Pd Anchored on Amine‐Functionalized Hollow Carbon Nanospheres for Highly Efficient Additive‐Free Formic Acid Dehydrogenation

ABSTRACT Hydrogen is a promising clean energy carrier for replacing fossil fuels in a sustainable energy future. However, its practical utilization is hampered by challenges in safe, efficient storage and transportation. Liquid organic hydrogen carriers, particularly formic acid (FA), offers a viable solution, yet their dehydrogenation requires active and selective catalysts that operate with additives. Herein, we report the design of ultrasmall Pd nanoparticles supported on amine‐functionalized hollow mesoporous carbon sphere (Pdx/NHMS) for efficient FA dehydrogenation without and additives. The optimized catalyst Pd0.05/NHMS exhibits a high turnover frequency of 5945 h‐1 at 333 K and a low activation energy of 55.17 kJ mol‐1. Structural and mechanistic studies reveal that the hollow mesoporous architecture facilitates mass transport, while surface amine groups stabilize Pd species and synergistically promote FA activation via a bifunctional mechanism. This work demonstrates a rational catalyst design strategy that integrates architectural and functional modulation of the support, advancing the development of efficient heterogeneous catalysts for practical hydrogen storage systems.