Ruthenium Complex-Incorporated Two-Dimensional Metal-Organic Frameworks for Cocatalyst-Free Photocatalytic Proton Reduction from Water

Ultrathin two-dimensional (2D) nanosheets with efficient light-driven proton reduction activity were obtained through the exfoliation of novel metal-organic frameworks (MOF), which were synthesized by using a bis(4'-carboxy-2,2':6',2 ''-terpyridine) ruthenium complex as a linker and 3d transition-metal (Mn, Co, Ni, and Zn) anions as nodes. The nanosheet of the Ni2+ node exhibits a photocatalytic hydrogen evolution rate of 923 +/- 40 mu mol g(-1) h(-1) at pH = 4.0, without the presence of any cocatalyst or cosensitizer. A combined experimental and theoretical study suggests a reductive quenched pathway for the photocatalytic hydrogen evolution by the nanosheet. The transition-metal nodes at the edge of the nanosheets are proposed as the active sites. Density functional theory (DFT) calculations attributed the different catalytic activities of the nanosheets to the discrepancy of H adsorption free energy at various transition-metal nodes.