Coupling of nanocrystal hexagonal array and two-dimensional metastable substrate boosts H 2 -production.

Designing well-ordered nanocrystal arrays with subnanometre distances can provide promising materials for future nanoscale applications. However, the fabrication of aligned arrays with controllable accuracy in the subnanometre range with conventional lithography, template or self-assembly strategies faces many challenges. Here, we report a two-dimensional layered metastable oxide, trigonal phase rhodium oxide (space group, P-3m1 (164)), which provides a platform from which to construct well-ordered face-centred cubic rhodium nanocrystal arrays in a hexagonal pattern with an intersurface distance of only 0.5 nm. The coupling of the well-ordered rhodium array and metastable substrate in this catalyst triggers and improves hydrogen spillover, enhancing the acidic hydrogen evolution for H 2 production, which is essential for various clean energy-related devices. The catalyst achieves a low overpotential of only 9.8 mV at a current density of -10 mA cm -2 , a low Tafel slope of 24.0 mV dec -1 , and high stability under a high potential (vs. RHE) of -0.4 V (current density of ~750 mA cm -2 ). This work highlights the important role of metastable materials in the design of advanced materials to achieve high-performance catalysis.