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Study of Interfacial Charge Transfer from an Electron Rich Organic Molecule to CdTe Quantum Dot by using Sterna??Volmer and Stochastic Kinetic Models

DOI:10.1002/cphc.201901159 期刊:ChemPhysChem 出版年份:2020 更新时间:2025-09-19 17:13:59
摘要: Photoinduced electron transfer from N-methylaniline (NMA) to a photoexcited CdTe quantum dot (QD*) is studied in toluene. The PET mechanism at low to moderate quencher (NMA) concentrations (< 0.08 M) remains mostly collisional with some contributions from QD-NMA complex formation. However, at high quencher concentrations (> 0.10 M), QDs form larger numbers of static complexes with NMA molecules leading to a steep positive deviation in the steady-state Stern–Volmer curves. An isothermal titration calorimetry (ITC) study confirms the formation of QD-NMA complexes (K ~ 150 M?1) at high quencher concentrations. Fitting our experimental data using a stochastic kinetic model indicates that the number of NMA molecules attached per QD at highest NMA concentration (~ 0.16 M) used in this study decreases from ~ 0.76 to ~ 0.47 with reducing the QD size from ~ 5.2 nm to ~ 3.2 nm. However, the PET rate increases with decreasing QD size, which is commensurate with the observation that the chemical driving force (ΔG) increases with decreasing the QD particle size. We have analyzed the PET kinetics mainly by using Stern-Volmer fittings. However, in some cases Tachiya’s stochastic kinetic model is used for stoichiometric analysis, which seems to be useful only at high quencher concentrations. The measured PET rate coefficients in all the cases are found to be at least an order of magnitude lower when compared to the diffusion-controlled rate of the reaction medium.
作者: Kiran Bharadwaj,Himanshu Choudhary,Soumitra Hazra,Subhadip Ghosh
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Investigating the photoinduced electron transfer (PET) mechanism from N-methylaniline (NMA) to photoexcited CdTe quantum dots (QD*) in toluene, focusing on the effects of quencher concentration and QD size on the PET kinetics.

The study provides a comprehensive understanding of the PET mechanism in QD-NMA systems, highlighting the dominance of collisional quenching at low quencher concentrations and complex formation at high concentrations. The findings are significant for the design of next-generation photovoltaic and light-emitting devices.

The stochastic kinetic model is limited to high quencher concentrations where complex formation dominates. The study does not account for ultrafast complex formations that could be detected with higher resolution time-resolved setups.

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