Out-of-plane CoRu nanoalloy axially coupling CosNC for electron enrichment to boost hydrogen production

Hydrogen production from borohydride hydrolysis is a green and sustainable route to convert hydrogen energy. In the progress, the regulation of electron enrichment and distribution around the active site is the key to promote hydrogen-adsorption during hydrogen production. Here, we fabricated an out-of-plane CoRu nanoalloy axially coupling Co s NC for high electron attachment in hydrolysis of ammonia borane. The axially coupling of out-of-plane CoRu nanoalloy on Co s NC surface for electron enrichment enhances the hydrogen bonding (H*) energy and cycle life. The hydrogen production efficiency (1068 mol H2 mol Ru −1 min −1 ) and activation energy (18.96 kJ mol −1 ) are the best among reported Co-based alloys. Theoretical calculations show that an electron-integration-boosting effect from axially accurate tailoring of CoRu alloy on Co s NC to reduce the reaction energy barrier for co-activation of AB and H 2 O. This work provides insight into structure-activity identification for efficient hydrogen production. Out-of-plane CoRu nanoalloy axial coupling Co s -N-C with multiatomic active sites is fabricated via solid-surfaces-situ-pyrolysis on Co s NC for efficient NH 3 BH 3 hydrolysis. Axially accurate tailoring of single site (Co s NC) by out-of-plane bimetallic coupling at nano level results in a superior hydrogen generation kinetics of NH 3 BH 3 hydrolysis. The optimized Co 0.5 Ru 0.5 /Co s NC present the highest hydrogen generation kinetics (1.068 ×10 3 mol H2 ·min −1 ·mol Ru −1 , 298 K) and the lowest activation energy (18.96 kJ·mol −1 ) among reported Co-based alloys. Combined with experiments and theoretical calculation, the highly coupled interface between CoRu nanoalloy and Co s NC for strong electron-integration-boosting effect. This axial coupling precisely modulated the local coordination environment and electronegativity around surface Co s NC sites and formed new double active site (CoRu nanoalloy and Co s NC) for optimizing the activation kinetics of ammonia borane and water. This work provides in-depth insights into the mechanism of NH 3 BH 3 hydrolysis and paves a new way towards the high-efficient and stable heterogeneous catalysis. • A multiatomic active sites of bimetallic nanoalloy was constructed via solid-surfaces-situ-pyrolysis on Co s NC. • The accurate tailoring of Co s NC by out-of-plane alloy coupling attains a superior hydrogen production of NH 3 BH 3 hydrolysis. • Co 0.5 Ru 0.5 /Co s NC expresses an excellent activity with 1068 mol H2 mol Ru -1 min -1 and lowest activation energy of 18.96 kJ mol -1 . • The hydrogen production is significantly enhanced by electron-integration-boosting effect on alloy axial regulation.