Dual-Site Relay Catalysis over La2O3-Engineered Pd Nanostructure for Additive-Free and CO-Free Hydrogen Release from Formic Acid

Abstract Formic acid (FA), when derived from captured CO2 and renewable H2, is a promising liquid hydrogen carrier, but its sustainable use requires catalysts that enable fast, CO-free, and additive-free hydrogen release under mild conditions. Herein, we report a nanoscale La2O3-modified porous N-doped carbon-anchored ultrafine Pd nanoparticle catalyst La2O3-engineered porous carbon-nitrogen-supported Pd catalyst, Pd−La3CN-750, for efficient FA dehydrogenation. The introduced nanosized La2O3 species are uniformly dispersed on the porous carbon-nitrogen support, which precisely regulates the interfacial microstructure of Pd nanoparticles. La2O3 incorporation reconstructs the Pd/support interface by creating defect-rich anchoring sites, introducing medium-strength basic sites, and inducing interfacial electron transfer to enrich electron-deficient Pdδ+ species. As a result, Pd−La3CN-750 achieves a complete aqueous FA dehydrogenation within 8 min at 313 K, with a TOF of 1431 h−1, a low apparent activation energy of 42.36 kJ mol−1, no detectable CO formation, and stable reusability over seven cycles. In situ DRIFTS and density functional theory calculations reveal a nanoscale interfacial dual-site relay mechanism, in which La−O basic sites activate the O−H bond of FA to generate formate intermediates, while adjacent Pd0−Pdδ+ ensembles promote C−H cleavage, H−H coupling, and H2 desorption. This interfacial synergy lowers the dehydrogenation barrier while suppressing the CO-forming dehydration route. From a sustainability perspective, the catalyst offers low-temperature atmospheric-pressure operation, eliminates sacrificial additives, maximizes the utilization efficiency of ultrafine Pd active nanoparticles, and produces a CO-free hydrogen stream, while future optimization should address synthesis-stage impacts from hard templating, high-temperature carbonization, alkaline etching, solvent use, and H2 reduction. This work provides a sustainability-oriented interfacial design strategy for efficient hydrogen release from carbon-recyclable liquid carriers.