Activating Inert Atomic Sites in Heterogeneous Catalysis: Multi-Scale Design Strategies
Heterogeneous catalysis underpins modern energy conversion, chemical manufacturing, and environmental remediation, yet its advancement is constrained by the scarcity and cost of noble metals. A sustainable alternative lies in activating intrinsically inert sites in earth-abundant materials such as transition metal oxides and carbon-based materials. This review systematically outlines recent advances in activating inert sites within low-cost catalytic materials. We begin by dissecting the physicochemical origins of catalytic inertness, including local atomic symmetry, electronic spin states, and coordination environments. Subsequently, we elucidate mechanisms by which multi-scale strategies—structural engineering, quantum state engineering, and microenvironment engineering—break symmetry, modulate spin states, and construct unique reaction microenvironments, transforming spectator atoms into highly efficient active centers. The review highlights performance breakthroughs in key reactions such as oxygen evolution reaction (OER) and alkane dehydrogenation, where catalytic metrics now rival or surpass noble metal benchmarks. For instance, triangular-ordered Co atoms achieve ampere-level hydrogen production, and tensile strain engineering activates inert non-defect Bi sites for CO2 electroreduction. We critically assess challenges—stability, scalable synthesis, and cost-effectiveness—that hinder industrial translation. Future directions emphasize multi-strategy synergy and artificial intelligence-assisted rational design. This review provides theoretical guidance and technological pathways for subverting noble-metal-dependent paradigms and developing next-generation efficient, low-cost catalytic systems.