Correlation between Electronic Descriptor and Proton-Coupled Electron Transfer Thermodynamics in Doped Graphite-Conjugated Catalysts

Graphite-conjugated catalysts (GCCs) provide a powerful framework for investigating correlations between electronic structure features and chemical reactivity of single-site heterogeneous catalysts. GCC-phenazine undergoes proton-coupled electron transfer (PCET) involving protonation of phenazine at its two nitrogen atoms with the addition of two electrons. Herein, this PCET reaction is investigated in the presence of defects, such as heteroatom dopants, in the graphitic surface. The proton-coupled redox potentials, EPCET, are computed using a constant potential periodic density functional theory (DFT) strategy. The electronic states directly involved in PCET for GCC-phenazine exhibit the same nitrogen orbital character as those for molecular phenazine. The energy ϵLUS of this phenazine-related lowest unoccupied electronic state in GCC-phenazine is identified as a descriptor for changes in PCET thermodynamics. Importantly, ϵLUS is obtained from only a single DFT calculation but can predict EPCET, which requires many such calculations. Similar electronic features may be useful descriptors for thermodynamic properties of other single-site catalysts.