CN113481546B - Zinc oxide/zinc sulfide composite film photoelectrode and recovery device for solar photo-deposited noble metal - Google Patents
Zinc oxide/zinc sulfide composite film photoelectrode and recovery device for solar photo-deposited noble metal Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 76
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 43
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 28
- 238000011084 recovery Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000008021 deposition Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 13
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- DTWCOCYXNRTSIA-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] DTWCOCYXNRTSIA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 41
- 238000000151 deposition Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000010931 gold Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 238000002256 photodeposition Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of photo-induced deposition and photocatalysis, in particular to a zinc oxide/zinc sulfide composite film photoelectrode and a recovery device of solar photo-induced deposition noble metal. The preparation method of the zinc oxide/zinc sulfide composite film photoelectrode comprises the following steps: sequentially cleaning conductive glass by using acetone, ethanol and water through ultrasonic waves, and drying to remove superfluous water on the surface; a zinc oxide film prepared by hydrothermal reaction is prepared; generating ZnO/ZIF-8 precursor in situ after secondary hydrothermal reaction; and vulcanizing the ZnO/ZIF-8 precursor into ZnO/ZnS to obtain the zinc oxide/zinc sulfide composite film photoelectrode. And assembling the ZnO/ZnS composite film photoelectrode and the blank conductive glass by utilizing an H-type electrolytic tank to obtain the recovery device for solar photo-induced deposition noble metal. The deposition device can directly deposit Au, ag and Pt noble metals from the solution by utilizing solar energy.
Description
Technical Field
The invention relates to the technical field of photo-deposition and photocatalysis, in particular to a zinc oxide/zinc sulfide composite film photoelectrode and a recovery device of solar photo-deposition noble metal.
Background
With excessive consumption of resources, environmental problems are increasingly prominent, and particularly sustainable recovery and utilization of noble metal resources are a problem to be solved. The noble metal resources are deficient, the mineral resources are non-renewable resources, and especially the industrial reserves of gold and silver are less. At present, most rare and noble metals in China are complex in recovery procedures, high in recovery cost, and a virtuous circle system for recycling is not established. The rare and noble metals in the waste are effectively recycled, so that the consumption of metal resources in China can be reduced, the harm to the environment can be reduced, and the method has remarkable economic and environmental benefits.
Photocatalysis is considered as one of the promising technologies for solving the problems of excessive energy consumption and environmental pollution at present, and the utilization of renewable energy sources is further widened by introducing light energy into the recovery of noble metals. Noble metals such as silver, platinum and gold are rare and expensive, the recovery cost is reduced by a photo-induced deposition method, the process is simple, the environment is friendly, and the photo-induced deposition technology has a large-scale industrial application prospect.
Metal resources such as gold, silver, platinum, etc. play an important role in the fields of battery systems, electrocatalysis, and photocatalysis. Also in the recently reported studies, there are those involving photo-deposition of Pt, au and loading it to TiO 2 Nanoparticle surfaces for improving their photoelectrochemical properties, while no report has been found on the collection of noble metals by photo-induced deposition.
Disclosure of Invention
In order to solve the problems, the invention aims to prepare the zinc oxide/zinc sulfide composite film photoelectrode with excellent photocatalytic activity by utilizing hydrothermal, calcining and vulcanizing methods, assemble the photoelectrode into an H-type photo-induced deposition device, and carry out photoelectrochemical tests, so that the material can deposit noble metals such as Au, ag, pt and the like from the solution under illumination. The invention provides a novel photo-induced noble metal material deposition technology, which realizes the cooperative conversion from solar energy and chemical energy to electric energy.
The technical scheme adopted by the invention is as follows: the preparation method of the zinc oxide/zinc sulfide composite film photoelectrode comprises the following steps:
1) Sequentially cleaning conductive glass by using acetone, ethanol and water through ultrasonic waves, and drying to remove superfluous water on the surface;
2) A zinc oxide film prepared by hydrothermal reaction is prepared;
3) Generating ZnO/ZIF-8 precursor in situ after secondary hydrothermal reaction;
4) And vulcanizing the ZnO/ZIF-8 precursor into ZnO/ZnS to obtain the zinc oxide/zinc sulfide composite film photoelectrode.
Preferably, in the above-mentioned zinc oxide/zinc sulfide composite film photoelectrode, in the step 2), the preparation method of the zinc oxide film includes the following steps: preparing zinc nitrate ethanol solution with the concentration of 0.005M, dripping the prepared zinc nitrate ethanol solution on the surface of a blank FTO, drying in a vacuum oven, transferring to a muffle furnace for high-temperature sintering, and naturally cooling to room temperature to obtain the FTO containing the ZnO seed layer; dissolving zinc nitrate hexahydrate and hexamethylenetetramine in deionized water, performing ultrasonic treatment to fully dissolve the zinc nitrate hexahydrate and the hexamethylenetetramine, transferring the mixed solution and the FTO containing the ZnO seed layer into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction, cooling to room temperature, respectively washing with ethanol and deionized water for several times, and drying overnight to obtain the ZnO film.
Preferably, in the step 2), the high-temperature sintering temperature is 450 ℃, the time is 0.25-0.5h, the hydrothermal reaction temperature is 100 ℃, and the reaction time is 6h.
Preferably, in the step 3), the preparation method of the ZnO/ZIF-8 precursor comprises the following steps: dissolving a certain amount of 2-methylimidazole in a mixed solution of N, N-dimethylformamide and water, putting the ZnO film obtained in the step 2) into the mixed solution, transferring the ZnO film into a polytetrafluoroethylene-lined reaction kettle for hydrothermal reaction, cooling to room temperature, respectively washing with N, N-dimethylformamide and ethanol for several times, and drying at 70 ℃ for 6 hours.
Preferably, the zinc oxide/zinc sulfide composite film photoelectrode comprises 2-methylimidazole according to the solid-to-liquid ratio: n, N-dimethylformamide: water = 0.05-0.2g:3-5ml:12-20ml.
Preferably, in the step 3), the temperature of the hydrothermal reaction is 80 ℃ and the time is 2 hours.
Preferably, in the zinc oxide/zinc sulfide composite film photoelectrode, step 4), the preparation method of the ZnO/ZnS film comprises the following steps: putting the ZnO/ZIF-8 precursor obtained in the step 3) into a mixed solution of thioacetamide and ethanol, transferring into an oven for reaction, cooling to room temperature, washing with ethanol for several times, and drying at 70 ℃ for 2 hours.
Preferably, in the above-mentioned zinc oxide/zinc sulfide composite film photoelectrode, in the step 4), thioacetamide is mixed according to the solid-to-liquid ratio: ethanol=0.01-0.1 g:10-50ml.
Preferably, in the step 4), the reaction temperature is 70 ℃ and the reaction time is 2 hours.
The recovery device for solar photo-induced deposition noble metal is obtained by assembling any one of the zinc oxide/zinc sulfide composite film photoelectrodes and blank conductive glass (FTO) by using an H-type electrolytic tank.
Compared with the prior art, the invention has the following remarkable advantages:
according to the invention, the semiconductor material is used as a photoelectrode, solar energy is introduced into a recovery method of photo-induced deposition noble metal, and the cooperative conversion from solar energy and chemical energy to electric energy is realized.
According to the invention, the zinc oxide/zinc sulfide heterostructure is designed and synthesized by utilizing the methods of in-situ growth and in-situ vulcanization, the separation and migration of the photo-generated electrons and the photo-generated holes are promoted under the illumination condition, the recombination of the photo-generated electrons and the photo-generated holes is inhibited, and the improvement of the photocatalytic performance of the zinc oxide/zinc sulfide heterostructure is realized.
The method has the remarkable advantages that the solar energy is introduced into the photo-induced deposition noble metal recovery method, so that the extra energy consumption is reduced, the green novel energy utilization way is widened, and meanwhile, the photo-induced deposition noble metal recovery method is simple in procedure and environment-friendly, and has a great practical application prospect.
The zinc oxide/zinc sulfide film based on the FTO conductive glass is used as a photo-induced deposition noble metal photoelectrode, the blank FTO is used as a counter electrode, electrolyte on one side of the zinc oxide/zinc sulfide photoelectrode is sodium sulfate solution, and electrolyte on one side of the blank FTO electrode is respectively 0.02% chloroplatinic acid, 0.02% chloroauric acid and 0.02% silver nitrate solution, and the middle is separated by a perfluorosulfonic acid proton exchange membrane. The invention designs a simple and effective strategy, synthesizes the photoelectrode material with excellent photocatalytic activity and stability, directly utilizes solar energy to deposit Au, ag and Pt noble metals from the solution, and opens up a simple and convenient way for reducing excessive consumption and recycling of noble metal resources. The invention realizes the cooperative conversion from solar energy and chemical energy to electric energy, is easy to operate and simple in flow, and is favorable for popularization and application of solar photo-induced deposition noble metal in actual industrial production.
The photo-deposition technology has obvious cost advantage by using the semiconductor electrode material as a photo-electrode to perform photo-deposition in the H-type electrolytic tank. Under illumination, when the energy received by the semiconductor is larger than the forbidden band width, the photo-generated electrons are transited to the conduction band, positive photo-generated holes are left in the valence band, the holes participate in the oxidation reaction of water and are continuously consumed, the photo-generated electrons are further transferred to the surface of the blank FTO through an external circuit, participate in the reduction process of metal ions, and are further deposited on the surface of the blank FTO. The electron and the hole realize the cooperative conversion of solar energy and chemical energy by participating in redox reaction without external power supply, and the photo-induced deposition technology based on directly utilizing solar energy is considered to be a safer and environment-friendly new technology for meeting the requirement of large-scale recycling of noble metals in the future.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a zinc oxide/zinc sulfide composite film electrode.
FIG. 2 is an electron microscope scanning photograph of a zinc oxide/zinc sulfide composite film electrode.
FIG. 3 is an XRD pattern of a zinc oxide/zinc sulfide composite film.
FIG. 4 is a schematic diagram of a photo-induced deposition apparatus based on a zinc oxide/zinc sulfide composite film as a photo-electrode
Fig. 5 is an electron micrograph of a photo-deposited Au film.
Fig. 6 is an electron micrograph of a photo-deposited Ag film.
Fig. 7 is an electron micrograph of a photo-deposited Pt film.
Fig. 8 is an XRD pattern of the photo-deposited Au thin film.
Fig. 9 is an XRD pattern of a photo-deposited Ag thin film.
Fig. 10 is an XRD pattern of a photo-deposited Pt film.
Detailed Description
The invention will be further illustrated by the following examples, which are intended to better illustrate the invention without limiting its scope.
Example 1 Zinc oxide/Zinc sulfide composite film photoelectrode
The preparation method comprises the following steps:
1) Preparing a zinc oxide film seed layer: the method comprises the following steps: dissolving zinc nitrate hexahydrate in ethanol, and performing ultrasonic treatment to fully dissolve the zinc nitrate hexahydrate to obtain a zinc nitrate ethanol solution with the concentration of 0.005M. And (3) dropwise adding 0.8mL of prepared zinc nitrate ethanol solution on the surface of the blank FTO, drying at 70 ℃ in a vacuum oven, repeating the process for three times, transferring to a muffle furnace, sintering at a high temperature of 450 ℃ for 15min, and naturally cooling to room temperature to obtain the ZnO seed layer. 0.1M zinc nitrate hexahydrate and 0.2M hexamethylenetetramine are dissolved in 50mL deionized water and are sonicated to dissolve them thoroughly. Transferring the mixed solution and the FTO containing the ZnO seed layer into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction for 6 hours at 100 ℃, cooling to room temperature, respectively washing with ethanol and deionized water for several times, and drying at 80 ℃ for overnight to obtain the ZnO film.
2) ZnO/ZIF-8 preparation: the preparation method of the ZnO/ZIF-8 precursor comprises the following steps: weighing 0.1mg of 2-methylimidazole, dissolving in a mixed solution of N, N-dimethylformamide and water, wherein the N, N-dimethylformamide is 4mL, the water is 16mL, putting a ZnO film into the mixed solution, transferring the ZnO film into a polytetrafluoroethylene lining reaction kettle, carrying out hydrothermal reaction for 2h at 80 ℃, cooling to room temperature, respectively washing with N, N-dimethylformamide and ethanol for several times, and drying at 70 ℃ for 6h to obtain the ZnO/ZIF-8 precursor.
3) ZnO/ZnS preparation: dissolving 0.05g of thioacetamide in 20mL of ethanol, and performing ultrasonic treatment to fully dissolve the thioacetamide; putting the ZnO/ZIF-8 film grown on the surface of the FTO into the mixed solution, transferring the mixed solution into an oven, reacting for 2 hours at 70 ℃, cooling to room temperature, washing with ethanol for several times, and drying for 2 hours at 70 ℃ to obtain the ZnO/ZnS film.
(II) characterization
The preparation flow of the zinc oxide/zinc sulfide composite film is shown in a figure 1, the appearance and the thickness of the zinc oxide/zinc sulfide composite film are represented by a scanning electron microscope, as shown in a figure 2, the zinc oxide/zinc sulfide composite film is densely distributed on an FTO substrate, the thickness of a zinc oxide/zinc sulfide micron rod array is about 2.5 mu m, the surface of a micron rod is unevenly distributed in a honeycomb shape, the surface area of the surface is increased by a honeycomb structure on the surface, the contact with electrolyte is promoted, the utilization of sunlight is improved, and the edge structure of a regular hexagon top surface belt is still clearly visible. XRD test is carried out on the zinc oxide/zinc sulfide composite film to characterize the crystal phase structure, the XRD characteristic spectrum of the sample is shown in figure 3, the sample can be obtained from the figure, the sample shows more obvious characteristic diffraction peaks of zinc oxide, the peak is sharp, the ZnO crystallinity is higher, the ZnO is corresponding to the standard card (JCPDS 36-1451), since ZnS is generated by ZIF-8 which grows on the ZnO surface in situ through further vulcanization, the XRD diffraction peak of ZnS is relatively weaker, the result is consistent with the result reported in the literature, the result corresponds to the ZnS standard card (JCPDS 05-0566), and the ZnO/ZnS is proved to be compounded by ZnO and ZnS.
Example 2 recovery apparatus for photo-deposition of noble metals Using solar energy
As shown in fig. 4, a recovery device structure of an H-type electrolytic cell for directly using solar energy to photo-deposit noble metal is as follows: the zinc oxide/zinc sulfide composite film electrode based on the FTO conductive glass is used as a photoelectrode, the blank FTO conductive glass is used as a counter electrode, and the electrolyte is respectively chloroplatinic acid with the mass percent of 0.02%, chloroauric acid with the mass percent of 0.02% and silver nitrate solution with the mass percent of 0.02%When in illumination, the sunlight is simulated (500W xenon lamp is used as a light source, an AM 1.5 type optical filter, and the incident light intensity is 100 mW/cm) 2 ) The following is performed. The right side of fig. 4 is a photograph of Au, ag, pt thin films photo-deposited on the FTO surface.
1) Scanning electron microscope test and XRD test of photo-induced deposited Au film
As shown in fig. 5, gold based on solar photo-induced deposition uniformly covers the FTO surface, gold nanoparticles exhibit an irregular spherical structure, have a relatively uniform shape and size, and as can be seen from a cross-sectional view, the thickness of the gold nanoparticles is about 400nm at a deposition time of 20 minutes. XRD test As shown in FIG. 6, diffraction peaks corresponding to 36.8 °, 44.5 °, 64.7 °, 77.7 ° are assigned to the (111), (200), (220), (311) crystal planes of gold, corresponding to their standard cards (JCPDS 65-8601).
2) Scanning electron microscope test and XRD test of photo-induced deposited Ag film
As shown in fig. 7, the morphology of the solar photo-deposited silver exhibits a regular rod-like structure and an irregular sphere-like structure, wherein the sphere-like structure has a large size, and the thickness of the solar photo-deposited silver is about 17 μm as seen in a cross-sectional view. XRD test As shown in FIG. 8, diffraction peaks corresponding to 38.1 degrees and 44.3 degrees are assigned to (111), (200) crystal planes of silver, and a stronger diffraction peak at 38.1 degrees indicates preferred orientation of silver at the (111) crystal plane and corresponds to the standard card (JCPDS 01-1194) thereof.
3) Scanning electron microscope test and XRD test of photo-induced deposited Pt film
As shown in fig. 9, the platinum based on solar photo-deposition is uniformly coated on the FTO surface, the thickness of the Pt film is about 1.8 μm at a deposition time of 20 minutes, and by XRD test, diffraction peaks corresponding to 40.0 ° and 46.5 ° are assigned to the (111) and (200) crystal planes of platinum, corresponding to the standard card (JCPDS 21-1276), and as can be obtained from fig. 10, the intensity of the diffraction peak of Pt is weak, which is consistent with the reported results of the literature.
Claims (3)
1. The recovery device for solar photo-induced deposition noble metal is characterized in that: the zinc oxide/zinc sulfide composite film photoelectrode and the blank conductive glass are assembled by utilizing an H-type electrolytic tank to obtain the recovery device of solar photo-induced deposition noble metal,
the preparation method of the zinc oxide/zinc sulfide composite film photoelectrode comprises the following steps:
1) Sequentially cleaning conductive glass by using acetone, ethanol and water through ultrasonic waves, and drying to remove superfluous water on the surface;
2) The preparation method of the zinc oxide film comprises the following steps: preparing zinc nitrate ethanol solution with the concentration of 0.005 and M, dripping the prepared zinc nitrate ethanol solution on the surface of a blank FTO, drying in a vacuum oven, transferring to a muffle furnace, sintering at 450 ℃ for 0.25-0.5h, and naturally cooling to room temperature to obtain the FTO containing a ZnO seed layer; dissolving zinc nitrate hexahydrate and hexamethylenetetramine in deionized water, performing ultrasonic treatment to fully dissolve the zinc nitrate hexahydrate and the hexamethylenetetramine, transferring the mixed solution and the FTO containing the ZnO seed layer into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction at 100 ℃ for 6h, cooling to room temperature, respectively washing with ethanol and deionized water for several times, and drying overnight to obtain a ZnO film;
3) The preparation method of the ZnO/ZIF-8 precursor comprises the following steps: dissolving a certain amount of 2-methylimidazole in a mixed solution of N, N-dimethylformamide and water, putting the ZnO film obtained in the step 2) into the mixed solution, transferring the ZnO film into a polytetrafluoroethylene-lined reaction kettle for hydrothermal reaction at 80 ℃ for 2h, cooling to room temperature, washing with N, N-dimethylformamide and ethanol for a plurality of times respectively, and drying at 70 ℃ for 6 h;
4) Putting the ZnO/ZIF-8 precursor obtained in the step 3) into a mixed solution of thioacetamide and ethanol, transferring the mixed solution into an oven to react at 70 ℃ for 2h, cooling the mixed solution to room temperature, washing the mixed solution with ethanol for several times, and drying the mixed solution at 70 ℃ for 2h to obtain the zinc oxide/zinc sulfide composite film photoelectrode.
2. The solar photo-deposited precious metal recovery device according to claim 1, wherein: according to the solid-to-liquid ratio, 2-methylimidazole: n, N-dimethylformamide: water = 0.05-0.2g:3-5ml:12-20ml.
3. The solar photo-deposited precious metal recovery device according to claim 1, wherein: in the step 4), thioacetamide is added according to the solid-to-liquid ratio: ethanol=0.01-0.1 g:10-50 and ml.
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