Chem p. 1080 - 1091 (2018)
Update date:2022-08-16
Topics:
Zhao, Xiaojing
Zhou, Lingyun
Zhang, Wuyong
Hu, Chengyi
Dai, Lei
Ren, Liting
Wu, Binghui
Fu, Gang
Zheng, Nanfeng
Surface and interfacial engineering of heterogeneous metal catalysts is effective and critical for optimizing selective hydrogenation for fine chemicals. By using thiol-treated ultrathin Pd nanosheets as a model catalyst, we demonstrate the development of stable, efficient, and selective Pd catalysts for semihydrogenation of internal alkynes. In the hydrogenation of 1-phenyl-1-propyne, the thiol-treated Pd nanosheets exhibited excellent catalytic selectivity (>97%) toward the semihydrogenation product (1-phenyl-1-propene). The catalyst was highly stable and showed no obvious decay in either activity or selectivity for over ten cycles. Systematic studies demonstrated that a unique Pd-sulfide/thiolate interface created by the thiol treatment was crucial to the semihydrogenation. The high catalytic selectivity and activity benefited from the combined steric and electronic effects that inhibited the deeper hydrogenation of C=C bonds. More importantly, this thiol treatment strategy is applicable to creating highly active and selective practical catalysts from commercial Pd/C catalysts for semihydrogenation of internal alkynes. The development of next-generation catalytic materials requires a methodological shift from trial-and-error to mechanism-directed design. It is highly desirable to build model catalyst systems with simplified structures to ensure maximized utilization of both state-of-the-art characterization tools and computational chemistry methods. In this work, thiol-treated palladium nanosheets are adopted as a model catalyst for the selective semihydrogenation of internal alkynes. Unexpectedly, thiol treatment created highly selective palladium catalysts with high activity toward the semihydrogenation reaction. The ultrathin nature of the as-prepared catalysts allows for the application of a variety of surface science and computational methods to resolve the complexity of metal-organic interfaces and thus elucidate the underlying mechanism. Driven by atomic-level understanding, we have realized practical, lead-free catalysts for semihydrogenation. Thiol treatment is demonstrated as a highly effective strategy for promoting the catalytic selectivity of Pd nanocatalysts in the hydrogenation of internal alkynes to alkenes.
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Doi:10.1080/00304940309355360
(2003)Doi:10.1039/c4cc04344h
(2014)Doi:10.1021/ja904150w
(2009)Doi:10.1016/S0040-4039(98)02636-7
(1999)Doi:10.1021/acs.orglett.5b02545
(2015)Doi:10.1002/cctc.201801086
(2018)