Chemically Robust, Cu-based Porous Coordination Polymer Nanosheets for Efficient Hydrogen Evolution: Experimental and Theoretical Studies.

Due to the extremely high number of accessible active sites and short diffusion path, porous coordination polymer (PCP) nanosheets have demonstrated a variety of promising applications, especially for energy conversion and mass transfer. However, the development of chemically stable PCP nanosheets with dense active sites and large lateral size is a great challenge in terms of feasible considerations. Herein, we first designed and prepared a kind of chemically stable PCP nanosheets via a bottom-up and a top-down integral strategy. Featuring densely exposed and periodic Cu2+ active sites (2.1 × 106 per μm2), as well as ultrathin nature (5 nm) and significant pores (18 Å), this nanosheet demonstrated remarkable performance of electrocatalytic hydrogen evolution. Furthermore, one plausible process and the effect of Cu2+ active sites were proposed and validated by density functional theory calculations.