MOFs, COFs and beyond: a theoretical perspective on the electrocatalytic activities of 2D materials toward sustainable energy conversion.

The rational design of advanced catalytic materials for sustainable electrochemical energy conversion hinges on a deep understanding of structure-property relationships at the atomic scale. In this mini-review, we highlight recent advances in the computationally driven design of framework-based and two-dimensional (2D) materials, including metal and covalent organic frameworks (MOFs and COFs), graphitic carbon nitride (g-C3N4) derivatives, and emerging nonmetallic sheets like borophene. Drawing primarily on first-principles density functional theory (DFT) studies from our group and others, we elucidate how atomic-scale engineering through defect creation, heteroatom doping, metal single-atom anchoring, and pore functionalization governs catalytic activity and selectivity for key energy conversion reactions. These include the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), nitrogen reduction reaction (NRR), and carbon dioxide reduction reaction (CO2RR). We place special emphasis on the mechanistic insights derived from free-energy landscapes, descriptor-based analyses, and ab initio molecular dynamics (AIMD) simulations which reveal the dynamic behavior of active sites under operating conditions. By synthesizing these theoretical advances, we aim to provide actionable design principles that guide experimental synthesis and accelerate the discovery of next-generation, noble-metal-free electrocatalysts for a sustainable energy future.