研究目的
通过部分硫化ZnIn2S4上的氧化铈纳米团簇来调控其电子特性,从而增强异相催化剂对二氧化碳还原的活性,旨在实现可见光下高效且选择性地将CO2光催化还原为CO。
研究成果
部分硫化策略成功制备出富含Ce3+和氧空位的CeOx-S纳米团簇,增强了CO2吸附、电子-空穴分离能力,并以高选择性实现光催化还原制CO。DFT计算证实Ce-S配位作用可降低反应活化能垒。该方法为设计高效太阳能驱动CO2转化光催化剂提供了新思路。
研究不足
该研究聚焦于特定催化剂组成与条件,未涉及工业化环境下的可扩展性与长期稳定性。使用三乙胺等牺牲电子供体可能无法满足大规模应用的可持续性要求。其反应机制依赖可见光及特定波长,限制了在弱光环境中的应用。
1:实验设计与方法选择:
采用一锅水热法制备CeOx-S/ZnIn2S4复合催化剂。表征技术包括XRD、TEM、STEM、HAADF-STEM、EDX面扫描、XAFS(EXAFS和XANES)、XPS、EPR、KPFM、TRPL、原位EPR、原位FTIR及DFT计算,用于分析结构、电子特性和催化性能。
2:样品与数据来源:
催化剂以ZnSO4·7H2O、InCl3·4H2O、CeCl3·7H2O、PEG-6000、TAA、乙二醇、三乙胺、水、乙腈及高纯CO?气体为原料合成。参比样品包含CeO?和Ce?S?。
3:2O、InCl3·4H2O、CeCl3·7H2O、PEG-TAA、乙二醇、三乙胺、水、乙腈及高纯CO?气体为原料合成。参比样品包含CeO?和Ce?S?。 实验设备与材料清单:
3. 实验设备与材料清单:仪器包括PANalytical X-Pert PRO衍射仪(XRD)、JEOL JEM-2100透射电镜、配备HAADF探测器的FEI Titan 80–200球差校正电镜、FEI-Titan 80–300高分辨电镜、ESCALAB250Xi XPS、带KPFM的Bruker Dimension V扫描探针显微镜、时间相关单光子计数??椋═RPL)、Bruker EPR谱仪、Bruker 70红外光谱仪(FTIR)、Techcomp GC 7900气相色谱仪、ICP-OES测铈含量、校准硅光电二极管测光强、自制455 nm LED光反应器及VASP软件(DFT计算)。
4:实验流程与操作规范:
催化剂经160°C水热反应20小时,洗涤干燥后使用。光催化CO?还原在石英反应器中进行,体系含催化剂、水、乙腈、三乙胺及CO?氛围,以455 nm LED光照并磁力搅拌,产物通过GC分析。表征涉及特定条件下的样品制备、辐照及数据采集。
5:数据分析方法:
EXAFS数据采用Demeter程序拟合与小波分析,XPS峰解卷积,EPR信号积分,FTIR峰归属,GC定量,AQY计算及DFT能量计算。
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PANalytical X-Pert PRO diffractometer
X-Pert PRO
PANalytical
Conducting powder X-ray diffraction patterns for structural characterization of catalysts.
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JEOL JEM-2100 transmission electron microscope
JEM-2100
JEOL
Observing morphologies of catalysts using transmission electron microscopy.
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FEI Titan 80–200 scanning transmission electron microscope
Titan 80–200
FEI
Performing STEM and HAADF-STEM for high-resolution imaging and compositional mapping.
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FEI-Titan 80–300 electron microscope
Titan 80–300
FEI
Conducting high-resolution TEM investigations with Cs corrector for objective lens.
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ESCALAB250Xi X-ray photoelectron spectrometer
ESCALAB250Xi
Thermo
Performing XPS analyses to determine surface oxidation states and compositions.
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Bruker Dimension V SPM system
Dimension V
Bruker
Measuring contact potential difference and surface photovoltage using Kelvin probe force microscopy.
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Bruker 70 IR spectrometer
70
Bruker
Collecting in situ FTIR spectra to study CO2 adsorption and reaction intermediates.
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Bruker EPR spectrometer
Bruker
Recording electron paramagnetic resonance spectra to detect oxygen vacancies and electron trapping.
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Techcomp GC 7900 gas chromatograph
GC 7900
Techcomp
Qualitatively and quantitatively analyzing gas products from photocatalytic reactions.
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Inductively coupled plasma optical emission spectrometer
Determining Ce content in catalysts.
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Calibrated Si photodiode
LS-100
EKO Instruments Co., Ltd.
Measuring the number of incident photons for AQY calculations.
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Home-made LED photoreactor
Conducting photocatalytic reactions with controlled light irradiation.
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Vienna Ab Initio Package
VASP
Performing density functional theory calculations to model catalyst structures and reaction energies.
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