Structure-sensitive scaling relations among carbon-containing species and their possible impact on CO2 electroreduction
| Autor: | Federico Calle-Vallejo, David Loffreda, Manuel J. Kolb, Philippe Sautet |
|---|---|
| Přispěvatelé: | Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Coordination number
CO2 electroreduction Structure (category theory) chemistry.chemical_element 010402 general chemistry 01 natural sciences Physical Chemistry Catalysis Adsorption Transition metal [CHIM]Chemical Sciences Physical and Theoretical Chemistry Scaling scaling relations 010405 organic chemistry Valency Chemical Engineering computational electrocatalysis 0104 chemical sciences chemistry Chemical physics structural sensitivity catalyst design Carbon Physical Chemistry (incl. Structural) |
| Zdroj: | Journal of Catalysis Journal of Catalysis, Elsevier, 2021, 395, pp.136-142. ⟨10.1016/j.jcat.2020.12.026⟩ Journal of Catalysis, 2021, 395, pp.136-142. ⟨10.1016/j.jcat.2020.12.026⟩ |
| ISSN: | 0021-9517 1090-2694 |
| Popis: | The arduous modelling of reactions at heterogeneous catalysts is greatly simplified when adsorption-energy scaling relations between intermediates exist. The offset of these linear relations is structure-independent when the slope is unity and otherwise depends on the coordination number of the active sites. Here we examine the adsorption of *C, *CH, *CH2, *CH3 and *COH on five different surface sites of nine transition metals to establish their structure-sensitive scaling relations. Interestingly, we show that the scaling relations of *C (valency 4) and C-containing species with valency 3 (*CH, *COH) have peculiar structure-independent offsets. These offsets stem from the analogous bonding of those adsorbates to the adsorption sites, in spite of their dissimilar valency. We show how this result implies that reaction pathways in catalysis involving *C, *CH and *COH, for instance CO2 electroreduction to CH4, will usually have sizable thermodynamic limits imposed to their optimization. F.C.-V acknowledges funding from Spanish MICIUN RTI2018-095460-B-I00, Ramón y Cajal RYC-2015-18996 and María de Maeztu MDM-2017-0767 grants and partly by Generalitat de Catalunya 2017SGR13. We thank Red Española de Supercomputación (RES) for supercomputing time at SCAYLE (projects QS-2019-3-0018, QS-2019-2-0023, and QCM-2019-1-0034) and MareNostrum (project QS-2020-1-0012). The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO. The authors also thank GENCI resources (Project 609) and PSMN in Lyon for CPU time and assistance, as well as the CPER/SYSPROD project (N° 2019-AURA-P5B) for financial support. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect