Reticulation of 2D Semiconductors by Metal-Organic Approach for Efficient Hydrogen Evolution

We report a universal approach to synthesize a series of three-dimensional (3D) metal-organic constructs by linking 2D metal dichalcogenides with organic amine molecules [p-phenylenediamine (PPDA), biphenyl diamine (BPDA), tetra(4-aminophenyl) methane) (TPMA)]. Accurate interlayer distances, ranging from 0.61 to 1.7 nm, are dialed-in by the organic components in 3D constructs of MoS2, MoSe2, and WS2. This allows for the exploitation of space between inorganic layers and internal active sites, as reflected in the reduction of band gap, from 2.05 eV in pristine MoS2 to 0.85 eV in a TPMA-MoS2 construct, and an increase in electrical conductivity by 3 X 10(3) times. Density functional theory calculation further confirms that the promotions in physical properties originate in the formation of 3D constructs. Electrodes based on TPMA-MoS, offer an overpotential of 103.1 mV at 10 mA cm(-2) in hydrogen evolution reactions, standing as the best molecule-based electrodes, with negligible decay in performance during a 12,000-cycle test.