Going Beyond Silver in Ethylene Epoxidation with First-Principles Catalyst Screening.

Autor: Huš M; Chalmers tekniska högskola, Department of Physics, Fysikgränd 3, SE-41296, Göteborg, Sweden.; Kemijski inštitut, Hajdrihova 19, SI-1000, Ljubljana, Slovenia.; Univerza v Novi Gorici, Vipavska 13, SI-5000, Nova Gorica, Slovenia.; Zveza za tehniško kulturo Slovenije, Zaloška 65, SI-1000, Ljubljana, Slovenia.; Zavod za varstvo kulturne dediščine, Poljanska 40, SI-1000, Ljubljana, Slovenia., Grilc M; Kemijski inštitut, Hajdrihova 19, SI-1000, Ljubljana, Slovenia.; Univerza v Novi Gorici, Vipavska 13, SI-5000, Nova Gorica, Slovenia., Teržan J; Kemijski inštitut, Hajdrihova 19, SI-1000, Ljubljana, Slovenia., Gyergyek S; Inštitut Jožef Stefan, Jamova 39, SI-1000, Ljubljana, Slovenia., Likozar B; Kemijski inštitut, Hajdrihova 19, SI-1000, Ljubljana, Slovenia.; Fakulteta za tehnologijo polimerov, Ozare 19, SI-2380, Slovenj Gradec, Slovenia., Hellman A; Chalmers tekniska högskola, Department of Physics, Fysikgränd 3, SE-41296, Göteborg, Sweden.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Aug 01; Vol. 62 (31), pp. e202305804. Date of Electronic Publication: 2023 Jun 22.
DOI: 10.1002/anie.202305804
Abstrakt: Ethylene epoxidation is industrially and commercially one of the most important selective oxidations. Silver catalysts have been state-of-the-art for decades, their efficiency steadily improving with empirical discoveries of dopants and co-catalysts. Herein, we perform a computational screening of the metals in the periodic table, identify prospective superior catalysts and experimentally demonstrate that Ag/CuPb, Ag/CuCd and Ag/CuTl outperform the pure-Ag catalysts, while they still confer an easily scalable synthesis protocol. Furthermore, we show that to harness the potential of computationally-led discovery of catalysts fully, it is essential to include the relevant in situ conditions e.g., surface oxidation, parasitic side reactions and ethylene epoxide decomposition, as neglecting such effects leads to erroneous predictions. We combine ab initio calculations, scaling relations, and rigorous reactor microkinetic modelling, which goes beyond conventional simplified steady-state or rate-determining modelling on immutable catalyst surfaces. The modelling insights have enabled us to both synthesise novel catalysts and theoretically understand experimental findings, thus, bridging the gap between first-principles simulations and industrial applications. We show that the computational catalyst design can be easily extended to include larger reaction networks and other effects, such as surface oxidations. The feasibility was confirmed by experimental agreement.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: