Electronic engineering induced ultrafine non-noble nanoparticles for high-performance hydrogen evolution from ammonia borane hydrolysis.

• For the first time, ultrafine CuNi@ZrO 2 /NC/RGO was successfully synthesized. • CuNi@ZrO 2 /NC/RGO exhibit impressive activities of ABH duo to strong EMSI. • ZrO 2 /NC/RGO can configure novel electronic distribution for high kinetics of ABH. The exploration of heterogeneous supported nanocatalysts with high performance as well as low cost is vital but still challenged for utilization of sustainable hydrogen fuel. In this work, bimetallic CuNi nanoparticles are immobilized on zirconia/nitrogen doped porous carbon/reduced graphene oxide (ZrO 2 /NC/RGO) derived from NH 2 -UiO-66/GO precursor. Thanks to the usage of ZrO 2 /NC/RGO, the well-dispersed CuNi NPs with the size of 2.5 nm were successfully obtained via a facile wet-chemical co-reduction method. By virtue of the synergistic effect induced by solid supports, the resulted Cu 0.8 Ni 0.2 @ZrO 2 /NC/RGO nanocatalysts display excellent activity of catalyzing ammonia borane hydrolysis, with an outstanding overall turnover frequency (TOF) value of as high as 40.9 mol H2 mol cat −1 min−1 at mild condition. Such an enhanced catalytic performance is attributed that zirconium oxide combined with N species could induce a strong synergistic effect to efficiently adjust the electronic distribution, optimize the d-band center as well as favor the Femi level of CuNi catalytic sites, resulting in an improving kinetics of ammonia borane hydrolysis (ABH). This work not only deeply explores the catalytic mechanism of ABH, but also provides a promising strategy for construction of heterogeneous nanocatalytic systems with high performance for industrial application. [ABSTRACT FROM AUTHOR]