, palladium porphyrin based MOF, and palladium porphyrin based MOF/indium zinc sulfide prepared in example 1 of the present invention.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
Example 1
Preparation of palladium porphyrin MOF: adding 0.5g of palladium nitrate, 1.20g of 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin and 70mL of N, N-dimethylformamide into a beaker, stirring and carrying out ultrasonic treatment to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, placing the reaction kettle in a baking oven at 120 ℃ for reaction for 4 hours, cooling to room temperature, filtering, washing, and drying at 70 ℃ to obtain palladium porphyrin based MOF powder.
Preparation of sulfur indium zinc: 0.4g of zinc chloride, 1.1g of indium chloride and 2.5g of thioacetamide are dissolved in 30mL of deionized water, stirred and sonicated to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, placing the reaction kettle in a baking oven at 150 ℃ for reaction for 6 hours, cooling to room temperature, filtering, washing, and drying at 80 ℃ to obtain the sulfur indium zinc powder.
Preparation of palladium porphyrin based MOF/sulfur indium zinc of heterostructure: 0.4g of zinc chloride, 1.1g of indium chloride and 2.5g of thioacetamide are dissolved in 30mL of deionized water, and then 0.3g of palladium porphyrin-based MOF powder prepared in example 1 is added, stirred and sonicated to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, placing the reaction kettle in a baking oven at 150 ℃ for reaction for 6 hours, cooling to room temperature, filtering, washing, and drying at 80 ℃ to obtain palladium porphyrin based MOF/sulfur indium zinc powder.
As shown in fig. 2, in the N1s spectra of 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin, c=n-C and C-NH-C groups of the porphyrin ring were observed, with corresponding binding energies at 397.2 and 399.5eV, respectively; in the N1s spectrum of palladium porphyrin MOF, a significant change in the binding energy of N after palladium modification of the porphyrin was observed, the binding energy at 398.2eV corresponding to the Pd-N group, indicating that the central ring of 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin was palladium-metallized to form a palladium porphyrin-based MOF.
As can be seen from fig. 3, the morphology structure of the sulfur indium zinc is microsphere formed by aggregated nano-sheets, the palladium porphyrin-based MOF is a rectangular block structure, and after the palladium porphyrin-based MOF/sulfur indium zinc heterojunction is formed, it can be observed that the sulfur indium zinc nano-sheets are uniformly dispersed on the framework of the palladium porphyrin MOF.
As can be seen from fig. 4, the palladium porphyrin-based MOF/indium zinc sulfide heterojunction synthesized in example 1 has a significantly enhanced visible light absorption range.
50mg of the palladium porphyrin-based MOF powder prepared in example 1 was weighed, added to 100mL of an aqueous solution containing 10mL of triethanolamine, the reactor was installed and evacuated, and the generated hydrogen was detected using a gas chromatograph (GC 9790 II-PLL-01) with a TCD detector and argon as carrier gas using a 300W xenon lamp as a light source. Calculated to reach the hydrogen evolution rate of 590 mu mol g –1 h –1 The above.
50mg of the palladium porphyrin-based MOF/indium zinc sulfide powder prepared in example 1 was weighed, added to 100mL of an aqueous solution containing 10mL of triethanolamine, the reactor was installed and evacuated, and the resultant hydrogen gas was detected using a gas chromatograph (GC 9790 II-PLL-01) having a TCD detector and argon gas as carrier gas with a 300W xenon lamp as a light source. Through calculation, the hydrogen evolution rate is up to 8000 mu mol g – 1 h –1 The hydrogen evolution rate of the pure sulfur indium zinc is more than 20 times of that of the pure sulfur indium zinc.
50mg of the zinc indium sulfide powder prepared in example 1 was weighed, added to 100mL of an aqueous solution containing 10mL of triethanolamine, the reactor was installed and evacuated, and the resultant hydrogen gas was detected using a gas chromatograph (GC 9790 II-PLL-01) having a TCD detector and argon gas as carrier gas, with a 300W xenon lamp as a light source. Calculated to have a hydrogen evolution rate of 300 mu mol g –1 h –1 The above.
As can be seen from fig. 5, compared with the single-component photocatalyst, the PL emission intensity of the palladium porphyrin-based MOF/indium zinc sulfide heterojunction is drastically reduced, which proves that the preparation of the binary shell heterojunction is favorable for inhibiting the recombination of photoexcited electron holes, thereby improving the photocatalytic hydrogen production performance.
Example 2
Preparation of palladium porphyrin based MOF/sulfur indium zinc of heterostructure: 0.8g of zinc chloride, 2.5g of indium chloride and 6.1g of thioacetamide are dissolved in 60mL of deionized water, and then 0.9g of palladium porphyrin-based MOF powder prepared in example 1 is added, stirred and sonicated to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, placing the reaction kettle in a 160 ℃ oven for reaction for 5 hours, cooling to room temperature, filtering, washing, and drying at 70 ℃ to obtain palladium porphyrin based MOF/sulfur indium zinc powder.
Example 3
Preparation of palladium porphyrin based MOF/sulfur indium zinc of heterostructure: 0.7g of zinc acetate, 2.4g of indium nitrate and 4.2g of thiourea are dissolved in 50mL of deionized water, and then 0.7g of palladium porphyrin-based MOF powder prepared in example 1 is added, stirred and sonicated to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, placing the reaction kettle in an oven at 155 ℃ for reaction for 5 hours, cooling to room temperature, filtering, washing, and drying at 60 ℃ to obtain palladium porphyrin based MOF/sulfur indium zinc powder.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst is characterized by comprising the following steps of:
s1, reacting metal salt with 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin to obtain porphyrin-based MOF;
s2, reacting the porphyrin-based MOF with a zinc source, an indium source and a sulfur source to obtain the porphyrin-based MOF/sulfur-indium-zinc heterojunction composite photocatalyst.
2. The method of manufacturing according to claim 1, wherein: the metal salt in the step S1 is Cu 2+ 、Co 2+ 、Ni 2+ 、Fe 3+ 、Ru 3+ 、Pt 2+ 、Pd 2+ At least one of the hydrochloride or nitrate salts of (a).
3. The method of manufacturing according to claim 1, wherein: the mass ratio of the metal salt to the 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin in the step S1 is 1 (2-6).
4. The method of manufacturing according to claim 1, wherein: the reaction temperature of the metal salt and the 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin in the step S1 is 110-140 ℃ and the reaction time is 3-6 h.
5. The method of manufacturing according to claim 1, wherein: the zinc source in the step S2 is at least one of zinc acetate and zinc chloride; the indium source is at least one of indium nitrate and indium chloride; the sulfur source is at least one of thioacetamide and thiourea.
6. The method of manufacturing according to claim 1, wherein: in the step S2, the mass ratio of the porphyrin-based MOF to the zinc source, the indium source and the sulfur source is 1 (1-1.5), 2-3 and 5-10.
7. The method of manufacturing according to claim 1, wherein: in the step S2, the reaction temperature of the porphyrin-based MOF and the zinc source, the indium source and the sulfur source is 120-160 ℃ and the reaction time is 4-10 h.
8. The porphyrin-based MOF/indium zinc sulfide heterojunction composite photocatalyst obtained by the preparation method according to any one of claims 1 to 7.
9. The use of the porphyrin-based MOF/indium zinc sulfide heterojunction composite photocatalyst of claim 8 in photocatalytic hydrogen production.
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