Specific Hydrogen Spillover Pathways Generated on Graphene Oxide Enabling the Formation of Non‐Equilibrium Alloy Nanoparticles

Abstract The phenomenon of hydrogen spillover is investigated as a means of realizing a hydrogen‐based society for over half a century. Herein, a graphene oxide having a precisely tuned architecture via calcination in air to introduce ether groups onto basal planes along with carbon defects is reported. This material provides specific pathways for the spillover of atomic hydrogen and has practical applications with regard to the synthesis of non‐equilibrium solid‐solution alloy nanoparticles. A combination of experimental work and simulations confirmed that the presence of ether groups associated with carbon defects facilitated hydrogen spillover within the basal planes of this graphene oxide. This enhanced hydrogen spillover ability, in turn, enables the simultaneous reduction of Ru³⁺ and Ni²⁺ ions to form RuNi alloy nanoparticles under hydrogen reduction conditions. Energy dispersive X‐ray and X‐ray absorption near edge structure simulations establish that this strategy forms unique alloy nanoparticles each comprising a Ru core with a RuNi solid‐solution shell having a hexagonal close‐packed structure. These non‐equilibrium RuNi alloy nanoparticles exhibit greater catalytic activity than monometallic Ru nanoparticles during the hydrolysis of ammonia borane.