On-Demand, Ultraselective Hydrogenation System Enabled by Precisely Modulated Pd−Cd Nanocubes

Yonggang Feng^†,∥, Weiwei Xu^‡,∥, Bolong Huang^§,∥, Qi Shao^†, Lai Xu^*,‡（徐来）, Shize Yang^⊥, and Xiaoqing Huang^*,†（黄小青）

^† College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123, China

^‡ Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Jiangsu 215123, China

^§ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR

^⊥Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States

^∥ Y.F., W.X., and B.H. contributed equally to this work

J. Am. Chem. Soc. 2020, 142, 962--972

The pursuit of efficient hydrogenation nanocatalysts with a desirable selectivity toward intricate substrates is state-of-the-art research but remains a formidable challenge. Herein, we report a series of novel PdCd_x nanocubes (NCs) for ultraselective hydrogenation reactions with flexible tuning features. Obtaining a desirable conversion level of the substrates (e.g., 4-nitrophenylacetylene (NPA), 4-nitrobenzaldehyde (NBAD), and 4-nitrostyrene (NS)) and competitive selectivity for all potential hydrogenation products have been achieved one by one under optimized hydrogenation conditions. The performance of these PdCd_x NCs displays an evident dependence on both the composition and the use of Cd and a need for a distinct hydrogen source (H₂ or HCOONH₄). Additionally, for the selectivity of hydrogen to be suitably high, the morphology of the NCs has a very well-defined effect. Density functional theory calculations confirmed the variation of adsorption energy for the substrate and hydrogenation products by carefully controlled introduction of Cd, leading to a desirable level of selectivity for all potential hydrogenation products. The PdCd_x NCs also exhibit excellent reusability with negligible activity/selectivity decay and structural/composition changes after consecutive reactions. The present study provides an advanced strategy for the rational design of superior hydrogenation nanocatalysts to achieve a practical application for desirable and selective hydrogenation reaction efficiency.

链接：https://pubs.acs.org/doi/abs/10.1021/jacs.9b10816