2 research outputs found
Dependence of Interfacial Charge Transfer on Bifunctional Aromatic Molecular Linkers in CdSe Quantum Dot Sensitized TiO<sub>2</sub> Photoelectrodes
Quantum dot (QD) sensitization of
TiO<sub>2</sub> is a powerful
method to improve its performance as a photoanode material in solar
energy conversion. The efficiency of sensitization depends strongly
on the rate of interfacial electron transfer (ET) from the QDs to
TiO<sub>2</sub>. To understand the key factors affecting the ET, arene-substituted
(ortho, meta, and para) bifunctional linkers with single or double
aromatic rings were employed to link CdSe QDs to TiO<sub>2</sub> and
control the strength of their interaction as well as the rate of interfacial
ET. Interestingly, the para-substituted aromatic linker, 4-mercaptobenzoic
acid (4MBA) with the longest distance between the carboxyl and thiol
groups, shows the best photoelectrochemical (PEC) performance, when
compared to those of ortho-subtituted (2-mercaptobenzoic acid,
2MBA) and meta-substituted (3-mercaptobenzoic acid, 3MBA) aromatic
linkers. Two other bifunctional linkers with double aromatic rings,
4′-mercapto-[1,1′-biphenyl]-4-carboxylic acid (4M1B4A)
and 6-mercapto-2-naphthioc acid (6M2NA), were also studied for comparison.
Ultrafast transient absorption (TA) spectroscopy was used to study
the exciton dynamics in CdSe QDs and determine the interfacial ET
rate constant (<i>k</i><sub>ET</sub>). The <i>k</i><sub>ET</sub> results are consistent with the trend of PEC measurements
in that 4MBA shows the highest <i>k</i><sub>ET</sub>. To
gain further insight into the ET mechanism, we performed density functional
theory (DFT) calculations to examine the intrinsic properties of the
linkers. The results revealed that the favorable wave function distribution
of the molecular orbitals of 4MBA and 4M1B4A are responsible for the
higher interfacial ET rate and PEC performance due to better interfacial
coupling, a factor that dominates over distance. The present study
provides important new insight into the mechanism of interfacial ET
using aromatic bifunctional linkers, which is useful in designing
QD sensitized semiconductor metal oxide nanostructures for applications
including photovoltaics and solar fuel generation
Experimental and Theoretical Investigations of the Bromination of Phenols with β and γ Aliphatic Substituents, including Rings
Bromination reactions of substituted
and ring fused phenols were
studied by both experiment (<i>t</i>-BuNH-Br) and computation
(density functional theory). The outcomes support each other, indicating
a clear and predictable regioselective preference among 3,4-bis-alkylated
and 3,4-ring-fused phenols