CN115990522A - Preparation and application of MOF/CdZnS composite material - Google Patents
Preparation and application of MOF/CdZnS composite material Download PDFInfo
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- CN115990522A CN115990522A CN202211580666.XA CN202211580666A CN115990522A CN 115990522 A CN115990522 A CN 115990522A CN 202211580666 A CN202211580666 A CN 202211580666A CN 115990522 A CN115990522 A CN 115990522A
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 4
- 239000013118 MOF-74-type framework Substances 0.000 claims description 35
- 239000012621 metal-organic framework Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000013206 MIL-53 Substances 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 60
- 238000003756 stirring Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009423 ventilation 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
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a MOF/Cd x Zn 1‑x A preparation method and application of an S composite material belong to the field of photocatalytic material preparation. The invention adopts an electrostatic self-assembly method to prepare the MOF/Cd x Zn 1‑x S composite material, which is simple and easy to implement, cost-effective, environment-friendly, easy to popularize in large scale, and the obtained MOF/Cd x Zn 1‑x The S composite material is in a sheet stacking shape, and can catalyze benzyl alcohol to selectively oxidize to generate hydrogenated benzoin under the irradiation of visible light and cooperatively produce hydrogen, thereby not only meeting the sustainable development requirement of green synthesis, but also being capable ofMeanwhile, industrial products with high added value and clean hydrogen energy are obtained, and the method has good application prospect.
Description
Technical Field
The invention belongs to the field of photocatalytic material preparation, and in particular relates to a MOF/Cd x Zn 1-x Preparation method and application of S composite material.
Background
The hydrogenated benzoin is an important organic synthesis intermediate and fine chemical products, can be used as chiral auxiliary agents, structural units and chiral ligands, is widely applied to industries such as medicines, dyes and the like, and can be synthesized by benzyl alcohol oxidation. However, the traditional oxidation method is often carried out under the harsh conditions of high temperature, high pressure, strong acid, strong alkali and the like, so that not only is energy consumed, but also environmental pollution is possibly caused, and the method does not accord with the concept of green environmental protection. The method for synthesizing the hydrogenated benzoin by oxidizing the benzyl alcohol by photocatalysis is a green synthesis method, has simple process and environment protection, can not only utilize solar energy to catalyze the benzyl alcohol to oxidize to generate the hydrogenated benzoin, but also obtain clean and efficient hydrogen energy. Solid solution sulfide Cd x Zn 1-x S is a visible light catalyst with easily available raw materials and simple preparation method, and the valence band potential of the visible light catalyst can oxidize benzyl alcohol to produce hydrogenated benzoin, but Cd x Zn 1-x The photo-generated carrier recombination rate of S is high, which limits the practical application. Thus, cd is developed x Zn 1-x The S-based material is applied to the green synthesis of high-added-value organic matters by catalyzing benzyl alcohol oxidation coupling to produce hydrogen through visible light.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a MOF/Cd x Zn 1-x Preparation method and application of S composite material, and preparation method is simple and easyThe method is cost-effective, environment-friendly and easy to popularize on a large scale, and the prepared MOF/Cd x Zn 1-x The S composite material has the advantages of high photocatalytic activity, high selectivity and good stability, and can be applied to the oxidative coupling of benzyl alcohol by visible light catalysis to produce hydrogen.
In order to achieve the above purpose, the invention adopts the following technical scheme:
MOF/Cd x Zn 1-x S (x is more than or equal to 0 and less than or equal to 1) composite material and is prepared from metal organic framework material MOF and solid solution sulfide Cd x Zn 1-x S is synthesized by an electrostatic self-assembly method; specifically, a certain amount of MOF and Cd x Zn 1-x S is dispersed in a mixed solution of deionized water and absolute ethyl alcohol (2:1, v/v), and stirred for 3-5 hours in an oil bath at a constant temperature of 60-100 ℃ to obtain the MOF/Cd x Zn 1-x S composite material.
Further, the MOF and Cd used x Zn 1-x The mass ratio of S is (0.05-0.65): 1.
Further, the MOF is any one of Ni-MOF-74, MIL-53 (Fe) and ZIF-67.
Further, the Cd x Zn 1-x The S is prepared by taking a cadmium source, a zinc source and a sulfur source as raw materials and synthesizing the raw materials through a solvothermal method, specifically, dispersing the cadmium source and the zinc source into a mixed solution of deionized water and ethylenediamine (1:1, v/v) according to a required proportion, stirring for 0.5-h, then adding the sulfur source, continuously stirring for 0.5-h, transferring the dispersion into a high-pressure reaction kettle, and reacting at the constant temperature of 150-180 ℃ for 10-24 hours.
The cadmium source is any one of cadmium acetate, cadmium nitrate and cadmium chloride, the zinc source is any one of zinc acetate, zinc nitrate and zinc chloride, and the sulfur source is any one of thioacetamide, sodium sulfide and thiourea.
MOF/Cd prepared by the method x Zn 1-x The S composite material can be used for catalyzing reaction of benzyl alcohol oxidative coupling to produce hydrogen by visible light.
The invention has the remarkable advantages that:
(1) The invention synthesizes MOF/Cd by using an electrostatic self-assembly method x Zn 1-x The S composite material has excellent photocatalytic activity and stability, can catalyze benzyl alcohol to be selectively oxidized to generate hydrogenated benzoin in an acetonitrile solvent system under the irradiation of visible light, and can reduce protons to generate H 2 。
(2) The preparation method disclosed by the invention is simple to operate, low in cost, environment-friendly, free from severe operation environment requirements and beneficial to large-scale popularization.
Drawings
FIG. 1 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 X-ray powder diffraction pattern of S;
FIG. 2 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S (a), ni-MOF-74 (b) and Ni-MOF-74/Cd 0.7 Zn 0.3 S (c) scanning electron microscope image;
FIG. 3 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 An ultraviolet-visible absorption spectrum of S;
FIG. 4 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 S, an activity comparison graph of oxidative coupling of benzyl alcohol to produce hydrogen;
FIG. 5 is a Ni-MOF-74/Cd as prepared in example 1 0.7 Zn 0.3 And S, a stability result diagram of the oxidative coupling of benzyl alcohol to produce hydrogen by visible light catalysis.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1: ni-MOF-74/Cd 0.7 Zn 0.3 Preparation of S composite material
1) Weighing 1.6791 g cadmium acetate and 0.5927 g zinc acetate, dispersing in a mixed solution composed of 30 mL deionized water and 30 mL ethylenediamine, stirring for 0.5 h, adding 1.8783 g thioacetamide, stirring for 0.5 h, transferring the dispersion into a 100 mL high-pressure reaction kettle, and stirring at 180deg.CKeeping the temperature for reaction 24 h, naturally cooling to room temperature, and washing with ethanol and deionized water to ion concentration<10 Drying 24. 24 h at 60℃to give yellow Cd 0.7 Zn 0.3 S powder;
2) Weighing 1.60 g nickel nitrate hexahydrate, 0.48 g terephthalic acid and 2.40 g polyvinylpyrrolidone, dissolving in 20 mL deionized water, 20 mL absolute ethyl alcohol and 20 mL of N, N-dimethylformamide, stirring 1 h, transferring the mixed solution into a 100 mL high-pressure reaction kettle, carrying out heat preservation reaction at 150 ℃ for 10 h, naturally cooling to room temperature, washing the obtained mixture with ethanol and deionized water until the ion concentration is less than 10 ppm, and drying at 60 ℃ for 24 h to obtain green Ni-MOF-74 powder;
3) Weigh 0.0175 g Ni-MOF-74 and 0.1 g Cd 0.7 Zn 0.3 S, dispersing in a mixed solution composed of 40 mL deionized water and 20 mL absolute ethyl alcohol, stirring at a constant temperature of 80 ℃ under an oil bath for 3.5 h, volatilizing the solvent, and drying at 60 ℃ for 24 h to obtain the composite Ni-MOF-74/Cd 0.7 Zn 0.3 S。
FIG. 1 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 X-ray powder diffraction pattern of S. As can be seen from the figure, cd was produced 0.7 Zn 0.3 S is in a cubic crystal form, and Ni-MOF-74/Cd 0.7 Zn 0.3 S composite material can be observed to be ascribed to cubic Cd 0.7 Zn 0.3 Characteristic diffraction peaks for S and Ni-MOF-74.
FIG. 2 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S (a), ni-MOF-74 (b) and Ni-MOF-74/Cd 0.7 Zn 0.3 S (c) scanning electron microscope image. As shown in the figure, cd 0.7 Zn 0.3 S is an irregular particle with a diameter of about 100 nm, ni-MOF-74 is a sheet-like stacked structure with a side length of about 10 μm, and the composite material is characterized in that Cd is uniformly distributed on the Ni-MOF-74 0.7 Zn 0.3 S particles.
FIG. 3 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 Ultraviolet-visible absorption spectrum of S. As shown in the figure, the composite Ni-MOF-74/Cd 0.7 Zn 0.3 S and Cd 0.7 Zn 0.3 The light response spectrum of S is not obviously different, and the absorption band edges are about 500 nm.
Application example 1 test of visible light catalytic benzyl alcohol oxidative coupling hydrogen production performance
Cd obtained in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 The S composite material is used for catalyzing benzyl alcohol oxidation coupling to produce hydrogen by visible light. The reaction was carried out in a closed system with a reactor volume of about 15 mL using a 300W xenon lamp fitted with a 400 nm filter as the light source. Weighing 10 mg sample, placing in a reactor, adding 10 mL acetonitrile, dropwise adding 100 μl benzyl alcohol, magnetically stirring, sealing with vacuum grease, introducing condensed water to maintain the reaction system temperature at 20deg.C, continuously introducing high purity argon gas 0.5 h to remove air, then closing a ventilation valve, quantitatively sampling after illumination for 3 h, and detecting the product by gas chromatography and liquid chromatography, with the result shown in figure 4.
FIG. 4 is a schematic diagram of Cd prepared in example 1 0.7 Zn 0.3 S, ni-MOF-74 and Ni-MOF-74/Cd 0.7 Zn 0.3 And S is an activity comparison graph for catalyzing benzyl alcohol oxidation coupling to produce hydrogen. As shown in the figure, ni-MOF-74/Cd 0.7 Zn 0.3 The yield of hydrogenated benzoin produced by the catalysis of the S composite material is 3.8 mmol g -1 h -1 The yield of the catalytically produced benzaldehyde was 0.08 mmol g -1 h -1 The hydrogen production rate reaches 3.74 mmol g -1 h -1 The selectivity is as high as 95%. Under the same conditions, ni-MOF-74 does not detect the product, cd 0.7 Zn 0.3 The yield of the benzaldehyde produced by S catalysis is 0.35 mmol g -1 h -1 Hydrogen production rate was 0.341 mmol g -1 h -1 Indicating Ni-MOF-74/Cd 0.7 Zn 0.3 The S composite material has excellent photocatalytic benzyl alcohol oxidation coupling hydrogen production activity.
Application example 2 test of stability of oxidative coupling hydrogen production of benzyl alcohol by visible light catalysis
The photocatalytic benzyl alcohol oxidative coupling hydrogen production activity test of application example 1 was performed for 5 times, namely, after one reaction, the catalyst was recovered by filtration and drying, and the next round of reaction was performed, and the measurement was continuously performed for 5 times, and the result is shown in fig. 5.
FIG. 5 is a Ni-MOF-74/Cd as prepared in example 1 0.7 Zn 0.3 And S, a stability result diagram of the oxidative coupling of benzyl alcohol to produce hydrogen by visible light catalysis. As shown in the figure, the Ni-MOF-74/Cd has undergone the reaction for a total duration of 15 h 0.7 Zn 0.3 The S composite material still has higher catalytic activity, which shows that the S composite material has good stability.
Example 2: MIL-53 (Fe)/Cd 0.8 Zn 0.2 Preparation of S composite material
1) Weighing 1.9190 g cadmium acetate and 0.3951 g zinc acetate, dispersing in a mixed solution composed of 30 mL deionized water and 30 mL ethylenediamine, stirring for 0.5 h, adding 1.8783 g thioacetamide, continuously stirring for 0.5 h, transferring the dispersion into a 100 mL high-pressure reaction kettle, reacting at 180deg.C under heat preservation for 24 h, naturally cooling to room temperature, and washing with ethanol and deionized water to ion concentration<10 Drying 24. 24 h at 60℃to give yellow Cd 0.8 Zn 0.2 S powder;
2) Weighing 0.2700 g ferric chloride and 0.1660 g terephthalic acid, dispersing in 5 mL of N, N-dimethylformamide, magnetically stirring 0.5 h, transferring into a 20 mL high-pressure reaction kettle, reacting at 150 ℃ under heat preservation 12 h, naturally cooling to room temperature, washing the obtained mixture with ethanol and deionized water until the ion concentration is less than 10 ppm, and drying at 60 ℃ for 24 h to obtain yellow MIL-53 (Fe) powder;
3) 0.010 g MIL-53 (Fe) and 0.1 g Cd were weighed out 0.8 Zn 0.2 S, dispersing in a mixed solution composed of 40 mL deionized water and 20 mL absolute ethyl alcohol, stirring for 5 h under a constant temperature oil bath at 60 ℃ to volatilize the solvent, and drying for 24 h at 60 ℃ to obtain the composite material MIL-53 (Fe)/Cd 0.8 Zn 0.2 S。
Example 3: ZIF-67/Cd 0.9 Zn 0.1 Preparation of S composite material
1) Weighing 2.1588 g cadmium acetate and 0.1976 g zinc acetate, dispersing in a mixed solution composed of 30 mL deionized water and 30 mL ethylenediamine, stirring for 0.5 h, adding 1.8783 g thioacetamide, stirring for 0.5 h, transferring the dispersion into a 100 mL high-pressure reaction kettle, reacting at 180deg.C under heat preservation for 24 h, naturally cooling to roomAfter the temperature is reached, the mixture is washed by ethanol and deionized water to reach the ion concentration<10 Drying 24. 24 h at 60℃to give yellow Cd 0.9 Zn 0.1 S powder;
2) Weighing 2.3282 g cobalt nitrate, stirring in 180 mL methanol (solution A) for 10 min, weighing 2.6272 g of 2-methylimidazole, stirring in 140 mL methanol (solution B) for 10 min, rapidly injecting solution B into solution A, standing at room temperature for 24 h, washing with methanol until the ion concentration is less than 10 ppm, and drying at 60 ℃ for 24 h to obtain purple ZIF-67 powder;
3) 0.020 g ZIF-67 and 0.1 g Cd were weighed out 0.9 Zn 0.1 S, dispersing in a mixed solution composed of 40 mL deionized water and 20 mL absolute ethyl alcohol, stirring for 4 h under a constant temperature oil bath at 70 ℃ to volatilize the solvent, and drying for 24 h at 60 ℃ to obtain the composite material ZIF-67/Cd 0.9 Zn 0.1 S。
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. MOF/Cd x Zn 1-x The preparation method of the S composite material is characterized by comprising the following steps of: the MOF/Cd x Zn 1-x The S composite material is composed of metal organic framework material MOF and solid solution sulfide Cd x Zn 1-x S is synthesized by an electrostatic self-assembly method; wherein MOF and Cd x Zn 1-x The mass ratio of S is (0.05-0.65), wherein x is more than or equal to 1 and less than or equal to 0 and less than or equal to 1.
2. The MOF/Cd of claim 1 x Zn 1-x The preparation method of the S composite material is characterized by comprising the following steps of: the MOF and Cd are added in certain amounts x Zn 1-x S is dispersed in a mixed solution of deionized water and absolute ethyl alcohol, and stirred for 3-5 hours in an oil bath at a constant temperature of 60-100 ℃ to obtain the MOF/Cd x Zn 1-x S composite material.
3. The MOF/Cd according to claim 1 or 2 x Zn 1-x The preparation method of the S composite material is characterized by comprising the following steps of: the MOF is Ni-MOF-74, MIL-53 (Fe),Any one of ZIF-67.
4. The MOF/Cd of claim 2 x Zn 1-x The preparation method of the S composite material is characterized by comprising the following steps of: the volume ratio of deionized water to absolute ethyl alcohol in the mixed solution is 2:1.
5. A MOF/Cd prepared by the method of claim 1 x Zn 1-x The application of the S composite material in the oxidative coupling of benzyl alcohol to produce hydrogen by visible light catalysis.
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