CN114192167A - Photocatalyst, preparation method thereof, photocatalyst system and application - Google Patents
Photocatalyst, preparation method thereof, photocatalyst system and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 claims 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000006104 solid solution Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 8
- 239000004246 zinc acetate Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration 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
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 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
- 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
-
- 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
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- 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
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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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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a photocatalyst, a preparation method thereof, a photocatalyst system and application thereof, and high-performance Zn is obtained by changing the pH value of a precursor solutionxCd1‑xS is in particular Zn0.5Cd0.5S solid solution nano-particles, and on the basis, a three-dimensional ordered macroporous 3DOMZrO is constructed2/Zn0.5Cd0.5The S (Zr3D/CZS) heterojunction material effectively improves the photoproduction electron-hole separation efficiency of the catalyst, widens the light absorption range of the catalyst and effectively improves the utilization rate of sunlight. The photocatalyst is used for photocatalytic water splitting hydrogen production, shows good photocatalytic performance, and has important significance for practical application of photocatalytic water splitting hydrogen production.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a photocatalyst, a preparation method thereof, a photocatalyst system and application.
Background
Human beings in the 21 st century face two challenges of environmental pollution and energy shortage, and therefore, there is a great need for developing clean, green and renewable energy sources. The hydrogen energy is widely applied to industrial production due to the advantages of no pollution, sustainability, high heat value and the like, and has wide application prospect as a substitute of the traditional fossil fuel. The hydrogen production by decomposing water by using solar energy is considered to be an effective way for solving the problem.
In the current catalyst study, ZnxCd1-xS photocatalytic materials are widely studied. ZnxCd1-xS is a solid solution material consisting of CdS and ZnS and has high photocatalytic hydrogen production performance. It has excellent physicochemical properties such as: has proper band gap (2.2-2.6eV), visible light response and small particle size, and can regulate and control the band gap by changing the molar ratio of Zn to Cd. It is reported that when the molar ratio of Zn to Cd is 1:1 hour, Zn0.5Cd0.5And S has the highest hydrogen production performance. However, the single zinc cadmium sulfide semiconductor catalyst also has the disadvantage of difficulty in avoiding the rapid recombination of electron holes and the lack of active sites, which limits its photocatalytic activity to some extent. Therefore, suitable semiconductors and pure Zn were sought0.5Cd0.5The matching of the S energy level to solve the defects is the key to improving the photocatalytic hydrogen production capability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a photocatalyst with excellent photocatalytic hydrogen production performance, a preparation method thereof, a photocatalyst system and application.
In a first aspect, the present invention provides a photocatalyst, wherein the photocatalyst adopts ZnxCd1-xS, particularly preferably Zn0.5Cd0.5S, and in the preparation of ZnxCd1-xAnd when S is used, the pH value of the precursor solution is effectively controlled to be 7-11, preferably 8-11, particularly preferably 9.95-10.05, so that the prepared photocatalyst has the best photocatalytic performance.
In a second aspect, the present invention further provides 3DOM ZrO for further improving the photocatalytic performance of the photocatalyst2/Zn0.5Cd0.5S heterojunction material by preparationThree-dimensional ordered macroporous ZrO2Material (3DOM ZrO2), adding 3DOM ZrO2With Zn0.5Cd0.5S is combined to prepare 3DOM ZrO2/Zn0.5Cd0.5The S heterojunction material greatly improves the photocatalytic performance of the photocatalyst.
In a third aspect, the photocatalyst is prepared into a photocatalytic system and applied to photocatalytic water decomposition for hydrogen production, the maximum hydrogen production rate can reach 83mmol/g/h, and the excellent performance of photocatalytic water decomposition for hydrogen production is shown.
Preferably, when the photocatalyst according to the first aspect or the photocatalyst obtained by the method for preparing a photocatalyst according to the second aspect is used for photocatalytic hydrogen production by water decomposition, Na is used2S·9H2O and Na2SO3The water solution is used as hydrogen-producing sacrificial agent.
In conclusion, the invention obtains high-performance Zn by changing the pH value of the precursor solutionxCd1-xS is in particular Zn0.5Cd0.5S solid solution nano-particles, and constructing three-dimensional ordered macroporous 3DOM ZrO based on the S solid solution nano-particles2/Zn0.5Cd0.5The S (Zr3D/CZS) heterojunction material effectively improves the photoproduction electron-hole separation efficiency of the catalyst, widens the light absorption range of the catalyst, effectively improves the utilization rate of sunlight, and has certain practical value and application prospect due to the construction of the high-performance heterojunction catalyst.
By adopting the technical scheme, the invention has the following beneficial technical effects:
1. the invention synthesizes Zn through effective control0.5Cd0.5The pH of the precursor solution in S can effectively improve the photocatalytic performance, and the solution has the maximum hydrogen production performance when the pH is close to 10;
2. 3DOM ZrO obtained by the invention2/Zn0.5Cd0.5The S heterojunction material effectively inhibits the recombination of photo-generated electrons and holes, and has the maximum hydrogen production rate of 83 mmol/g/h;
3. the invention realizes high-efficiency simulation of solar photocatalytic hydrogen production by water decomposition, and the photocatalyst can be used for photocatalytic hydrogen production by water decomposition, and has certain practical value and application prospect.
Drawings
FIG. 1 shows Zn prepared0.5Cd0.5Powder diffractogram of S solid solution;
FIG. 2 is a powder diffraction pattern of the prepared Zr3D/CZS10 heterojunction material;
FIG. 3 shows CZS7, CZS10 and 3DOM ZrO2And 3DOM 2ZrO2A Field Emission Scanning Electron Microscope (FESEM) image of/CZS 10;
FIG. 4 shows Zn prepared0.5Cd0.5(S) the ultraviolet-visible diffuse reflectance spectrum of the solid solution;
FIG. 5 is a UV-VIS diffuse reflectance spectrum of the prepared Zr3D/CZS10 heterojunction material;
FIG. 6 shows Zn under simulated solar radiation0.5Cd0.5The performance schematic diagram of photocatalytic hydrogen production of the S sample;
FIG. 7 is a diagram showing the performance of photocatalytic hydrogen production by a Zr3D/CZS10 system under simulated sunlight irradiation.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1: preparation of Zn0.5Cd0.5S (CZS7) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; then weighing 150mg Thioacetamide (TAA) and adding into the solution, continuously stirring for 20-30 min, finally heating in a 100mL autoclave with polytetrafluoroethylene lining at 180 ℃ for 16h, precipitating and centrifuging the obtained precipitate solution, washing, and drying at 80 ℃ for 6h to obtain Zn0.5Cd0.5S (CZS7) nano material.
Example 2: preparation of Zn0.5Cd0.5S (CZS8) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting with sodium hydroxide solution (NaOH,10M) under pH meterAdjusting pH to 7.95-8.05, adding 150mg Thioacetamide (TAA) into the solution, stirring for 20-30 min, heating at 180 deg.C in 100mL autoclave with polytetrafluoroethylene lining for 16h, precipitating, centrifuging, washing, and drying at 80 deg.C for 6h to obtain Zn0.5Cd0.5S (CZS8) nano material.
Example 3: preparation of Zn0.5Cd0.5S (CZS9) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting pH with sodium hydroxide solution (NaOH,10M) under pH meter to 8.95-9.05, adding 150mg Thioacetamide (TAA) into the solution, stirring for 20-30 min, heating at 180 deg.C in 100mL autoclave with polytetrafluoroethylene lining for 16 hr, centrifuging the precipitate, washing, and drying at 80 deg.C for 6 hr to obtain Zn0.5Cd0.5S (CZS9) nano material.
Example 4: preparation of Zn0.5Cd0.5S (CZS10) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting pH with sodium hydroxide solution (NaOH,10M) under pH meter to 9.95-10.05, adding 150mg Thioacetamide (TAA) into the solution, stirring for 20-30 min, heating at 180 deg.C in 100mL autoclave with polytetrafluoroethylene lining for 16 hr, centrifuging the precipitate, washing, and drying at 80 deg.C for 6 hr to obtain Zn0.5Cd0.5S (CZS10) nano material.
Example 5: preparation of Zn0.5Cd0.5S (CZS11) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting the pH with sodium hydroxide solution (NaOH,10M) under pH meter, pH rangeThe reaction temperature is 10.95-11.05, 150mg Thioacetamide (TAA) is weighed and added into the solution, the solution is continuously stirred for 20-30 minutes, finally the solution is heated for 16 hours at 180 ℃ in a 100mL autoclave with a polytetrafluoroethylene lining, the obtained precipitation solution is precipitated and centrifuged, the solution is washed and dried for 6 hours at 80 ℃ to obtain Zn0.5Cd0.5S (CZS11) nano material.
Example 6: preparation of three-dimensional ordered macroporous ZrO2(3DOM ZrO2) Template semiconductor material
6.445g of ZrOCl2·8H2O was dissolved in 10ml of methanol solution, 3g of a polymethyl methacrylate (PMMA) pellet template was poured, and after standing overnight, vacuum filtration was carried out, and the resulting sample was dried overnight at 50 ℃ in a vacuum oven (filtration was not carried out without washing). And (3) heating the dried sample to 310 ℃ at the speed of 1 ℃/min in a nitrogen atmosphere, maintaining for 3h, cooling to room temperature, switching nitrogen into air, and heating to 550 ℃ at the speed of 1 ℃/min, and maintaining for 10 h. Finally obtaining three-dimensional ordered macroporous ZrO2Material (3DOM ZrO)2)。
Example 7: preparation of 3DOM ZrO2/Zn0.5Cd0.5S (Zr3D/CZS10) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting the pH value with a sodium hydroxide solution (NaOH,10M) under the pH meter, wherein the pH value range is 9.95-10.05, then weighing 150mg Thioacetamide (TAA) and adding the thioacetamide into the solution, continuously stirring for 20-30 minutes, adding 123.2mg of the prepared 3D zirconium oxide template, continuously stirring for 2 hours, finally heating the solution in a 100ml polytetrafluoroethylene-lined autoclave at 180 ℃ for 16 hours, precipitating and centrifuging the obtained precipitate solution after the reaction, washing the precipitate solution, and drying the precipitate solution at 80 ℃ for 6 hours to obtain the Zr3D/CZS10 heterojunction material.
Example 8: preparation of 23 DOM ZrO2/Zn0.5Cd0.5S (2Zr3D/CZS10) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; using sodium hydroxide solution (NaO) under pH meterH,10M) is carried out, the pH value is adjusted to be 9.95-10.05, then 150mg of Thioacetamide (TAA) is weighed and added into the solution, after the continuous stirring is carried out for 20-30 minutes, 246.4mg of prepared 3D zirconium oxide template is added, the stirring is continued for 2 hours, finally, the solution is heated for 16 hours at 180 ℃ in a 100mL polytetrafluoroethylene lining autoclave, the obtained precipitation solution is precipitated and centrifuged, and after the washing, the solution is dried for 6 hours at 80 ℃, and the 2Zr3D/CZS10 heterojunction material is obtained.
Example 9: preparation of 33 DOM ZrO2/Zn0.5Cd0.5S (2Zr3D/CZS10) nano material
219.5mg of zinc acetate (Zn (Ac))2·2H2O), 266.5mg of cadmium acetate (Cd (Ac)2·2H2O) was dissolved in 50mL of ultrapure water and stirred at room temperature for 20 minutes; adjusting the pH value with a sodium hydroxide solution (NaOH,10M) under the pH meter, wherein the pH value range is 9.95-10.05, then weighing 150mg Thioacetamide (TAA) and adding the thioacetamide into the solution, continuously stirring for 20-30 minutes, adding 349.6mg of the prepared 3D zirconium oxide template, continuously stirring for 2 hours, finally heating the 3D zirconium oxide template in a 100mL polytetrafluoroethylene lining autoclave at 180 ℃ for 16 hours, precipitating and centrifuging the obtained precipitation solution after the reaction, washing, and drying at 80 ℃ for 6 hours to obtain the 3Zr3D/CZS10 heterojunction material.
Example 10: zn0.5Cd0.5Phase characterization of S solid solution and Zr3D/CZS10 heterojunction material
FIG. 1 and FIG. 2 show Zn prepared0.5Cd0.5Powder diffraction patterns of S solid solution and Zr3D/CZS10 heterojunction material. As can be seen from fig. 1, CZS7 shows a different pattern from other CZS samples because CZS7 was prepared without adding NaOH solution to adjust pH (pH 7), and the diffraction peak of CZS7 shows that it is a mixture of cubic ZnS (PDF #77-2100) and CdS (PDF #80-0019), pH-adjusted Zn0.5Cd0.5S and hexagonal solid solution Zn0.5Cd0.5S (PDF #89-2943) are identical. By the spectrogram analysis of FIG. 2, Zn can be observed in the Zr3D/CZS10 heterojunction material0.5Cd0.5S and ZrO2Two phases of which ZrO2The diffraction peak of (A) was consistent with that of the monoclinic phase (PDF #86-1451), and the Zr3D/CZS10 heterojunction exhibited almost all diffraction peaks of the two pure samples. Further, as the proportion of zirconia increasesIn addition, the diffraction peak intensity of zirconia gradually increases. Zn can be clearly determined in the figure0.5Cd0.5Typical XRD patterns of S solid solution and Zr3D/CZS10 heterojunction material show that Zn exists in the heterojunction0.5Cd0.5S and ZrO2. In addition, no other impurity-related diffraction peaks were detected in the sample, indicating that the prepared sample had good crystallinity and purity.
Example 11: prepared Zn0.5Cd0.5Morphology characterization of S solid solution and Zr3D/CZS10 heterojunction material
Shown in fig. 3 are Field Emission Scanning Electron Microscope (FESEM) images of CZS7, CZS10, 3DOM ZrO2, and 2Zr3D/CZS 10. From the figure, it can be seen that CZS7 is a mixture of CdS and ZnS, presumably with large (500 nm) and small (30 nm) particles stacked, in contrast to CZS10, which is a solid solution of uniform nano-small particles stacked, indicating that pH changes affect Zn to some extent0.5Cd0.5The morphology of S makes it become even and smaller in size. The zirconia prepared by the colloid template method shows a regular and ordered three-dimensional network structure. It can be seen from FIG. 3d that Zn is loaded by hydrothermal load CZS100.5Cd0.5S can well and uniformly grow on the three-dimensional ordered reticular zirconia to form a Zr3D/CZS10 heterojunction material, and the electron transmission efficiency of the semiconductor is effectively improved.
Example 12: prepared Zn0.5Cd0.5Optical characterization of S solid solution and Zr3D/CZS10 heterojunction Material
FIG. 4 and FIG. 5 show Zn prepared0.5Cd0.5And the ultraviolet-visible light diffuse reflection spectrums of the S solid solution and the Zr3D/CZS10 heterojunction material. From FIG. 4, it can be seen that Zn is present after pH adjustment0.5Cd0.5S (CZS8, CZS9, CZS10 and CZS11) all have only one absorption peak and are in the visible light region. Zn without pH adjustment0.5Cd0.5S (CZS7) appears with two absorption edges corresponding to the absorption edges of CdS and ZnS, respectively, indicating that a single solid solution phase Zn is obtained after pH adjustment0.5Cd0.5And S. As can be seen from fig. 5, all samples except for zirconia have strong absorption in the visible region,the Zr3D/CZS10 heterojunction material is an excellent visible light-light response type catalyst.
Example 13: prepared Zn0.5Cd0.5Performance test of S solid solution and Zr3D/CZS10 heterojunction material for photocatalytic water decomposition hydrogen production under simulated sunlight
The photocatalytic hydrogen evolution experiment is carried out in a 250mL quartz Pyrex reactor under the illumination of simulated sunlight at the top, and the operation is as follows:
stirring the mixture to obtain 100mg of Zn0.5Cd0.5The S series catalyst and 10mg of Zr3D/CZS10 catalyst were placed in a 100mL aqueous solution (0.35M Na)2S and 0.25M Na2SO3) The preparation method comprises the following steps of (1) vacuumizing a plane light window Pyrex flask for 30min, measuring 20mL of high-purity argon by using an injector, introducing the argon into a reactor, bubbling to remove oxygen in a reaction system, and keeping the light reaction system in a vacuum state until a pressure gauge is stable. The solution was irradiated with a 300W xenon lamp simulated sunlight, and the amount of hydrogen gas produced by the final reaction was measured and analyzed by GC-9790/gas chromatograph with Ar as the carrier gas and TCD as the detector.
As can be seen from FIGS. 6 and 7, Zn is observed under the irradiation of the simulated sunlight0.5Cd0.5The S and Zr3D/CZS10 system samples both have good sunlight response.
Specifically, the method comprises the following steps: as can be seen from FIG. 6, Zn is present when the pH is equal to 100.5Cd0.5The catalytic performance of S is best.
As can be seen from FIG. 7, ZrO in the Zr3D/CZS10 heterojunction material2And Zn0.5Cd0.5The molar ratio of S is 2:1, 2Zr3D/CZS10 has the best catalytic performance.
In this embodiment, Zn0.5Cd0.5The optimal yield of S (CZS10) is 40.86mmol/g/h, and the optimal yield of 2Zr3D/CZS10 is 83.12 mmol/g/h.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. The photocatalyst is characterized in that the photocatalyst is ZnxCd1-xS, and preparing said ZnxCd1-xThe pH value of the precursor solution of S is 7-11.
2. The photocatalyst as set forth in claim 1, wherein said Zn isxCd1-xS is Zn0.5Cd0.5S。
3. A photocatalyst as claimed in claim 2, wherein said Zn is preparedxCd1-xThe pH value of the S precursor solution is 8-11, preferably 9.95-10.05.
4. The photocatalyst of claim 3, wherein the photocatalyst is 3DOM ZrO2/Zn0.5Cd0.5An S heterojunction material.
5. A photocatalyst in accordance with claim 4, wherein said 3DOM ZrO2/Zn0.5Cd0.5ZrO in S heterojunction material2And Zn0.5Cd0.5The molar ratio of S is 1:1 to 1:3, preferably 2: 1.
6. A preparation method of a photocatalyst is characterized by comprising the following steps:
s1: weighing zinc acetate dihydrate and cadmium acetate dihydrate according to a molar ratio, dissolving the zinc acetate dihydrate and the cadmium acetate dihydrate into ultrapure water, and continuously stirring for 10-30 minutes to obtain a precursor solution;
s2: adjusting the pH value of the precursor solution obtained in the step S1 to 7-11 by using a NaOH solution, adding thioacetamide after adjusting to a corresponding value, and continuously stirring for 20-40 minutes;
s3: transferring the mixed solution obtained in the step S2 into a high-pressure kettle with a polytetrafluoroethylene lining, and heating for 16-20 hours at 160-180 ℃ by adopting a hydrothermal synthesis method;
s4: washing the obtained product in the step S3 with ultrapure water and absolute ethyl alcohol for multiple times, and drying for 8-12 hours to obtain ZnxCd1-xAnd (3) S nanoparticles.
7. The method for preparing a photocatalyst according to claim 6, wherein: the molar ratio of zinc acetate dihydrate to cadmium acetate dihydrate in S1 is 1:1, and Zn is obtainedxCd1-xS nanoparticles are Zn0.5Cd0.5And (3) S nanoparticles.
8. The method for preparing a photocatalyst according to claim 7, wherein: the pH value of the precursor solution in the step S2 is adjusted to be 8-11, preferably 9.95-10.05.
9. The method for preparing a photocatalyst according to claim 7, wherein: also comprises the preparation of 3DOM ZrO2The steps of the material are as follows:
s21: ZrOCl is prepared by adopting a colloid template method2·8H2Dissolving O in the methanol solution, adding a PMMA pellet template, and standing overnight;
s22: vacuum-filtering the obtained product in the step S21, and then vacuum-drying for 10-12 hours;
s23: calcining the mixture obtained in the step S22 in nitrogen and air for a certain time, removing the template to obtain 3DOM ZrO2A material.
10. The method for preparing a photocatalyst as claimed in claim 9, wherein: also comprises the preparation of 3DOM ZrO2/Zn0.5Cd0.5S heterojunction material: after the steps of S1 and S2 are completed, 3DOM ZrO is mixed according to the molar ratio of 1:1-3:12Adding the material into the solution obtained in the step S2, performing ultrasonic treatment for 30-40 minutes, and then continuously stirring for 1-3 hours; continuing the steps S3 and S4 to obtain 3DOM ZrO2/Zn0.5Cd0.5An S heterojunction material.
11. A photocatalytic system comprising a sacrificial agent and a photocatalyst, characterized in thatThe sacrificial agent is Na2S and Na2SO3The composite aqueous solution, the photocatalyst is the photocatalyst according to any one of claims 1 to 5 or the photocatalyst prepared by the preparation method of any one of claims 6 to 10.
12. Use of a photocatalyst according to any one of claims 1 to 5 or prepared by a method according to any one of claims 6 to 10, or a photocatalyst system according to claim 11 for the photocatalytic decomposition of water to produce hydrogen.
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| Title |
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| CONG-CONG SHEN等: "Large improvement of visible-light photocatalytic H2-evolution based on cocatalyst-free Zn0.5Cd0.5S synthesized through a two-step process", 《CATAL. SCI. TECHNOL.》, vol. 7, pages 961 * |
| YU TIAN等: "A direct dual Z-scheme 3DOM SnS2–ZnS/ZrO2 composite with excellent photocatalytic degradation and hydrogen production performance", 《CHEMOSPHERE》, vol. 279, pages 130882 - 1 * |
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