Photochemical Kinetics of Maleic to Fumaric Acid on Silver Nanoparticle Surfaces

A visible photochemistry of maleic to fumaric acid adsorbed on silver nanoparticle surfaces was investigated as probed by SERS using a simple flow method. Photoisomerization of maleic to fumaric acid was consecutively observed in the condition of various flow rates, which varied the exposure time of laser beam. The sequential SERS spectra of maleic acid indicated that the photochemical isomerization and desorption took place simultaneously on silver nanoparticle surfaces as a function of laser fluency and wavelength. For 530.9nm laser line excitation, the rate constant coefficients were obtained with a = 5.9 $sec^{-1}$ mW for isomerization and b = 13.9 $sec^{-1}$ mW for desorption, which $k_1\;=\;aI^n\;and\;k_2\;=\;bI^m$. Both reactions were one photon process (n = 1, m = 1) of a visible light and relatively fast process whose decay time was in the range of milli-second for 50 mW laser power. The rate of photochemical reaction increased on going toward the blue and photodesorption was a dominant process. A simple flow method used in this study was very useful to study a relatively fast photochemical reaction of molecules adsorbed on silver nanoparticle surfaces.