Synergistic Engineering of Architecture and Composition in NixCo1-xMoO4@CoMoO4 Nanobrush Arrays towards Efficient Overall Water Splitting Electrocatalysis
Implementing hierarchical structures of non-noble-metal-based electrocatalysts and modulating their composition can help accelerate surface reactions and fulfills the promise of renewable energy devices via water splitting Herein, molybdenum-based compounds are constructed on activated nickel foam (act-NF) by a one-step hydrothermal growth. The product generated on the act-NF is NixCo1-xMoO4@CoMoO4, with a novel 3D hierarchical heterostructure, wherein the one-dimensional CoMoO4 nanorods are hierarchically integrated with the two-dimensional NixCo1-xMoO4 nanosheets (NCMO@CMO/act-NF). The formation of NixCo1-xMoO4@CoMoO4 attributes to release and diffusion of Ni2+ from act-NF. Heterogeneous NixCo1-xMoO4@CoMoO4 has compositional differences, and synergistic interaction between cobalt and nickel results in the modulated electronic states. Meanwhile, the hierarchical structure facilitates the exposure of active sites. Combining these two advantages, NCMO@CMO/act-NF presents low η10 of 61 and 180 mV in 1.0 M KOH for HER and OER, respectively, and shows a low cell voltage of 1.46 V for overall water splitting with robust stability. DFT calculations reveal that Ni doping leads to charge depletion of Co, which further optimizes d-band center of metal sites and which tuning adsoption of adsorbates to facilitate the water splitting reaction. Thus, a promising strategy of incorporating nanostructure design with compositional modulation is presented to develop functional materials for energy conversion.