Kaiser Selina K, Fako Edvin, Manzocchi Gabriele, Krumeich Frank, Hauert Roland, Clark Adam H, Safonova Olga V, López Núria, Pérez-Ramírez Javier
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland.
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
Nat Catal. 2020 Apr;3(4):376-385. doi: 10.1038/s41929-020-0431-3. Epub 2020 Mar 2.
A worldwide replacement of the toxic mercuric chloride catalyst in vinyl chloride manufacture acetylene hydrochlorination is slowed down by the limited durability of alternative catalytic systems at high space velocities. Here, we demonstrate that platinum single atoms on carbon carriers are substantially more stable (up to 1073 K) than their gold counterparts (up to 473 K), enabling facile and scalable preparation and precise tuning of their coordination environment by simple temperature control. By combining kinetic analysis, advanced characterisation, and density functional theory, we assess how the Pt species determines the catalytic performance and thereby identify Pt(II)-Cl as the active site, being three times more active than Pt nanoparticles. Remarkably, we show that Pt single atoms exhibit outstanding stability in acetylene hydrochlorination and surpass the space-time-yields of their gold-based analogues after 25 h time-on-stream, qualifying as candidate for sustainable vinyl chloride production.
氯乙烯制造乙炔氢氯化过程中有毒氯化汞催化剂在全球范围内的替代，因替代催化体系在高空速下耐久性有限而放缓。在此，我们证明碳载体上的铂单原子在高达1073 K时比金单原子（高达473 K）稳定得多，通过简单的温度控制即可实现其简便且可扩展的制备以及对其配位环境的精确调控。通过结合动力学分析、先进表征和密度泛函理论，我们评估了铂物种如何决定催化性能，从而确定Pt(II)-Cl为活性位点，其活性是铂纳米颗粒的三倍。值得注意的是，我们表明铂单原子在乙炔氢氯化中表现出出色的稳定性，在25小时的连续运行后超过了其金基类似物的时空产率，有资格成为可持续生产氯乙烯的候选者。
