MOF-derived doped porous carbon-based catalysts for CO2 electroreduction: design, mechanisms, and scale-up

Abstract

The electrochemical reduction of CO₂ (CO₂RR) enables renewable-electricity-driven conversion of CO₂ into value-added chemicals and fuels, but practical deployment is limited by competing hydrogen evolution, incomplete structure–function understanding, and the need for high-rate, durable operation. MOF-derived porous carbon-based catalysts—especially those embedding transition-metal sites and/or alkali-metal promoters—have emerged as a versatile platform because their pore architecture, heteroatom environment, and metal dispersion can be programmed through precursor design and thermal transformation. In this review, we critically synthesize recent progress in MOF-derived carbon-based electrocatalysts for the CO₂RR, linking precursor selection, pyrolysis/activation parameters, and doping strategies to the formation of well-defined active-site motifs (e.g., M–N_x single-atom sites, metal clusters, and bimetallic configurations) and transport-relevant hierarchical porosity. We highlight how transition-metal centers govern key elementary steps (CO₂ activation, *COOH formation, and *CO binding/desorption), while alkali cations regulate the interfacial microenvironment by tuning electric double-layer fields, local pH, and intermediate stabilization, thereby reshaping selectivity—particularly toward C₂₊ products. To improve discoverability and reproducibility, we summarize best practices for reporting catalyst structure and CO₂RR metrics across reactor configurations, and we discuss emerging operando/in situ characterization and multiscale modeling workflows that resolve active-site dynamics under working conditions. Finally, we outline scale-up considerations—from GDE/MEA operation at industrially relevant current densities to manufacturable electrode fabrication—and propose data-driven, high-throughput discovery strategies to accelerate translation. Collectively, this review provides a design-and-evaluation roadmap for developing efficient, mechanistically understood, and scalable MOF-derived porous carbon-based catalysts for CO₂ electroreduction.