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

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 (Ea) 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.