posted on 2022-01-31, 17:39authored byPengfei Han, Cheng Tang, Sarina Sarina, Eric R. Waclawik, Aijun Du, Steven E. Bottle, Yanfen Fang, Yingping Huang, Kun Li, Huai-Yong Zhu
Research
on visible-light photocatalysts of metal nanoparticles
(NPs) has focused on increasing the reactant conversion by light-excited
charges (electrons and positively charged holes). However, light irradiation
can accelerate catalysis by other mechanisms. Here, we report that
650 nm wavelength irradiation of 0.75 W·cm–2 significantly increases nitrile yield of ammoxidation of primary
aromatic alcohols with an ammonium salt over supported Pd NPs at 80
°C in air. We found that the desorption of the nitrile product
from the catalyst is the rate-determining step; the irradiation promotes
not only alcohol oxidation and subsequent aldehyde cyanation over
the Pd NPs but also the nitrile desorption selectively via resonance
energy transfer to achieve a high nitrile yield. This new mechanism
provides a knob for the exquisite control of catalytic reaction pathways
for ecofriendly synthesis.