Surface complexation of colloidal titanium dioxide nanoparticles
(40−60 Å) with cysteine was investigated
by electron paramagnetic resonance (EPR) and infrared (diffuse
reflectance infrared Fourier transform−DRIFT) spectroscopies. Cysteine was found to bind strongly to the
TiO2 surface, resulting in formation of
new trapping sites where photogenerated electrons and holes are
localized. Illumination of cysteine-modified
TiO2 at 77 K resulted in formation of cysteine radicals
with the unpaired electron localized on the carboxyl
group. Upon warming to 150 K, these radicals are transformed into
sulfur-centered radicals as observed by
EPR spectroscopy. We have demonstrated the existence of two
surface Ti(III) centers on cysteine-modified
TiO2 particles having different extents of tetragonal
distortion of the octahedral crystal field. Upon
addition
of lead ions, a new complex of cysteine that bridges surface titanium
atoms and lead ions was detected by IR
spectroscopy. Illumination of lead/cysteine-modified
TiO2 did not result in the formation of
sulfur-centered
radicals. Instead, a symmetrical, lattice defect type EPR signal
for trapped holes was observed. Addition of
methanol to this system resulted in the formation of a
·CH2OH radical at 8.2 K. After the
temperature was
raised to 120 K, doubling of the signal associated with electrons
trapped at the particle surface
(Ti(III)surf)
was observed. On further increase of the temperature to 200 K, the
EPR signal for trapped electrons disappeared
due to the reduction of Pb2+ ions, and metallic lead
precipitated at room temperature. Conversion of
photogenerated holes in the presence of methanol into trapped electrons
can lead to the doubled quantum
efficiency of metallic lead precipitation.