研究目的
To enhance solar hydrogen production efficiency by developing a novel photocatalyst with improved light-harvesting and charge transfer properties through the modification of a low-cost metal sulfide semiconductor with few-layered 1T-MoS2 and ZnCoS solid-solution structure.
研究成果
The novel few-layered 1T-MoS2-modified ZnCoS solid-solution hollow dodecahedra exhibit significantly enhanced photocatalytic H2 production due to extended light absorption, improved charge transfer, and abundant active sites. The catalyst achieved a high H2 evolution rate of 15.47 mmol h-1 g-1 with 30.3% quantum efficiency at 420 nm and excellent stability over 35 hours. This work demonstrates a facile method for stabilizing metallic 1T-MoS2 and forming solid-solution structures, offering a promising alternative to noble metal co-catalysts for sustainable hydrogen production.
研究不足
The synthesis requires precise control of conditions to stabilize the metallic 1T-MoS2 phase, which may be sensitive to environmental factors. The use of sacrificial agents like TEA and photosensitizer EY may not be sustainable for large-scale applications. The hollow structure's small cavity might limit light penetration depth, and the catalyst's performance under natural sunlight or long-term industrial conditions is not fully assessed. Potential photocorrosion of metal sulfides could affect long-term stability.
1:Experimental Design and Method Selection:
The study employs a two-step synthetic route involving pyrolysis of bimetallic ZnCo-ZIFs to form oxides, followed by hydrothermal sulfidation with Na2MoO4 and CH3CSNH2 to simultaneously form ZnCoS solid-solution and load few-layered 1T-MoS2. This design leverages MOF templating for structural control and mutual sulfur sharing for phase stabilization.
2:This design leverages MOF templating for structural control and mutual sulfur sharing for phase stabilization. Sample Selection and Data Sources:
2. Sample Selection and Data Sources: ZnxCo1-x-ZIFs (x=1,0.9,0.7,0.5,0.3,0.1,0) were synthesized via solvothermal method using Zn(CH3COO)2, Co(CH3COO)2, and 2-methylimidazole in methanol. Derivatives and composites were prepared with varying compositions and MoS2 loadings (0.5-5%).
3:9,7,5,3,1,0) were synthesized via solvothermal method using Zn(CH3COO)2, Co(CH3COO)2, and 2-methylimidazole in methanol. Derivatives and composites were prepared with varying compositions and MoS2 loadings (5-5%). List of Experimental Equipment and Materials:
3. List of Experimental Equipment and Materials: Chemicals include Zn(CH3COO)2, Co(CH3COO)2, 2-methylimidazole, Na2MoO4·2H2O, CH3CSNH2, methanol, deionized water, ethanol, triethylamine (TEA), Eosin Y (EY), acetonitrile. Equipment includes centrifuges, autoclaves, ovens, XRD (Bruker D8 ADVANCE), SEM (ZEISS MERLIN), TEM (JEOL JEM-2100F), XPS (Thermo ESCALAB 250XI), BET analyzer (Micromeritics ASAP 2020M), AAS (HITACHI Z-2300), ICP-AES, UV-Vis DRS (HITACHI U-3010), PL spectrometer (HITACHI F-7000), Raman spectrometer (HORIBA Jobin Yvon LabRAM Aramis), gas chromatograph (TECHCOMP GC 7900), electrochemical system (CHI 760E), Xe lamp (Perfect Light Microsolar300).
4:0). Experimental Procedures and Operational Workflow:
4. Experimental Procedures and Operational Workflow: Synthesis involves: a) Preparation of ZnxCo1-x-ZIFs by mixing metal acetates and 2-methylimidazole in methanol, stirring, and drying. b) Pyrolysis at 350°C in air to form oxides. c) Hydrothermal sulfidation at 180°C with Na2MoO4 and CH3CSNH2 to form composites. Photocatalytic tests are conducted in a Pyrex cell with catalyst, EY, TEA, water, and acetonitrile, degassed and irradiated with Xe lamp, with H2 quantified by GC.
5:Data Analysis Methods:
XRD for phase identification, SEM/TEM for morphology, XPS for elemental states, BET for surface area, UV-Vis DRS for optical properties, PL for charge recombination, EIS for charge transfer resistance, Mott-Schottky for band structure, and GC for H2 quantification. Data analyzed using instrument-specific software and standard calibration methods.
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X-ray Diffractometer
D8 ADVANCE
Bruker
Record powder X-ray diffraction patterns for phase identification of samples.
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Scanning Electron Microscope
MERLIN
ZEISS
Investigate surface morphology of materials, equipped with energy dispersive X-ray spectrometer.
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Transmission Electron Microscope
JEM-2100F
JEOL
Determine size, morphology, and elemental distribution of samples with EDX analysis.
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X-ray Photoelectron Spectrometer
ESCALAB 250XI
Thermo
Analyze electronic states and surface interactions among elements.
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Atomic Absorption Spectrometer
Z-2300
HITACHI
Quantitatively determine metal contents of Zn and Co.
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UV-Vis Spectrophotometer
U-3010
HITACHI
Record diffuse reflectance ultraviolet-visible spectra for optical properties.
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Photoluminescence Spectrometer
F-7000
HITACHI
Measure photoluminescence emission spectra at room temperature.
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Raman Spectrometer
LabRAM Aramis
HORIBA Jobin Yvon
Obtain Raman spectra for phase validation.
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BET Surface Area Analyzer
ASAP 2020M
Micromeritics
Obtain surface areas and pore volumes from N2 adsorption/desorption isotherms at 77 K.
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Gas Chromatograph
GC 7900
TECHCOMP
Determine amount of evolved H2 with thermal conductivity detector.
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Electrochemical System
CHI 760 E
Shanghai, China
Perform photoelectrochemical measurements including transient photocurrent, EIS, and Mott-Schottky plots.
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Xenon Lamp
Microsolar300
Perfect Light
Serve as light source for photocatalysis experiments.
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