南开大学李兰冬团队报道了沸石包裹的孤立铂离子实现杂化氢活化和选择性氢化。相关研究成果发表在2021年12月2日出版的《美国化学会杂志》。

理解原子分散催化剂的独特行为及其起源是一个具有挑战性的课题。

该文中，研究人员展示了一种简单的策略，将Ptδ⁺物种封装在Y型沸石中，并在Pt@Y模型催化剂上揭示了选择性加氢的性质。Pt@Y独特配置，即原子分散的Ptδ⁺由方钠石笼和超笼共享的六元环周围氧原子稳定，使二氢在Ptδ+···O^2–单元上的异构化活化成为可能，类似于众所周知的经典Lewis对。带电荷的氢物种，即H⁺和Hδ，是选择性氢化的活性试剂，因此Pt@Y催化剂在α，β-不饱和醛选择性加氢制不饱和醇和硝基芳烃选择性加氢制芳胺方面表现出优异的性能。

附：英文原文

Title: Zeolite-Encaged Isolated Platinum Ions Enable Heterolytic Dihydrogen Activation and Selective Hydrogenations

Author: Xin Deng, Bin Qin, Runze Liu, Xuetao Qin, Weili Dai, Guangjun Wu, Naijia Guan, Ding Ma, Landong Li

Issue&Volume: December 2, 2021

Abstract: Understanding the unique behaviors of atomically dispersed catalysts and the origin thereof is a challenging topic. Herein, we demonstrate a facile strategy to encapsulate Ptδ+ species within Y zeolite and reveal the nature of selective hydrogenation over a Pt@Y model catalyst. The unique configuration of Pt@Y, namely atomically dispersed Ptδ+ stabilized by the surrounding oxygen atoms of six-membered rings shared by sodalite cages and supercages, enables the exclusive heterolytic activation of dihydrogen over Ptδ+···O2– units, resembling the well-known classical Lewis pairs. The charged hydrogen species, i.e., H+ and Hδ, are active reagents for selective hydrogenations, and therefore, the Pt@Y catalyst exhibits remarkable performance in the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols and of nitroarenes to arylamines.

DOI: 10.1021/jacs.1c09535

Source: https://pubs.acs.org/doi/10.1021/jacs.1c09535