Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

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Date
2021-06-10
Authors
Chen, Minda
Yan, Yu
Gebre, Mebatsion
Ordonez, Claudio
Liu, Fudong
Qi, Long
Lamkins, Andrew
Jing, Dapeng
Dolge, Kevin
Zhang, Biying
Heintz, Patrick
Shoemaker, Daniel
Wang, Bin
Huang, Wenyu
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Ames Laboratory
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Chemistry
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Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd-based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd3Sn2 phase. Instead, using a thermal quenching method, we prepared a pure-phase PdSn nanocatalyst. PdSn shows an >96 % selectivity toward hydrogenating C=O bonds of various α,β-unsaturated aldehydes, highest in reported Pd-based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn- to Pd3Sn2-structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.

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