sp‐Carbon Incorporated Conductive Metal‐Organic Framework as Photocathode for Photoelectrochemical Hydrogen Generation

Metal‐organic frameworks (MOFs) have attracted increasing interest for broad applications in catalysis and gas separation due to their high porosity. However, the insulating feature and the limited active sites hindered MOFs as photocathode active materials for application in photoelectrocatalytic hydrogen generation. Herein, we develop a layered conductive two‐dimensional conjugated MOF (2D c‐MOF) comprising sp‐carbon active sites based on arylene‐ethynylene macrocycle ligand via CuO(4) linking, named as Cu(3)HHAE(2). This sp‐carbon 2D c‐MOF displays apparent semiconducting behavior and broad light absorption till the near‐infrared band (1600 nm). Due to the abundant acetylene units, the Cu(3)HHAE(2) could act as the first case of MOF photocathode for photoelectrochemical (PEC) hydrogen generation and presents a record hydrogen‐evolution photocurrent density of ≈260 μA cm(−2) at 0 V vs. reversible hydrogen electrode among the structurally‐defined cocatalyst‐free organic photocathodes.