CN115382557A - ZnIn 2 S 4 /Zn 2 GeO 4 Bimetallic sulfur oxide photocatalyst and preparation method and application thereof - Google Patents
ZnIn 2 S 4 /Zn 2 GeO 4 Bimetallic sulfur oxide photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004246 zinc acetate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002073 nanorod Substances 0.000 claims abstract description 14
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
Abstract
The invention relates to ZnIn 2 S 4 /Zn 2 GeO 4 A preparation method of a bimetallic sulfur oxide photocatalyst and application thereof in photocatalytic decomposition of water for hydrogen evolution. The catalyst is prepared by synthesizing Zn from zinc acetate, germanium oxide and sodium hydroxide by hydrothermal method 2 GeO 4 Nanorod, and ZnIn is prepared by taking zinc germanate, zinc acetate, indium nitrate and thioacetamide as raw materials through solvothermal method 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst. The preparation method is simple to operate, easy to regulate and control, low in cost and environment-friendly. Preparation of ZnIn 2 S 4 /Zn 2 GeO 4 The bimetallic sulfur oxide photocatalyst has more excellent light absorption performance and separation efficiency of photon-generated carriers, and shows high-efficiency photocatalytic hydrogen production activity.
Description
Technical Field
The invention belongs to the technical field of photocatalysis for decomposing water to produce hydrogen, and particularly relates to ZnIn synthesized by adopting a solvothermal method 2 S 4 /Zn 2 GeO 4 A bimetallic oxysulfide photocatalyst; also relates to a preparation method of the catalyst and application of the catalyst in the aspect of water decomposition and hydrogen evolution through photocatalytic analysis.
Background
Environmental pollution and energy shortage become main problems to be solved urgently in the development process of the human society. Therefore, there is an increasing interest in developing a replacement for fossil fuels with renewable, environmentally friendly chemical fuels. The hydrogen energy is a clean, environment-friendly and efficient renewable energy source and is the most ideal substitute of fossil fuel. The preparation of hydrogen by photocatalytic water decomposition driven by solar energy is one of the most promising and important ways with the most practical application prospect, and the key to obtaining a large amount of hydrogen energy is to design an excellent photocatalyst with strong visible light absorption, low recombination rate of photon-generated carriers and chemical stability to improve the photocatalytic hydrogen production efficiency.
Sulfur indium zinc (ZnIn) 2 S 4 ) The photocatalyst is a bimetallic sulfide photocatalyst, the forbidden band width of the photocatalyst is about 2.0-2.4eV, and due to the advantages of unique photoelectric property, low toxicity and the like, the photocatalyst has been widely researched in the application of preparing hydrogen by decomposing water through photocatalysis and degrading organic pollutants through photocatalysis. However, the problems of high recombination rate of photo-generated electrons and holes, short carrier life, limited light absorption capacity and the like cause ZnIn 2 S 4 The photocatalytic performance of the catalyst cannot meet the requirements of practical application. In order to solve the problems, the heterojunction composite material needs to be designed and compounded with other materials, the prepared heterojunction composite material can accelerate charge transmission, effectively inhibit the recombination of photo-generated electrons and hole pairs, widen the photoresponse range and improve the photocatalysis.
Zinc germanate (Zn) 2 GeO 4 ) Is a bimetallic oxide photocatalyst consisting of zinc oxide tetrahedron (ZnO 4) and germanium oxide tetrahedron (GeO) 4 ) The photocatalyst is formed by connecting at a common angle, generates internal dipole moment, can inhibit the recombination of photo-generated electrons and hole pairs from the inside to a certain extent, and is a photocatalyst with application potential. However, the wider forbidden band width (about 4.5 eV) can only absorb and utilize ultraviolet light, and the utilization efficiency of sunlight is low, so that further practical application is hindered. Zn is added 2 GeO 4 The composition with other semiconductors is an effective way for improving the photocatalytic performance, can effectively adjust and reduce the forbidden band width and widen the light absorption range, thereby promoting the photocatalytic performanceThe transfer of photogenerated carriers inhibits the recombination of photogenerated electrons and hole pairs, and improves the photocatalytic hydrogen production performance.
In order to design and prepare a novel stable photocatalyst with high visible light response, the invention firstly uses zinc acetate, germanium oxide and sodium hydroxide as raw materials to prepare a zinc germanate nanorod photocatalyst by a hydrothermal method, then uses zinc acetate, indium nitrate and thioacetamide as raw materials to prepare a zinc sulfur photocatalyst by a solvothermal method, and finally adds a certain amount of prepared zinc germanate nanorods in the process of preparing zinc sulfur to obtain ZnIn 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst. The method is adopted to prepare ZnIn at present 2 S 4 /Zn 2 GeO 4 The bimetallic sulfur oxide photocatalyst and the research of the catalyst for photocatalytic water splitting to produce hydrogen have not been reported. The photocatalyst prepared by the method not only widens the light absorption range, but also effectively inhibits the recombination of photo-generated electrons and holes, and shows remarkably improved activity of photocatalytic decomposition of water to produce hydrogen in the photocatalytic process. Has important theoretical guidance and practical significance for solving the problem of energy crisis.
Disclosure of Invention
An object of the present invention is to provide a ZnIn 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst. The method comprises the steps of firstly preparing a zinc germanate nanorod photocatalyst by using zinc acetate, germanium oxide and sodium hydroxide as raw materials and using a hydrothermal method, then preparing a zinc sulfur photocatalyst by using zinc acetate, indium nitrate and thioacetamide as raw materials and using a solvothermal method, and finally adding a certain amount of prepared zinc germanate nanorods in the process of preparing zinc sulfur to obtain ZnIn 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst.
Another object of the present invention is to provide a ZnIn 2 S 4 /Zn 2 GeO 4 The preparation method of the bimetallic sulfur oxide photocatalyst specifically comprises the following steps:
1.Zn 2 GeO 4 preparation of
(1) Weighing 2mmol of zinc acetate, dispersing into a 20mL0.5M sodium hydroxide solution, and magnetically stirring until the zinc acetate is fully dissolved to obtain a colorless transparent solution;
(2) Weighing 1mmol of germanium oxide dispersion solution into the solution (1), magnetically stirring until the germanium oxide dispersion solution is completely dissolved, and then continuously magnetically stirring for 1-60 min to obtain a milky white solution;
(3) Transferring the stirred solution in the step (2) into a 50mL high-pressure reaction kettle to react for 12h at 200 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 8h at 50 ℃ to obtain Zn 2 GeO 4 Nano rods for later use;
2.ZnIn 2 S 4 preparation of (2)
(1) 0.8mmol of Zn (ac) was weighed 2 ·2H 2 O、1.6mmol In(NO 3 ) 3 ·6H 2 O and 3.5mmol CH 3 CSNH 2 Dissolved in 60mL of a mixed solvent of deionized water and absolute ethanol under magnetic stirring (v) Water (W) :v Ethanol = 1:1) to give a colorless clear solution;
(2) Transferring the stirred solution in the step (1) into a high-pressure reaction kettle to react for 24 hours at 180 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 12 hours at 60 ℃ to obtain a product for later use;
3.ZnIn 2 S 4 /Zn 2 GeO 4 preparation of bimetallic sulfur oxide photocatalyst
(1) Weigh 100mg of Zn 2 GeO 4 The nano-rods are ultrasonically dispersed in 60mL of mixed solvent (v) Water (W) :v Ethanol = 1:1), magnetic stirring for 30min;
(2) Respectively adding 0.26-0.5 mmol of zinc acetate, 0.52-1.0 mmol of indium nitrate and 1.14-2.18 mmol of thioacetamide into the solution, and magnetically stirring for 30min;
(3) The mixed solution obtained in (2) was transferred to a 50mL stainless steel autoclave and kept at 180 ℃ for 24 hours. The product is washed three times with ethanol and dried at 60 ℃ to obtain ZnIn 2 S 4 /Zn 2 GeO 4 Photocatalyst, noted InGe-x wherein x represents ZnIn 2 S 4 The nanosheets being Zn 2 GeO 4 Weight ratio of nano rod
Another object of the present invention is to provideSeed ZnIn 2 S 4 /Zn 2 GeO 4 The application of bimetallic sulfur oxide photocatalyst in photocatalytic water decomposition and hydrogen evolution.
Drawings
FIG. 1 shows Zn obtained in example 1 2 GeO 4 Scanning electron micrograph (a); znIn 2 S 4 Scanning electron micrograph (b); znIn 2 S 4 /Zn 2 GeO 4 Scanning electron microscopy (c) and high-resolution transmission electron microscopy (d).
FIG. 2 shows ZnIn obtained in example 2 2 S 4 /Zn 2 GeO 4 Photocatalytic hydrogen evolution rate (a) and hydrogen evolution circulation stability chart (b) under a xenon lamp light source.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples, which are provided in connection with the accompanying drawings and are not intended to limit the invention in any way.
Example 1
(a).Zn 2 GeO 4 Preparation of (2)
(1) Weighing 2mmol of zinc acetate, dispersing into 20mL of 0.5M sodium hydroxide solution, and magnetically stirring until the zinc acetate is fully dissolved to obtain colorless transparent solution;
(2) Weighing 1mmol of germanium oxide dispersion solution into the step (1), and stirring by magnetic force until the germanium oxide dispersion solution is completely dissolved to obtain milky white solution;
(3) Transferring the stirred solution in the step (2) into a 50mL high-pressure reaction kettle to react for 12 hours at 200 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 8 hours at 50 ℃ to obtain Zn 2 GeO 4 Nanorods, as shown in FIG. 1 (a).
(b)ZnIn 2 S 4 Preparation of
(1) 0.8mmol of Zn (ac) 2 ·2H 2 O、1.6mmol In(NO 3 ) 3 ·6H 2 O and 3.5mmol CH 3 CSNH 2 Dissolved in 60mL of a mixed solvent of deionized water and absolute ethanol under magnetic stirring (v) Water (W) :v Ethanol = 1:1) to give a colorless transparent solution;
(2) Transferring the stirred solution in the step (1) into a high-pressure reaction kettle to react for 24 hours at 180 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 12 hours at 60 ℃ to obtain the product, wherein the product is shown in a figure 1 (b).
(c)ZnIn 2 S 4 /Zn 2 GeO 4 Preparation of bimetallic sulfur oxide photocatalyst
(1) 100mg of zinc germanate nanorod is weighed and ultrasonically dispersed in 60mL of mixed solvent (v) Water (W) :v Ethanol = 1:1), magnetic stirring for 30min;
(2) Respectively adding 0.45mmol of zinc acetate, 0.90mmol of indium nitrate and 1.97mmol of thioacetamide into the solution, and magnetically stirring for 30min;
(3) The mixed solution obtained in (2) was transferred to a 50mL stainless steel autoclave and kept at 180 ℃ for 24 hours. The product is washed three times with ethanol and dried at 60 ℃ to obtain ZnIn 2 S 4 /Zn 2 GeO 4 The photocatalyst, denoted InGe-1.9, is shown in FIGS. 1 (c) and 1 (d)
Example 2
(a).Zn 2 GeO 4 Preparation of
Prepared according to the method and conditions of step (a) in example 1;
(b)ZnIn 2 S 4 preparation of
Prepared according to the method and conditions of step (b) in example 1;
(c)ZnIn 2 S 4 /Zn 2 GeO 4 preparation of bimetallic sulfur oxide photocatalyst
Prepared according to the method and conditions of step (c) in example 1;
(d) Evaluation of photocatalytic Hydrogen production application
The photocatalytic activity evaluation system for testing the hydrogen production performance of the photocatalyst is used for testing, and the specific experimental steps are as follows:
adding 100mL of 10% methanol aqueous solution into a quartz reaction vessel, and adding 50mg of ZnIn 2 S 4 /Zn 2 GeO 4 Dispersing the bimetallic sulfur oxide photocatalyst in the solution, placing the reactor in an ultrasonic machine for ultrasonic treatment for 2 seconds after ultrasonic stirring uniformly, repeating for 2-3 times until the catalyst at the bottom of the reactor is completely and uniformly dispersed. Quartz reactorAnd (3) continuing vacuumizing the vessel access system until no bubbles are emitted from the solution, turning off a vacuum pump, turning on a lamp (a lamp source is a 300W xenon lamp) → accessing hydrogen generated by the reaction into a gas chromatograph, starting analysis, and recording a peak area (the retention time is about 1 min). Circulating cooling water (6 ℃) is connected below the instrument to ensure constant temperature in the reaction process, and finally, the hydrogen evolution quantity and the hydrogen evolution rate are calculated according to the peak area and the hydrogen production time and are plotted, as shown in fig. 2 (a).
(e) Cyclic stability testing of photocatalysts
ZnIn obtained in example 1 was tested 2 S 4 /Zn 2 GeO 4 The cyclic stability of bimetallic sulfur oxide photocatalysts. Under the test condition that four circulation tests are carried out under the irradiation of a xenon lamp, each circulation test is carried out for 4 hours, the test result is shown in figure 2 (b), and the result shows that the hydrogen production rate basically has no descending trend after 5 circulation tests (20 hours). Description of ZnIn 2 S 4 /Zn 2 GeO 4 The bimetallic oxysulfide photocatalyst has good cyclability.
Claims (5)
1. ZnIn 2 S 4 /Zn 2 GeO 4 The preparation method of the bimetallic sulfur oxide photocatalyst is characterized in that the catalyst firstly synthesizes Zn by taking zinc acetate, germanium oxide and sodium hydroxide as raw materials through a hydrothermal method 2 GeO 4 Nanorod, and ZnIn is prepared by taking zinc acetate, indium nitrate and thioacetamide as raw materials by a solvothermal method 2 S 4 Photocatalyst, finally preparation of ZnIn 2 S 4 In the process of (A), a certain amount of prepared Zn is added 2 GeO 4 Nanorod to obtain ZnIn 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst.
The preparation method of the bimetallic sulfur oxide photocatalyst is characterized by comprising the following steps:
(a)Zn 2 GeO 4 preparation of
(1) Dispersing 2mmol of zinc acetate into 20mL of 0.5M sodium hydroxide solution, and magnetically stirring until the zinc acetate is fully dissolved to obtain a colorless transparent solution;
(2) 1mmol of germanium oxide dispersion solution is added into the solution (1), and magnetic stirring is carried out until the germanium oxide dispersion solution is completely dissolved to obtain milky white solution;
(3) Transferring the stirred solution in the step (2) into a 50mL high-pressure reaction kettle to react for 12h at 200 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 8h at 50 ℃ to obtain Zn 2 GeO 4 Nano rods for later use;
(b)ZnIn 2 S 4 preparation of
(1) 0.8mmol of Zn (ac) was weighed 2 ·2H 2 O、1.6mmol In(NO 3 ) 3 ·6H 2 O and 3.5mmol CH 3 CSNH 2 Dissolved in 60mL of a mixed solvent of deionized water and absolute ethanol under magnetic stirring (v) Water (I) :v Ethanol = 1:1) to give a colorless transparent solution;
(2) Transferring the stirred solution in the step (1) into a high-pressure reaction kettle to react for 24 hours at 180 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 12 hours at 60 ℃ to obtain a product;
(c)ZnIn 2 S 4 /Zn 2 GeO 4 preparation of bimetallic sulfur oxide photocatalyst
(1) Weigh 100mg of Zn 2 GeO 4 The nano-rod is ultrasonically dispersed in 60mL of mixed solvent (v) Water (W) :v Ethanol = 1:1), magnetic stirring for 30min;
(2) Respectively adding 0.26-0.5 mmol of zinc acetate, 0.52-1.0 mmol of indium nitrate and 1.14-2.18 mmol of indium nitrate into the solution, and magnetically stirring for 30min;
(3) The mixed solution obtained in (2) was transferred to a 50mL stainless steel autoclave and kept at 180 ℃ for 24 hours. The product was washed three times with ethanol and dried at 60 ℃ to obtain ZnIn 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst.
2. The method according to claim 1, characterized in that the preparation of ZnIn is carried out solvothermally 2 S 4 /Zn 2 GeO 4 A bimetallic sulfur oxide photocatalyst.
3. The process according to claim 1, characterized in that the ratio of the amounts of said substances of zinc acetate, indium nitrate, thioacetamide in step (b) is 1.
4. The process according to claim 1, characterized in that the amount of zinc acetate used in step (c) is 0.45mmol; 0.90mmol of indium nitrate; thioacetamide 1.97mmol.
5. ZnIn synthesized according to the method of claim 1 2 S 4 /Zn 2 GeO 4 The bimetallic sulfur oxide photocatalyst is characterized in that the catalyst is used for photocatalytic hydrogen production and shows remarkably improved photocatalytic hydrogen production activity.
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| CN202210429977.XA CN115382557A (en) | 2022-04-22 | 2022-04-22 | ZnIn 2 S 4 /Zn 2 GeO 4 Bimetallic sulfur oxide photocatalyst and preparation method and application thereof |
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| CN202210429977.XA CN115382557A (en) | 2022-04-22 | 2022-04-22 | ZnIn 2 S 4 /Zn 2 GeO 4 Bimetallic sulfur oxide photocatalyst and preparation method and application thereof |
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Citations (4)
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|---|---|---|---|---|
| CN104998634A (en) * | 2015-08-04 | 2015-10-28 | 华东理工大学 | Synthetic method for zinc germanium oxide with visible-light response function |
| CN109847766A (en) * | 2019-01-31 | 2019-06-07 | 中国地质大学（北京） | A kind of coplanar ZnIn2S4/WO3Z architecture catalyst material |
| US20200165148A1 (en) * | 2018-05-22 | 2020-05-28 | Dalian University Of Technology | A method using photocatalytic electrode coupled with microbial fuel cell to promote treatment of coking wastewater |
| CN111229205A (en) * | 2020-01-22 | 2020-06-05 | 青岛科技大学 | WO3/Zn2GeO4Non-noble metal bimetal oxide photocatalyst and preparation method and application thereof |
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Patent Citations (4)
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|---|---|---|---|---|
| CN104998634A (en) * | 2015-08-04 | 2015-10-28 | 华东理工大学 | Synthetic method for zinc germanium oxide with visible-light response function |
| US20200165148A1 (en) * | 2018-05-22 | 2020-05-28 | Dalian University Of Technology | A method using photocatalytic electrode coupled with microbial fuel cell to promote treatment of coking wastewater |
| CN109847766A (en) * | 2019-01-31 | 2019-06-07 | 中国地质大学（北京） | A kind of coplanar ZnIn2S4/WO3Z architecture catalyst material |
| CN111229205A (en) * | 2020-01-22 | 2020-06-05 | 青岛科技大学 | WO3/Zn2GeO4Non-noble metal bimetal oxide photocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| SUDIP K. BATABYAL ET AL.: "Synthesis, Characterization, and Photocatalytic Properties of In2S3, ZnIn2S4, and CdIn2S4 Nanocrystals", 《CRYSTAL GROWTH &DESIGN》, vol. 16, pages 2231 * |
| TAO YAN ET AL.: "Fabrication of In2S3/Zn2GeO4 composite photocatalyst for degradation of acetaminophen under visible light", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 506, pages 197 * |
| 邹晓莉: "ZnIn2S4基复合材料的制备与光催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 014 - 823 * |
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