화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.109, No.39, 18230-18236, 2005
Monitoring hole trapping in photoexcited TiO2(110) using a surface photoreaction
The hole-induced photodesorption of chemisorbed O-2 from a TiO2(110) single crystal has been employed to monitor the kinetics of electron-hole pair (e-h) formation and hole trapping. Excitation is produced by 3.4 +/- 0.05 eV photons at 110 K. Two separate O-2 desorption processes have been found which are characteristic of low photon fluxes and high photon fluxes. At a critical photon flux, F-hv(crit), the slow O-2 photodesorption process suddenly converts to a fast process, signaling the saturation of hole traps in the TiO2 crystal. Consequently, this allows photogenerated holes to more efficiently reach the surface, causing more rapid O-2 photodesorption. The estimated bulk concentration of hole traps is approximately 2.5 x 10(18) cm(-3), involving a fraction of about 3 x 10(-5) of the atomic sites in the bulk. Both the slow and fast O-2 photodesorption processes are described by a rate law that is proportional to F-hv(1/2), indicating that the steady-state concentration of holes, [h], is governed by second-order e-h pair recombination kinetics. Effective use is made of a hole scavenger molecule, adsorbed methanol (CH3OH), to probe the role of added hole traps on the rate of the photodesorption of adsorbed O-2 molecules and on the magnitude of F-hv(crit).