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

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 CoCuN6 moieties with double-N-bridged adjacent metal-N4 clusters decorated on a nitrogen-doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L·gmetal-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 CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raise the d-band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.