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Electronic interactions between a stable electride and a nano-alloy control the chemoselective reduction reaction.


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 ?,?-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.

SUBMITTER: Ye TN 

PROVIDER: S-EPMC6022174 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Electronic interactions between a stable electride and a nano-alloy control the chemoselective reduction reaction.

Ye Tian-Nan TN   Li Jiang J   Kitano Masaaki M   Sasase Masato M   Hosono Hideo H  

Chemical science 20160524 9


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 [Ca<sub>24</sub>Al<sub>28</sub>O<sub>64</sub>]<sup>4+</sup>·(e<sup>-</sup>)<sub>4</sub>, with extremely low work function, promotes the superior activity and selectivity of a Ru-Fe nano-alloy  ...[more]

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