Breaking the Brønsted–Evans–Polanyi Relation with Dual-Metal Sites

Chen, Yiming; Song, Haohong; Wu, Zili; Jiang, De-en

doi:10.1021/acs.jpclett.5c02446

Breaking the Brønsted–Evans–Polanyi Relation with Dual-Metal Sites

Journal Article · Thu Oct 23 00:00:00 EDT 2025 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5c02446· OSTI ID:3001499

Chen, Yiming ^[1]; ^[1]; ^[2]; ^[1]

Vanderbilt Univ., Nashville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Linear scaling relationships impose inherent limitations on catalyst activity; the Brønsted−Evans−Polanyi (BEP) relation, which correlates activation and reaction energies, is a prominent example. Here we report a dual-metal site catalyst (DMSC) on ceria that breaks the BEP relation for C−C coupling of methyl intermediates an elementary step in methane coupling to form ethane. The DMSC structure on CeO₂(111) was discovered by density-functional theory (DFT) structural exploration and confirmed to be stable via ab initio thermodynamics and ab initio molecular dynamics. Homonuclear and heteronuclear DMSCs of Ni, Pd, Pt, Fe, Ru, Os, Co, Rh, and Ir (45 pairs in total) were examined for methyl affinity and methyl−methyl coupling activation energy. We found that many heteronuclear DMSCs break the BEP linear scaling due to a mixed low-affinity/high-affinity coadsorption of the two methyl groups, decoupling the step responsible for the activation energy (E_a) at the low-affinity site from the overall reaction energy (ΔE) determined by both sites. This mechanism of breaking the BEP relationship via the DMSCs offers a catalyst design principle for C−C coupling reactions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 3001499

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 43 Vol. 16; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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