Ruthenium Nanoparticles Anchored on Cobalt Oxide Married with Nitrogen and Phosphorus Co-Doped Carbon for Hydrolytic Dehydrogenation of Ammonia Borane

The development of cost-effective and high-efficiency catalysts for hydrogen generation through ammonia borane (AB) hydrolysis remains a significant challenge in the field of clean energy production. Controlled introduction of dopants into catalysts offers a promising strategy to enhance the intrinsic activity of noble metals, such as ruthenium (Ru), by tuning their electronic energy levels. Herein, we explored the interactions between cobalt oxide and Ru nanoparticles (NPs) supported on N and P co-doped carbon-based nanostructures. Notably, the N, P co-doping uniquely modulates the electronic structures, simultaneously tuning the electronic properties of carbon support and cobalt oxide. Therefore, this composite catalyst demonstrates the distinctly enhanced metal–support interactions, achieving a 3.5-fold increase in turnover frequency (TOF) to 1429 molH2·molRu–1·min–1 at 25 °C, compared to the undoped counterparts. Moreover, the catalyst retains over 90% of its initial activity after five cycles of reuse. Experimental and theoretical analyses attribute the superior catalytic activity of Ru@CoOx/NPC to the optimized electronic configuration of CoOx and the downward shift in its d-band center induced by N and P doping. This microstructural alteration further modifies the electronic state of Ru, enhancing H2O adsorption and dissociation. These findings offer a pragmatic tactic for electronic structure modulation to design highly active and selective noble-metal-based catalysts for AB hydrolysis.