Li Zehua, Öztuna Eylül, Skorupska Katarzyna, Vinogradova Olga V, Jamshaid Afshan, Steigert Alexander, Rohner Christian, Dimitrakopoulou Maria, Prieto Mauricio J, Kunkel Christian, Stredansky Matus, Kube Pierre, Götte Michael, Dudzinski Alexandra M, Girgsdies Frank, Wrabetz Sabine, Frandsen Wiebke, Blume Raoul, Zeller Patrick, Muske Martin, Delgado Daniel, Jiang Shan, Schmidt Franz-Philipp, Köhler Tobias, Arztmann Manuela, Efimenko Anna, Frisch Johannes, Kokumai Tathiana M, Garcia-Diez Raul, Bär Marcus, Hammud Adnan, Kröhnert Jutta, Trunschke Annette, Scheurer Christoph, Schmidt Thomas, Lunkenbein Thomas, Amkreutz Daniel, Kuhlenbeck Helmut, Bukas Vanessa J, Knop-Gericke Axel, Schlatmann Rutger, Reuter Karsten, Cuenya Beatriz Roldan, Schlögl Robert
Department of Inorganic Chemistry, Fritz-Haber Institute of the Max Planck Society, Berlin, Germany.
Bessy II, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin, Germany.
Nat Commun. 2024 Dec 10;15(1):10660. doi: 10.1038/s41467-024-54784-z.
Future carbon management strategies require storage in elemental form, achievable through a sequence of CO hydrogenation reactions. Hydrogen is recycled from molecular intermediates by dehydrogenation, and side product acetylene selectively hydrogenated to ethylene. Existing Pd alloy catalysts for gas purification underperform in concentrated feeds, necessitating novel concepts. Atomistic simulations unveil superior selectivity of Pd:C solid solutions that optimize chemisorption energies and preclude sub-surface hydrides, verified here with model thin films. Multiple design criteria deduced from conventional catalysts facilitate synthesizing a self-repairing Pd:C system of a laterally condensed catalyst (LCC). A Pd layer prepared on a designated SiO buffer layer enables control of reactive interface, sub-surface volume and extended functional interface towards the buffer. Function and metric are supervised by operando micro-spectroscopy. This catalyst design shows, ethylene productivity >1 kmol/g/hour is reproducibly achieved and benchmarked against known catalysts. Photovoltaics deposition technologies enable scalability on real-world substrates saving active metal. A design-of-experiment approach demonstrates the improvement potential of the LCC approach.
未来的碳管理策略需要以元素形式储存，这可通过一系列CO加氢反应实现。氢气通过脱氢从分子中间体循环利用，副产物乙炔选择性加氢生成乙烯。现有的用于气体净化的钯合金催化剂在浓缩进料中表现不佳，因此需要新的概念。原子模拟揭示了钯碳固溶体具有卓越的选择性，可优化化学吸附能并防止亚表面氢化物的形成，本文通过模型薄膜对此进行了验证。从传统催化剂推导得出的多个设计标准有助于合成一种具有横向凝聚催化剂（LCC）的自修复钯碳体系。在指定的SiO缓冲层上制备的钯层能够控制反应界面、亚表面体积以及朝向缓冲层的扩展功能界面。功能和指标由原位微光谱监测。这种催化剂设计表明，可重复性地实现乙烯生产率>1 kmol/（g·小时），并与已知催化剂进行了基准对比。光伏沉积技术能够在实际应用的基材上实现规模化，同时节省活性金属。实验设计方法证明了LCC方法的改进潜力。
