Going Beyond Silver in Ethylene Epoxidation with First-Principles Catalyst Screening |
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Authors: | Dr Matej Huš Dr Miha Grilc Dr Janvit Teržan Dr Sašo Gyergyek Prof Blaž Likozar Prof Anders Hellman |
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Institution: | 1. Chalmers tekniska högskola, Department of Physics, Fysikgränd 3, SE-41296 Göteborg, Sweden;2. Kemijski inštitut, Hajdrihova 19, SI-1000 Ljubljana, Slovenia
Univerza v Novi Gorici, Vipavska 13, SI-5000 Nova Gorica, Slovenia;3. Kemijski inštitut, Hajdrihova 19, SI-1000 Ljubljana, Slovenia;4. Inštitut Jožef Stefan, Jamova 39, SI-1000 Ljubljana, Slovenia;5. Kemijski inštitut, Hajdrihova 19, SI-1000 Ljubljana, Slovenia
Fakulteta za tehnologijo polimerov, Ozare 19, SI-2380 Slovenj Gradec, Slovenia |
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Abstract: | 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. |
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Keywords: | Catalyst Screening DFT Ethylene Epoxidation Experimental Validation Modelling |
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