Wavelength-Specific Product Desorption as a Key to Raising Nitrile Yield of Primary Alcohol Ammoxidation over Illuminated Pd Nanoparticles

作者：Han, Pengfei; Tang, Cheng; Sarina, Sarina^*; Waclawik, Eric R.; Du, Aijun; Bottle, Steven E.; Fang, Yanfen; Huang, Yingping; Li, Kun; Zhu, Huai-Yong^*

来源：ACS Catalysis, 2022, 12(4): 2280-2289.

DOI：10.1021/acscatal.1c05486

• light-induced desorption
• nitrile synthesis
• Pd nanoparticles
• selective catalysis
• visible-light photocatalysis

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 degrees 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.