The activation of inert C–H bonds under mild conditions with high selectivity remains a central challenge in catalysis. Metal–organic frameworks (MOFs) and polyoxometalate-based MOFs (POMOFs) offer atomically precise, tunable structures that integrate light absorption, charge separation, and catalytic sites. This review systematically summarizes recent progress in the development of MOFs/POMOFs for light-mediated C–H bond activation over the past decade. We discuss design strategies for active sites, including metal nodes, functionalized ligands, guest encapsulation, defect engineering, and single-site regulation. The synergistic role of POMs as electron sponges in promoting charge separation and modulating reactive oxygen species (·O₂⁻, ¹O₂, and ·OH) pathways is discussed. Structure–activity relationships governing the activation of aromatic, benzylic, allylic, and aliphatic C–H bonds are discussed. Finally, perspectives on operando characterization, precision synthesis, green manufacturing, and AI-assisted design are provided to guide the development of next-generation photocatalysts.

The development of nonprecious metals and green hydrogen evolution reaction (HER) electrocatalysts is a major research focus in the context of a two-carbon strategy. In this study, we synthesized a high-efficiency molybdenum phosphide (MoP) catalyst anchored to a porous nitrogen-doped carbon layer (MoP@NC-C₃N₄) via self-assembly and in situ phosphating processes with a clean phosphorus source (ammonium polyphosphate) and a pore-forming agent (F-108). The electrochemical test results demonstrate that the synthesized MoP@NC-C₃N₄ catalyst exhibits outstanding catalytic activity and durability in acidic and alkaline environments with overpotentials of 131 and 127 mV and Tafel slopes of 67 and 89 mV·dec⁻¹ (10 mA·cm⁻²), respectively. In the catalyst system, g-C₃N₄ provides both C and N atoms. In addition, the amorphous carbon and MoP nanoparticles exhibit a synergistic effect to promote charge transfer, thereby enhancing catalytic activity. The overpotential of MoP@NC-C₃N₄ in KOH electrolytes is lower than that of commercial Pt/C at current densities greater than 110 mA·cm⁻². This performance provides a valuable reference for potential industrial applications. The density functional theory results indicate that the Mo atom of MoP has the lowest hydrogen adsorption free energy and serves as the optimal catalytic active site for MoP@NC-C₃N₄. This study paves the way for the design and development of efficient HER electrocatalysts based on graphitic carbon nitrides (g-C₃N₄).

The development of cost-effective and stable electrocatalysts using electrochemical energy conversion systems is an effective strategy for enhancing the efficiency of energy production. In this study, we propose a straightforward one-step synthetic method for fabricating an efficient bimetallic hydrogen evolution electrocatalyst, named Co/Mo₂C@NC. Co/Mo₂C@NC exhibits excellent catalytic activity in basic and acidic electrolytes with overpotentials (η₁₀) of 115 and 121 mV, respectively. Furthermore, Co/Mo₂C@NC exhibits good stability, maintaining its performance for over 100 h. Density functional theory calculations demonstrate that the C atoms on Mo₂C provide the best catalytic active sites, with the Gibbs free energy of hydrogen adsorption approaching 0 eV. Furthermore, Mo₂C possesses exceptional mechanical properties, ensuring the durability of the catalyst during the hydrogen evolution reaction. This study holds experimental significance for developing simple bimetallic electrocatalysts to improve the slow kinetics of the hydrogen evolution reaction.

Polyoxometalates (POMs) are known for their well-established catalytic properties, particularly in photocatalysis, and have made significant strides in achieving selective C(sp³)−H functionalization. However, due to the complexity of the POM structures, the reactivity and regioselectivity of POMs in organic conversions remain unclear. Here, the reactivity and regioselectivity of the C(sp³)–H trifluoromethylation of pyrrolidine via decatungstate anion/copper ([W₁₀O₃₂]⁴⁻/Cu) dual catalysis were theoretically investigated. Density functional theory (DFT) computations revealed that the β-regioselective activation of pyrrolidine occurs more readily than does α-regioselective activation; this is due to the reduction in activity of the ortho α-C–H bond by protonation. Furthermore, the reactivity of hydrogen atom transfer (HAT) catalysts for C(sp³)–H bond activation follows the order [W₁₀O₃₂]⁴⁻ > amine radical cation > fluorescein. The outstanding reactivity of [W₁₀O₃₂]⁴⁻ is attributable to its rigid structure and exposed active surface sites. We demonstrate a linear relationship between the steric volume of the protective group on pyrrolidine and the C–H bond selectivity catalyzed by [W₁₀O₃₂]⁴⁻. In other words, a larger steric volume of the protective group on pyrrolidine leads to easier attainment of a single C_β–H bond activation product. We hope that this theoretical analysis will provide valuable guidance for obtaining high selectivity target products in experimental setups.