Study of Diffusion-Assisted Bimolecular Electron Transfer Reactions: CdSe/ZnS Core-Shell Quantum Dot Acts as an Efficient Electron Donor and Acceptor

摘要

Excited-state lifetimes and steady-state emission of two different size CdSe/ZnS core-shell quantum dots (QDs) in toluene were quenched by an electron donor molecule N-methyl aniline (NMA) and an electron acceptor molecule 2,4-dinitrotoluene (DNT) in two separate sets of experiments. Static quenching Collins-Kimball (SACK) diffusion model enabled a conclusive fitting only to the electron transfer (ET) kinetics of QD-NMA pairs. However, for QD-DNT pairs, a clear break down of SACK model was observed. Interestingly, when we considered a QD-to-DNT static complex formation, we observed even a classic Stern-Volmer (SV) fitting equation can provide an adequate fitting to the ET kinetics. ET kinetics we studied here are strongly controlled by the chemical driving forces (AG). For example, electron injection rates (by NMA) to the two QDs with core dimensions similar to 3.4 nm (QD560) and similar to 1.5 nm (QD480) were found to be similar (similar to 1.50 x 10(9)-1.60 x 109 M-1 S-1), which is nicely correlated with their nearly same values of the chemical driving force (-Delta G similar to 0.18-0.19 eV) associated with their ET reactions. Conversely, electron donating rates (to DNT) of the same two QDs are found to be similar to 7.0 X 10(9) M-1 S-1 (QD480) and similar to 3.7 X 10(9) M-1 S-1 (QD560), respectively, for QD480 and QD560, which is again congruent to their chemical free energy changes (-Delta G(QD480-DNT) similar to 1.18 eV and -Delta G(QD560-DNT) similar to 0.44 eV). A nonadiabatic sink term of ET kinetics from QD-NMA pair shows distinct regimes associated with the ET reaction (i.e., static, nonstationary, and stationary).