Engineering Ru atomic structures toward enhanced kinetics of hydrogen generation

Abstract

Herein, we demonstrate a strategy of engineering Ru atomic structures by fine-tuning Cl and Co coordination to synergize the quantity and quality of Ru active sites for boosting hydrogen generation from ammonia borane hydrolysis, via engineering the Cl-free/Cl-containing monometallic Ru catalysts and Co-leaching/Co-containing bimetallic Ru-Co catalysts. Under similar Ru particle sizes, the correlation between Ru binding energy and hydrogen generation activity affords a quantitative discrimination of Ru electronic and geometric contributions, where the site blockage and steric hindrance of Ru by Cl are more detrimental to hydrogen generation compared with the electronic modification by charge donation from Co to Ru. Reversely, the acid-leaching of Co from bimetallic catalysts creates abundant edge-like Ru active sites with much lower H2O activation barrier, as indicated by the kinetics switch from a Cl coverage-limited regime to a reactant activation regime, thus yielding a significant 4.1-fold increase in hydrogen generation activity.