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Published on: July 1, 2014
Electronic interactions between a stable electride and a nano-alloy control the chemoselective reduction reaction
Tian-Nan Ye1,2, Jiang Li1,2, Masaaki Kitano1
1Materials Research Center for Element Strategy , Tokyo Institute of Technology , 4259 Nagatsuta, Midori-ku , Yokohama 226-8503 , Japan . Email: kitano.m.aa@m.titech.ac.jp ;
Abstract:
Controlling the electronic structure of heterogeneous metal catalysts is considered an efficient method to optimize catalytic activity. Here, we introduce a new electronic effect induced by the synergy of a stable electride and bimetallic nanoparticles for a chemoselective reduction reaction. The electride [Ca24Al28O64]4+·(e-)4, with extremely low work function, promotes the superior activity and selectivity of a Ru-Fe nano-alloy for the conversion of α,β-unsaturated aldehydes to unsaturated alcohols in a solvent-free system. The catalyst is easily separable from the product solution and reusable without notable deactivation. Mechanistic studies demonstrate that electron injection from the electride to the Ru-Fe bimetallic nanoparticles promotes H2 dissociation on the highly charged active metal and preferential adsorption of C[double bond, length as m-dash]O bonds over C[double bond, length as m-dash]Cs bond of the unsaturated aldehydes, to obtain the thermodynamically unfavorable but industrially important product.
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