Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic‐Nitrogen‐Doped Carbon

The use of formic acid (FA) to produce molecular H 2 is a promising means of efficient energy storage in a fuel‐cell‐based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H 2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic‐N‐doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H 2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN 0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h −1 at 25 °C) and the reversible process of CO 2 hydrogenation into FA. This system can lead to a full carbon‐neutral energy cycle.