Atomically Dispersed Cobalt/Copper Dual‐Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid

Abstract

Abstract The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual‐metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN 6 moieties with double‐N‐bridged adjacent metal‐N 4 clusters decorated on a nitrogen‐doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ g metal −1 ⋅ h −1 ) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so‐called formate pathway with the C−H dissociation of HCOO* as the rate‐determining step. Theoretical calculations reveal that Cu in the CoCuN 6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d‐band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.