Asymmetric Ru-In atomic pairs promote highly active and stable acetylene hydrochlorination

• Published in: Nature communications 2024-07, Vol.15 (1), p.6035-12, Article 6035
• Main Authors: Fan, Yurui, Xu, Haomiao, Gao, Guanqun, Wang, Mingming, Huang, Wenjun, Ma, Lei, Yao, Yancai, Qu, Zan, Xie, Pengfei, Dai, Bin, Yan, Naiqiang
• Format: Article
• Language: English
• Subjects: 140/146; 147/135; 147/137; 147/143; 639/301/299; 639/638/77/887; Acetylene; Asymmetry; Atomic properties; Catalysts; Chemical synthesis; Chloride; Chlorination; Couplings; Humanities and Social Sciences; Hydrochlorination; Hydrogen chloride; Mercuric chloride; Mercury compounds; multidisciplinary; Orbital stability; Science; Science (multidisciplinary); Selective adsorption; Single atom catalysts; Thermodynamics; Vinyl chloride
• ISSN: 2041-1723; 2041-1723
• 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 −1 , 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. Stable operation of acetylene hydrochlorination remains a challenge due to over-chlorination of Ru. Here, the authors propose a Ru-In atom pair with d - p orbital coupling that switches the thermodynamics of chlorination process and improves stability.