CN116328792A - Zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water and preparation method thereof - Google Patents
Zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 73
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 69
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 54
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 31
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 19
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 15
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- TZNSLBQRBDSHQV-UHFFFAOYSA-N cadmium(2+) manganese(2+) disulfide Chemical compound [S-2].[Mn+2].[Cd+2].[S-2] TZNSLBQRBDSHQV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002073 nanorod Substances 0.000 claims abstract description 10
- 239000002077 nanosphere Substances 0.000 claims abstract description 8
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910052793 cadmium Inorganic materials 0.000 claims description 19
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 19
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention belongs to the technical field of photocatalysts, and in particular relates to a zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water and a preparation method thereof. Mn by zinc sulfide 0.3 Cd 0.7 S is subjected to in-situ ion exchange modification, so that zinc sulfide nanospheres are loaded on the surface of a manganese cadmium sulfide nanorod to obtain ZnS/Mn 0.3 Cd 0.7 S composite photocatalyst. The preparation method is simple and convenient to operate, the preparation conditions are well controlled, and the prepared zinc sulfide/manganese cadmium sulfide composite photocatalyst shows remarkable enhancement under the irradiation of visible lightThe catalyst can be applied to the field of visible light photocatalysis.
Description
Technical Field
The invention belongs to the technical field of photocatalysis nano materials, and relates to a zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water and a preparation method thereof.
Background
The problems of environmental pollution and energy crisis are getting more serious at the same time of the rapid development of modern economy and society. The growing energy demand and environmental concerns have accelerated active research into the development of new sustainable green energy technologies. Since Fujishima and Honda first demonstrated photocatalytic decomposition of water on a photoactive semiconductor catalyst in 1972, efforts have been made to develop efficient photocatalysts capable of collecting solar energy and converting it into chemical energy. Over the past few decades, various photocatalysts have been developed, including metal oxides, metal sulfides, and organic polymers. Among them, cadmium sulfide is receiving a great deal of attention due to its narrow bandgap (2.4 eV) and relatively high catalytic performance. However, the hydrogen generation activity of cadmium sulfide is severely limited due to rapid recombination of carriers and photo-etching problems. Various solid solutions composed of cadmium sulfide and other semiconductors have been developed to overcome the above problems due to their similar crystal structures.
Sulfide-based materials are considered to be good candidates for photocatalytic hydrogen production due to their suitable conduction band edges and narrow band gaps. Wherein the sulfide solid solution (e.g. ZnIn 2 S 4 、CuInS 2 And Zn 1-x Cd x S) is popular because of its adjustable band gap width and superior visible hydrogen production performance. Novel ternary solid solution cadmium manganese sulfide (Mn) x Cd 1-x S) has been used for photocatalytic hydrogen production. Although cadmium manganese sulfide has great potential in photocatalytic hydrogen production, there is still great room for improvement.
Disclosure of Invention
Based on the problems, the invention aims to provide a zinc sulfide/manganese cadmium sulfide composite photocatalyst for photolysis of water to produce hydrogen and a preparation method thereof. The invention uses zinc sulfide to produce Mn 0.3 Cd 0.7 S is subjected to in-situ ion exchange modification, so that zinc sulfide nanospheres are loaded on the surface of manganese cadmium sulfide nanorods, and the prepared photocatalyst shows remarkable enhancement under the irradiation of visible lightThe catalyst can be applied to the field of visible light photocatalysis.
The preparation method of the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis water comprises the following steps:
mn is added to 0.3 Cd 0.7 S, ultrasonic dispersion is carried out in deionized water to form suspension; slowly adding zinc acetate solution into the suspension, stirring to obtain Mn 0.3 Cd 0.7 S is uniformly mixed with zinc acetate to obtain a mixture; transferring the mixture into an oil bath, sealing, heating to react completely, centrifuging, collecting the product, washing with deionized water and ethanol, and drying at 60deg.C to obtain zinc sulfide/manganese cadmium sulfide composite photocatalyst (ZnS/Mn) 0.3 Cd 0.7 S)。
Further, mn 0.3 Cd 0.7 The mass concentration of S in the suspension is 5-10 mg/ml; preferably 7 to 9mg/ml.
Further, zinc acetate and Mn 0.3 Cd 0.7 The mole percentage of S is 0.1mol percent to 2mol percent; preferably 0.1mol% to 1mol%, more preferably 1mol%.
Further, the temperature of the heating reaction is 50-70 ℃; preferably 55 ℃ to 65 ℃; more preferably 60 ℃.
Further, the heating reaction time is 3-5 h; preferably 3.5 to 4.5 hours; more preferably 4h.
Further, the temperature of the heating reaction was 60℃and the heating reaction time was 4 hours.
ZnS/Mn of the invention 0.3 Cd 0.7 The S composite photocatalyst is used for producing hydrogen by photocatalytic hydrolysis, and is particularly used for producing hydrogen by visible light catalytic hydrolysis.
Further, the method for preparing hydrogen by photocatalysis of the catalyst of the invention is to prepare ZnS/Mn 0.3 Cd 0.7 S composite photocatalyst is dispersed in water to obtain suspension; sodium sulfide and sodium sulfite are added into the suspension as sacrificial agents to carry out photocatalysis hydrogen production reaction.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the invention is simple and easy to implement, the preparation conditions are easy to control, and the ZnS/Mn is prepared 0.3 Cd 0.7 The highest hydrogen production rate of the S composite photocatalyst for producing hydrogen by photolysis water can reach 82.34mmol/g/h, and the S composite photocatalyst is Mn 0.3 Cd 0.7 6.4 times of S; and the catalyst still has 91.3 percent of catalytic activity after 4 times of circulation, and has good stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of a composite photocatalyst of cadmium manganese sulfide, zinc sulfide/cadmium manganese sulfide prepared in example 1 and comparative example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a 1mol% zinc sulfide/cadmium manganese sulfide composite photocatalyst prepared in example 1 of the present invention;
FIG. 3 is a graph showing the effect of hydrogen production of cadmium manganese sulfide in different proportions prepared in example 1 of the present invention;
FIG. 4 is a graph showing the effect of hydrogen production by the composite photocatalyst of cadmium manganese sulfide, zinc sulfide, and zinc sulfide/cadmium manganese sulfide prepared in example 1 and comparative example 1 of the present invention;
FIG. 5 is a cycle chart of a photocatalytic hydrogen production experiment of a 1mol% zinc sulfide/cadmium manganese sulfide composite photocatalyst prepared in example 1 of the present invention.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are intended to illustrate the invention and not to limit it further.
Example 1
(1) Cadmium manganese sulphide (Mn) x Cd 1-x S (0.ltoreq.x.ltoreq.1)) is prepared:
20mmol of cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution and stirred for 0.5 hour; then 25mmol Thioacetamide (TAA) is added to make it fully dissolved and continuously stirred until fully and uniformly mixed; and then heating the mixture in a reaction kettle at 200 ℃ for 24 hours, cooling, centrifuging and washing after the reaction is finished, drying the mixture in an oven at 60 ℃ for 24 hours, and collecting the powder product to obtain the CdS.
20mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) is dissolved in 30ml deionized water and stirred for 0.5 hour; then 25mmol of Thioacetamide (TAA) is added to dissolve it sufficiently andcontinuously stirring until the materials are completely and uniformly mixed. And then heating the mixture in a reaction kettle at 200 ℃ for 24 hours, cooling, centrifuging and washing after the reaction is finished, drying the mixture in an oven at 60 ℃ for 24 hours, and collecting the powder products to respectively prepare MnS.
2mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) was dissolved in 30ml deionized water, 18mmol cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution, stirred for 0.5 hour and then mixed; 25mmol of Thioacetamide (TAA) was then added to the mixed solution, allowed to dissolve well and stirred continuously until thoroughly mixed. Then heating for 24 hours at 200 ℃ in a reaction kettle, cooling, centrifuging and washing after the reaction is finished, drying for 24 hours at 60 ℃ in an oven, and collecting to obtain a powder product to obtain Mn 0.1 Cd 0.9 S。
6mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) was dissolved in 30ml deionized water, 14mmol cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution, stirred for 0.5 hour and then mixed; other steps are same as Mn 0.1 Cd 0.9 S is prepared, and the powder product obtained by collection is Mn 0.3 Cd 0.7 S。
10mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) was dissolved in 30ml deionized water, 10mmol cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution, stirred for 0.5 hour and then mixed; other steps are same as Mn 0.1 Cd 0.9 S is prepared, and the powder product obtained by collection is Mn 0.5 Cd 0.5 S。
14mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) was dissolved in 30ml deionized water, 6mmol cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution, stirred for 0.5 hour and then mixed; other steps are same as Mn 0.1 Cd 0.9 S is prepared, and the powder product obtained by collection is Mn 0.7 Cd 0.3 S。
18mmol of manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O) was dissolved in 30ml deionized water, 2mmol cadmium acetate (Cd (CH) 3 COO) 2 ·2H 2 O) is dissolved in 30ml of ethylenediamine solution, stirred for 0.5 hour and then mixed; other steps are same as Mn 0.1 Cd 0.9 S is prepared, and the powder product obtained by collection is Mn 0.9 Cd 0.1 S。
Different proportions of cadmium manganese sulfide are used for producing hydrogen by the photocatalyst. 5mg of the synthesized photocatalyst was added to 50ml of deionized water to achieve uniform suspension, and then an amount of 1.3657g of sodium sulfide (0.35M) and 1.5756g of sodium sulfite (0.25M) were added as a sacrificial agent to the suspension, the reactor was sealed, and a vacuum was drawn to exclude air from the reactor. Each measurement was continuously carried out for 3 hours under irradiation with a 300W xenon lamp with a 420nm filter as a light source, and a photocatalytic hydrogen production reaction was carried out. After illumination, 6 samples are sequentially taken from 30min,60min,90min,120min,150min and 180min, the instrument is automatically injected into a gas chromatograph to analyze the content, and the experimental result is shown in figure 3, because the photo-induced rapid recombination of holes and electrons, the photo-catalytic hydrogen evolution rate of pure CdS is relatively low, and is 1.80mmol g -1 h -1 . The band gap of pure MnS is wider, the photocatalytic activity is low, the hydrogen production activity is almost 0, and the pure MnS does not have the photocatalytic hydrogen evolution performance. In the solid solution synthesis process, along with Mn 2+ Is added with Mn x Cd 1-x The oxidation-reduction reaction capability of S solid solution is improved, the hydrogen production activity is gradually enhanced, and the S solid solution is formed in Mn 0.3 Cd 0.7 The highest activity at S reaches 12.96mmol g -1 h -1 . With Mn 2+ Promote the introduction of Mn x Cd 1-x The band gap of S gradually widens and the conduction band moves to a more negative position with respect to CdS, resulting in an improvement in the reducing ability. The forbidden bandwidth is widened, the visible light absorption is reduced, and the Mn is continuously increased 2+ After the content, the band gap of the sample is further enlarged, the utilization rate of visible light is reduced, and the e generated by the semiconductor is caused - The amount is reduced, thus H 2 The yield of (a) decreases. As can be seen from fig. 3, the ratio of manganese source to cadmium source is optimal when the regulation ratio is 3:7, so that the ratio solid solution is selected for the subsequent experiments.
(2) Preparation of zinc sulfide/cadmium manganese sulfide composite photocatalyst: 0.5. 0.5gMn prepared in the step (1) 0.3 Cd 0.7 After the S powder is ultrasonically dispersed in 60ml of deionized water for 1 hour, a zinc acetate solution (0.005 mol/L0.79 ml) is slowly added into the mixed solution, and the mixed solution is stirred for 1 hour, then the mixture is transferred into an oil bath, sealed and heated for 4 hours at 60 ℃, the product is collected by centrifugation, washed by deionized water and ethanol, and dried for 24 hours at 60 ℃, and the zinc sulfide/cadmium manganese sulfide composite photocatalyst (0.1 mol% ZnS/Mn 0.3 Cd 0.7 S)。
Example 2
(1)Mn 0.3 Cd 0.7 S, preparation: as in example 1;
(2) 0.5g Mn prepared in step (1) 0.3 Cd 0.7 After ultrasonic dispersion of S powder in 60ml of deionized water for 1 hour, a zinc acetate solution (0.005 mol/L7.89 ml) was slowly added to the above mixed solution, stirred for 1 hour, and then the mixture was transferred to an oil bath, sealed and heated at 60℃for 4 hours, and the product was collected by centrifugation, washed with deionized water and ethanol, and dried at 60℃for 24 hours to prepare a zinc sulfide/cadmium sulfide composite photocatalyst (1 mol% ZnS/Mn) containing zinc sulfide and cadmium sulfide in a molar ratio of 1mol% 0.3 Cd 0.7 S)。
Example 3
(1)Mn 0.3 Cd 0.7 S, preparation: as in example 1;
(2) 0.5g Mn prepared in step (1) 0.3 Cd 0.7 After ultrasonic dispersion of S powder in 60ml of deionized water for 1 hour, a zinc acetate solution (0.01 mol/L7.89 ml) was slowly added to the above mixed solution, stirred for 1 hour, then the mixture was transferred to an oil bath, sealed and heated at 60℃for 4 hours, the product was collected by centrifugation, washed with deionized water and ethanol, and dried at 60℃for 24 hours to prepare a zinc sulfide/cadmium sulfide composite photocatalyst (2 mol% ZnS/Mn) containing zinc sulfide and cadmium sulfide in a molar ratio of 2mol% 0.3 Cd 0.7 S)。
Comparative example 1
Preparation of zinc sulfide: after 1.50g of thioacetamide was ultrasonically dispersed in 100ml of deionized water for 1 hour, a zinc acetate solution (0.5 mol/L10 ml) was slowly added to the above solution, and stirred for another 1 hour, and then the mixture was transferred to an oil bath to be sealed and heated at 60℃for 4 hours, and the product was collected by centrifugation, washed with deionized water and ethanol, and dried at 60℃for 24 hours, to finally obtain a white powder product.
The crystalline phase structures of the cadmium manganese sulfide, zinc sulfide and zinc sulfide/cadmium manganese sulfide visible-light catalysts prepared in examples 1 to 3 and comparative example 1 were analyzed by Japanese physics D/max2500PC autorotation X-ray diffractometer, wherein X-rays were Cu targets
The voltage is 40kV, the current is 100mA, the step size is 0.02 DEG, and the scanning range is 10 DEG-80 deg. The X-ray diffraction pattern is shown in figure 1, the peak shapes of all positions are consistent with CdS standard cards, and the peak shapes are consistent with Mn 2+ The addition of ions, the diffraction peak of pure CdS gradually shifted to higher angles, indicating Mn formation 0.3 Cd 0.7 Solid solutions of S, rather than simple mixtures of CdS and MnS, are sufficient to demonstrate successful synthesis of cadmium manganese sulfide materials. Meanwhile, no obvious diffraction peak of zinc sulfide is found in all zinc sulfide/cadmium manganese sulfide composite materials, which is probably caused by less zinc sulfide loaded on the cadmium manganese sulfide.
A Japanese JSM-6360A scanning electron microscope was used to observe the zinc sulfide/cadmium manganese sulfide composite photocatalyst (1 mol% ZnS/Mn) prepared in example 1 and containing 1mol% of zinc sulfide to cadmium manganese sulfide 0.3 Cd 0.7 S), as can be seen from the scanning electron microscope image of FIG. 2, the composite visible light catalyst prepared by the embodiment reveals that ZnS nano-spheres are loaded on Mn 0.3 Cd 0.7 Phenomenon of S nanorod surface. Pure Mn prepared 0.3 Cd 0.7 S is about a nanorod with a length between 200 and 800 nm. Pure ZnS consists of nanospheres of about 50nm or more in diameter. Mn can be observed after ZnS nano-spheres are introduced 0.3 Cd 0.7 The overall morphology structure of the S nano rod is not changed obviously, and a perfect nano rod structure is still maintained. From the figure, znS can be clearly observedNanospheres and Mn 0.3 Cd 0.7 S nanorods were in close contact, indicating Mn 0.3 Cd 0.7 The S nano rod substrate is favorable for the dispersion of the loaded ZnS nano spheres, and the interface contact between the S nano rod substrate and the ZnS nano spheres is good, so that the transfer and separation of mobile carriers are facilitated.
The zinc sulfide/cadmium manganese sulfide composite material prepared in the embodiment is used for producing hydrogen by a photocatalyst. 5mg of the synthetic photocatalyst was added to 50ml of deionized water to achieve uniform suspension, then 1.3657g of sodium sulfide (0.35M) and 1.5756g of sodium sulfite (0.25M) were added as sacrificial agents to the suspension, the reactor was sealed, and a vacuum was drawn to exclude air from the reactor. Each measurement was continuously carried out for 3 hours under irradiation with a 300W xenon lamp with a 420nm filter as a light source, and a photocatalytic hydrogen production reaction was carried out. After illumination, 6 samples are sequentially taken from 30min,60min,90min,120min,150min and 180min, an instrument is automatically injected into a gas chromatograph to analyze the content, the experimental result is shown in figure 4, the pure zinc sulfide has no catalytic hydrogen production activity, the pure cadmium manganese sulfide has a hydrogen production rate of 12.96mmol/g/h, the 1mol% zinc sulfide/cadmium manganese sulfide composite photocatalyst has a hydrogen production rate of 82.34mmol/g/h, the hydrogen production rate is about 6.4 times that of the pure cadmium manganese sulfide, and the photocatalytic hydrogen production activity of the composite photocatalyst can be effectively improved by the loaded zinc sulfide.
In order to verify the stability of the zinc sulfide/cadmium manganese sulfide composite photocatalyst for producing hydrogen by photolysis water, the invention prepares 1mol percent ZnS/Mn with higher hydrogen production efficiency 0.3 Cd 0.7 S, performing a photocatalytic hydrogen production cycle experiment. The experimental result is shown in figure 5, after 4 times of circulation, the hydrogen production rate of the 1mol percent zinc sulfide/manganese cadmium sulfide composite photocatalyst is 75.18mmol/g/h, and the initial catalytic activity of the 1mol percent zinc sulfide/manganese cadmium sulfide composite photocatalyst is 91.3 percent, which shows that the prepared zinc sulfide/manganese cadmium sulfide composite photocatalyst has good stability.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (9)
1. A zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water is characterized in that the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis of water is prepared by adding Mn to Mn by zinc sulfide 0.3 Cd 0.7 S, carrying out in-situ ion exchange modification to load the zinc sulfide nanospheres on the surface of the manganese cadmium sulfide nanorod.
2. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolysis of water to produce hydrogen, which is characterized in that Mn 0.3 Cd 0.7 S, ultrasonic dispersion is carried out in deionized water to form suspension; adding zinc acetate solution into the suspension, stirring to Mn 0.3 Cd 0.7 S is uniformly mixed with zinc acetate to obtain a mixture; transferring the mixture into an oil bath, sealing and heating until the reaction is complete, centrifugally collecting the product, washing with deionized water and ethanol, and drying at 60 ℃ to obtain the zinc sulfide/manganese cadmium sulfide composite photocatalyst.
3. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolyzing water to produce hydrogen according to claim 2, wherein Mn 0.3 Cd 0.7 The mass concentration of S in the suspension is 5-10 mg/ml.
4. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolyzing water to produce hydrogen according to claim 2, wherein the zinc acetate and the Mn are as follows 0.3 Cd 0.7 The mole percentage of S is 0.1mol percent to 2mol percent.
5. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolyzing water to produce hydrogen according to claim 2, wherein the temperature of the heating reaction is 50-70 ℃.
6. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolyzing water to produce hydrogen according to claim 2, wherein the heating reaction time is 3-5 h.
7. The method for preparing the zinc sulfide/cadmium manganese sulfide composite photocatalyst for photolytic water production of hydrogen according to claim 2, wherein the heating reaction temperature is 60 ℃, and the heating reaction time is 4 hours.
8. The application of the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis water as claimed in claim 1, wherein the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis water is used for producing hydrogen by visible light catalytic hydrolysis.
9. The application of the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis water according to claim 8, wherein the method for producing hydrogen by visible light catalytic hydrolysis is to disperse the zinc sulfide/manganese cadmium sulfide composite photocatalyst for producing hydrogen by photolysis water in water to obtain a suspension; sodium sulfide and sodium sulfite are added into the suspension as sacrificial agents to carry out photocatalysis hydrogen production reaction.
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| BO WANG ET AL.: ""Rational design and fabrication of MoSx nanoclusters decorated Mn0.3Cd0.7S nanorods with promoted interfacial charge transfer toward robust photocatalytic H2 generation"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 630, pages 37 - 46 * |
| CHUCHU CHENG ET AL.: ""Thermal-assisted photocatalytic H2 production over sulfur vacancy-rich Co0.85Se/Mn0.3Cd0.7S nanorods under visible light"", 《APPLIED SURFACE SCIENCE》, vol. 557, pages 1 - 10 * |
| YANLING HAN ET AL.: ""Synthesis of MnxCd1−xS nanorods and modification with CuS for extraordinarily superior photocatalytic H2 production"", 《CATALYSIS SCIENCE & TECHNOLOGY》, vol. 9, pages 1 - 2 * |
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