Potential-Functional Reaction Energetics: Marrying Electrochemical Double-Layer DPFT with Catalytic DFT

Couple conventional Kohn–Sham DFT reaction energetics with the density-potential functional theory (DPFT) of the electrochemical double layer (Huang, 2023) to compute “potential-functional” free energies of intermediates (e.g., *OOH, *O2) that respond self-consistently to interfacial electronic structure, electrolyte, and field. Apply to the boron–carbon heterostructure catalysts of Wu et al. (2025), where inductive –OH effects on B atoms tune *OOH binding. This integration explicitly captures metal-electron responses and electrolyte asymmetries, yielding potential-dependent binding energies that naturally include double-layer reorganization and local field effects. It directly addresses the limitation of voltage-independent adsorption energies and explains observed deviations from universal scaling on heterostructure carbons. The framework also provides an avenue to connect in situ Raman observables with computed potential-dependent intermediate populations. The impact is a new class of potential-resolved activity maps for electrocatalyst discovery consistent with capacitance data and mechanistic spectroscopy, improving the reliability of computational screening for H2O2 electrosynthesis and beyond.

References:

1. Hydroxylated Boron Crystal Domain-Modulated Heterostructure Carbon Catalysts for Efficient Hydrogen Peroxide Generation.. Yuhan Wu, Qixin Yuan, Yuying Zhao, Kang Sun, Hao Sun, Kui Wang, Shengchun Hu, Geoffrey I. N. Waterhouse, Jingjie Wu, Ziyun Wang, Jianchun Jiang, Mengmeng Fan (2025). Journal of the American Chemical Society.
2. Density-Potential Functional Theory of Electrochemical Double Layers: Calibration on the Ag(111)-KPF6 System and Parametric Analysis. Jun Huang (2023). Journal of Chemical Theory and Computation.