Ultrathin Two-Dimensional Polyoxometalate-Based Metal-Organic Framework Nanosheets for Efficient Electrocatalytic Hydrogen Evolution.

The rational design of 2D polyoxometalate-based metal-organic framework (POMOF) nanosheets on a conductive substrate as a self-supporting electrode is highly attractive but a great challenge. Herein is the first demonstration of POMOF nanopillar arrays consisting of 2D nanosheets as a self-supported electrode for the hydrogen evolution reaction (HER) in acidic conditions. Single-crystal X-ray analysis reveal that our as-prepared 2D [Co2(TIB)2(PMo12O40)]·Cl·4H2O [named CoMo-POMOF; TIB = 1,3,5-tris(1-imidazoly)benzene] crystalline materials are connected by Co-α-Keggin polymolybdate units act as secondary building blocks and TIB as the organic ligands. The 2D CoMo-POMOF nanosheets were successfully arrayed on a conductive nickel foam substrate by a facile CoO nanorod template-assisted strategy. Remarkably, the CoMo-POMOF nanopillar arrays demonstrate superior electrocatalytic performance toward the HER with an overpotential of 137 mV and Tafel slope of 59 mV dec-1 at 10 mA cm-2, which are comparable to those of state-of-the-art POMOF-based electrocatalysts. Density-functional theory (DFT) calculations demonstrate that the exposed bridging oxygen active sites (Oa) of Co-α-Keggin polymolybdate units in CoMo-POMOF optimize the Gibbs free energy of H* adsorption (ΔGH* = -0.11 eV) and increase the intrinsic HER activity.