Engineering the Pore and Functionality of Carbon Nanospheres to Immobilize Metal Nanoparticles for Liquid Formic Acid Dehydrogenation

Liquid formic acid (FA) dehydrogenation is a promising chemical hydrogen storage technology, while the relatively low mass transferability and active site accessibility of catalysts during the catalytic process prevent their practical applications. Herein, a facile etching ‐ co‐doping hyphenated (ECoDH) strategy is developed to fabricate a porous carbon nanosphere (C K ‐BN), which is used as the support for immobilizing metal nanoparticles (NPs) for FA dehydrogenation. The synthesized catalysts are analyzed by X‐ray diffraction, scanning electron microscopy, Brunner–Emmett–Taylor, X‐ray photoelectron spectroscopy, transmission electron microscopy, and so on, and the results display that the combination of alkaline ions etching and B,N co‐doping can efficiently adjust the surface structure of carbon supports. Comparing to Pd/C, whose support is neither etching with alkaline ions nor doping heteroatoms, the catalytic property of Pd/C K ‐BN is several times higher than the former. Additionally, alloying Pd with Co can further improve the catalytic performance of composite nanocatalysts. The PdCo alloy NPs (≈2.34 nm) immobilized on the C K ‐BN exhibit an impressive turnover frequency of 3123 h −1 at 50 °C for the FA dehydrogenation. Moreover, this ECoDH strategy can extend to other carbon supports such as XC‐72 or Ketjenblack, which shows great potential in fields of catalysis and energy storage.