研究目的
To investigate the photoluminescence characteristics of post-synthetically modified CdSe and ZnS nanoparticles with trivalent lanthanide cations, focusing on host sensitized emission, elemental composition changes, and the mechanisms of energy transfer and protection.
研究成果
Host sensitized Ln3+ emission is observed only for Eu, Tb in CdSe and Eu, Tb, Yb in ZnS nanoparticles post-synthetically modified. No complete cation exchange occurs, but significant anionic content alteration and lanthanide incorporation are evident. Ln3+ are protected in nanoparticles, with differences in photophysical properties between hosts. The findings are rationalized by charge trapping mediated sensitization and environment-induced quenching, offering a less demanding synthesis protocol for lanthanide-doped nanoparticles.
研究不足
The study is limited to CdSe and ZnS nanoparticles and specific lanthanides; it does not cover all lanthanides (e.g., La, Ce, Lu, Pm, Gd were excluded). The EDS provides relative elemental composition, not absolute concentrations. The lifetime distribution analysis has sensitivity to fitting parameters, and structural aspects require further investigation. The post-synthetic modification may not achieve complete cation exchange, and the mechanisms are not fully elucidated.
1:Experimental Design and Method Selection:
The study involves post-synthetic modification of CdSe and ZnS nanoparticles with various Ln3+ nitrates at room temperature to form CdSe/Ln and ZnS/Ln nanoparticles, followed by characterization using FTIR, TEM, EDS, electronic absorption, steady-state and time-resolved photoluminescence spectroscopy, and quantum yield measurements. The rationale is to understand the photophysical properties and cation exchange processes.
2:Sample Selection and Data Sources:
CdSe and ZnS nanoparticles were synthesized using established methods, and post-synthetically treated with Ln(III) nitrates (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb). Samples were purified and dispersed in chloroform for analysis.
3:List of Experimental Equipment and Materials:
Chemicals include CdO, TOPO, TOP, tetracosane, ZnSt, octadecene, KBr, C153, selenium, sulfur, lanthanide nitrate hydrates, chloroform, methanol, argon. Equipment includes TEM (JEOL JEM-2100), SEM (Zeiss EVO 18), FTIR spectrometer (Jasco FTIR 6300), UV-visible absorption spectrometer (Perkin Elmer Lambda 1050), luminescence spectrometer (Horiba Fluorolog 3-22), TCSPC setup (Horiba Jobin Yvon Fluorocube-01-NL).
4:Experimental Procedures and Operational Workflow:
Nanoparticles were synthesized, purified, and treated with Ln3+ nitrates. Characterization involved FTIR for purity, TEM for size and structure, EDS for elemental composition, absorption and emission spectroscopy for optical properties, lifetime measurements for decay kinetics, and quantum yield calculations using a relative method with C153 as reference.
5:Data Analysis Methods:
Data were analyzed using Origin 8.5 software for spectral and decay fitting, FAST decay analysis software for lifetime distribution, and thermodynamic calculations for cation exchange feasibility.
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Transmission Electron Microscope
JEM-2100
JEOL
Used for imaging nanoparticles to determine size, structure, and morphology.
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Scanning Electron Microscope
EVO 18
Zeiss
Used to collect energy dispersive X-ray spectra (EDS) for elemental composition analysis.
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FTIR Spectrometer
FTIR 6300
Jasco
Used for Fourier transform infrared spectroscopy to analyze capping ligands and purity of nanoparticles.
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UV-visible Absorption Spectrometer
Lambda 1050
Perkin Elmer
Used to collect electronic absorption spectra of nanoparticles.
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Luminescence Spectrometer
Fluorolog 3-22
Horiba
Used for steady-state photoluminescence spectroscopy, including excitation and emission spectra.
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Time-Correlated Single Photon Counting Setup
Fluorocube-01-NL
Horiba Jobin Yvon
Used for time-resolved luminescence decay kinetics measurements.
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Xenon Flash Lamp
Not specified
Not specified
Used as excitation source for Eu3+ and Tb3+ emission decay measurements.
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