Yang Baoying, Liu Kunlong, Ma Yuhui, Ma Jian-Jie, Chen Yi-Yu, Huang Meirong, Yang Can, Hou Yidong, Hung Sung-Fu, Yu Jimmy C, Zhang Jinshui, Wang Xinchen
State Key Laboratory of Photocatalysis on Energy and Environment College of Chemistry, Fuzhou University, Fuzhou, 350108, P. R. China.
Department of Applied Chemistry and Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, Hsinchu, 300, Taiwan.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202410394. doi: 10.1002/anie.202410394. Epub 2024 Sep 12.
Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single-atom sites in perovskite lattices such as SrTiO can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host-guest interaction with SrTiO during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO (Pd-SrTiO) exhibits an excellent time-independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high-performance photocatalysts for selective hydrogenation reactions.
半氢化是一个关键的工业过程。诸如钯之类的贵金属因其对氢活化具有独特的催化活性，已在半氢化反应中得到广泛研究。然而，由于烯烃在钯活性相上的吸附相当强烈，烯烃过度氢化为烷烃的情况经常发生。在此，我们证明，在钙钛矿晶格（如SrTiO）中将钯活性相作为单原子位点引入，可以极大地改变钯活性相的电子结构和配位环境，从而促进烯烃的脱附而非进一步氢化。此外，在氢化反应中活化氢物种的过程中，引入的钯位点通过与SrTiO形成强烈的主客体相互作用而得以很好地稳定，不会烧结。结果，钯掺杂的SrTiO（Pd-SrTiO）对苯乙炔光催化半氢化为苯乙烯表现出优异的与时间无关的选择性（>99.9%）和强大的耐久性。这种基于在钙钛矿晶格中引入活性相的策略将对开发用于选择性氢化反应的高性能光催化剂具有广泛的意义。
