Fan Yurui, Xu Haomiao, Gao Guanqun, Wang Mingming, Huang Wenjun, Ma Lei, Yao Yancai, Qu Zan, Xie Pengfei, Dai Bin, Yan Naiqiang
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 200240, Shanghai, China.
College of Chemical and Biological Engineering, Zhejiang University, 310058, Hangzhou, China.
Nat Commun. 2024 Jul 17;15(1):6035. doi: 10.1038/s41467-024-50221-3.
Ru single-atom catalysts have great potential to replace toxic mercuric chloride in acetylene hydrochlorination. However, long-term catalytic stability remains a grand challenge due to the aggregation of Ru atoms caused by over-chlorination. Herein, we synthesize an asymmetric Ru-In atomic pair with vinyl chloride monomer yield (>99.5%) and stability (>600 h) at a gas hourly space velocity of 180 h, far surpassing those of the Ru single-atom counterparts. A combination of experimental and theoretical techniques reveals that there is a strong d-p orbital interaction between Ru and In atoms, which not only enables the selective adsorption of acetylene and hydrogen chloride at different atomic sites but also optimizes the electron configuration of Ru. As a result, the intrinsic energy barrier for vinyl chloride generation is lowered, and the thermodynamics of the chlorination process at the Ru site is switched from exothermal to endothermal due to the change of orbital couplings. This work provides a strategy to prevent the deactivation and depletion of active Ru centers during acetylene hydrochlorination.
钌单原子催化剂在乙炔氢氯化反应中具有取代有毒氯化汞的巨大潜力。然而，由于过度氯化导致钌原子聚集，长期催化稳定性仍然是一个巨大挑战。在此，我们合成了一种不对称的钌-铟原子对，在气体时空速为180 h⁻¹的条件下，氯乙烯单体产率（>99.5%）和稳定性（>600 h）远超过钌单原子催化剂。实验和理论技术相结合表明，钌和铟原子之间存在强烈的d-p轨道相互作用，这不仅能使乙炔和氯化氢在不同原子位点选择性吸附，还能优化钌的电子构型。结果，氯乙烯生成的本征能垒降低，并且由于轨道耦合的变化，钌位点氯化过程的热力学从放热转变为吸热。这项工作提供了一种在乙炔氢氯化反应过程中防止活性钌中心失活和消耗的策略。
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