上海交通大学环境科学与工程学院晏乃强小组在研究中取得进展。他们发现了氧介导的氢溢出促进Ru单原子催化剂稳定合成氯乙烯。该项研究成果发表在2025年2月18日出版的《德国应用化学》上。

本文采用序贯氧蚀刻策略合成了一种氧掺杂Ru单原子催化剂，该催化剂具有显著的氯乙烯单体产率（>99.38%）和稳定性（>900 h, 180 h^-1），远远超过已有报道的同类Ru催化剂。实验结果和理论计算表明，单原子Ru的不对称结构在氯化氢活化后促进了一种非常规的氧介导的氢溢出反应，使得反应通过Eley-Rideal机制进行，与传统的Langmuir-Hinshelwood途径相比，反应的能量势垒降低了。因此，增强的反应动力学进一步限制了单原子Ru的过氯化反应，从而保证了优异的耐久性。这项工作为设计具有增强乙炔加氢氯化性能的多功能催化剂提供了一种策略。

研究人员表示，钌单原子催化剂在乙炔加氢氯化法制备氯乙烯方面具有广阔的应用前景。但反应过程中Ru原子容易发生过氯化反应，抑制了催化活性和稳定性。

附：英文原文

Title: Oxygen-Mediated Hydrogen Spillover Promotes Stable Synthesis of Vinyl Chloride on Ru Single-Atom Catalysts

Author: Yurui Fan, Haomiao Xu, Mingming Wang, Zhisong Liu, Hongyuan Qi, Wenjun Huang, Lei Ma, Feng Yu, Zan Qu, Pengfei Xie, Bin Dai, Naiqiang Yan

Issue&Volume: 2025-02-18

Abstract: Ru single-atom catalysts hold great promise for the robust synthesis of vinyl chloride through acetylene hydrochlorination. However, the easy over-chlorination of Ru atoms during reaction suppress the catalytic activity and stability. Herein, we have synthesized an oxygen doped Ru single-atom catalyst by a sequential oxygen etching strategy, which delivers the remarkable yield of vinyl chloride monomer (>99.38%) and stability (>900 h, 180 h^-1), far beyond those reported Ru counterparts. Experimental results and theoretical calculations reveal that the asymmetric structure of single-atom Ru promotes an unconventional oxygen-mediated hydrogen spillover after the activation of hydrogen chloride, which enables the reaction to proceed through Eley-Rideal mechanism with a reduced energy barrier of acetylene hydrochlorination compared to the traditional Langmuir-Hinshelwood pathway. As a result, the enhanced reaction kinetics further restrict over-chlorination of single-atom Ru, thereby ensuring the excellent durability. This work offers a strategy for designing multifunctional catalysts with enhanced performances for acetylene hydrochlorination.

DOI: 10.1002/anie.202501040

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202501040