Interfacial electronic modulation of pd-ZnO-CN catalysts via in-situ pyrolysis for efficient CO-free formic acid dehydrogenation

Room-temperature formic acid (FA) dehydrogenation is critical for sustainable hydrogen storage but remains challenged by sluggish kinetics and CO poisoning. Herein, an in-situ pyrolysis strategy is developed to construct strongly coupled Pd-ZnO-CN interfaces. Sub-nanometer ZnO clusters are dispersed on defect-rich carbon nitride, anchoring ultrafine Pd nanoparticles (~2.25 nm) through geometric confinement. Interfacial charge transfer from Pd to ZnO/CN creates abundant electron-deficient Pd δ+ active sites. These sites downshift the d -band center, optimizing hydrogen adsorption thermodynamics, lowering the rate-determining C H cleavage barrier to 42.91 kJ/mol, and accelerating hydrogen spillover. Consequently, the optimized Pd-Zn 4 @CN-750 catalyst exhibits exceptional intrinsic activity with a TOF of 1048 h −1 , complete FA conversion within 8 min near room temperature, and 100% CO-free H 2 selectivity, with no activity decay after seven cycles. These findings highlight the key role of interfacial electronic modulation in boosting both activity and stability. This work provides a new paradigm for designing robust, CO-tolerant catalysts with strong metal-support interactions for sustainable hydrogen supply.