Among them, molybdenum carbide (Mo2C) has garnered tremendous attention as HER/OER catalysts owing to its Pt-like electronic structure and wide-pH-range catalytic performance. [2] Unfortunately, the catalytic activity of Mo2C towards HER or OER is still inferior to most advanced catalysts. One effective strategy to enhance electrocatalytic performance involves coupling and doping of Mo2C with late transition metals, e.g., Fe, Co, and Ni, which modifies electronic structure and adds active sites, metal-Mo2C interfaces. Unfortunately, similar to Mo2C, metal nanoparticles also tend to aggregate during preparation and operation. A semiconductive carbon catalyst support alleviating aggregation is usually the solution by not only conformally dispersing nanocatalysts but also providing heteroatom dopants and forming metal-semiconductor Mott-Schottky interface for further enhancing catalytic activity.[3] Besides the selection of catalysts with optimized structure and composition at the material level, the structure of electrodes derived from assembled catalysts at the device level also have a crucial influence on the water electrolyzer. Compared with powdery electrocatalysts with relatively large overpotential and easier peeling off from the electrode, self-supported hierarchical nanoarrayed electrodes are more promising for water electrolyzer because these electrodes facilitate transportation of charges and matter and thus reaction kinetics during HER/OER due to binder-free feature, catalysts-substrate seamless contact and highly exposed surface area.[4]

We develop here the making of nickel-molybdenum carbide heterostructures embedded in large-area (100 cm2) hierarchically assembled nitrogen-enriched carbon, forming Mott-Schottky array on nickel foam (Ni-Mo2C/NC@NF).[5] The Ni-Mo2C/NC array is directly applied as the bifunctional catalyst with high activity and durability in alkaline electrolyte. Particularly, an extremely low overpotential of 40 mV is needed to generate hydrogen. Density functional theory calculation revealed that the formation of Ni-Mo2C Mott/NC Schottky interfaces enables favorable electronic structures for electrocatalytic water splitting. Besides, 3D hierarchical structure provides exposed active sites, facilitates mass and charge transfer, graphitic shells enhance stability. A symmetric electrolyzer using Ni-Mo2C/NC@NF generates 10 mA cm-2 at 1.59 V and operates steadily for 150 h, which even outperforms the noble metal couple, Pt/C//RuO2 for water electrolysis. The scalability, activity and durability renders Ni-Mo2C/NC@NF potential industrial application.

Reference
1. M. Walter, N. Lewis et al, Chem. Rev. 2010, 110, 11, 6446.
2. M. Miao, B. Y. Xia, X. Wang et al, Chem. Eur. J. 2017, 23, 10947.
3. F. Yu, Y. Li et al Nanoscale, 2018,10, 6080.
4. H. Sun, F. Cheng., J. Chen et al. Adv. Mater. 2020, 32, 1806326.
5. Z. Xu, S. Jin, M. H. Seo, X. Wang, Appl. Catal. B: Environ. 2021, 292, 120168