Charge Separation by Creating Band Bending in Metal–Organic Frameworks for Improved Photocatalytic Hydrogen Evolution

Abstract Metal–organic frameworks (MOFs) have been intensively studied as a class of semiconductor‐like materials in photocatalysis. However, band bending, which plays a crucial role in semiconductor photocatalysis, has not yet been demonstrated in MOF photocatalysts. Herein, a representative MOF, MIL‐125‐NH2, is integrated with the metal oxides (MoO3 and V2O5) that feature appropriate work functions and energy levels to afford the corresponding MOF composites. Surface photovoltage results demonstrate band bending in the MOF composites, which gives rise to the built‐in electric field of MIL‐125‐NH2, boosting the charge separation. As a result, the MOF composites present 56 and 42 times higher activities, respectively, compared to the pristine MOF for photocatalytic H2 production. Upon depositing Pt onto the MOF, ∼6 times higher activity is achieved. This work illustrates band bending of MOFs for the first time, supporting their semiconductor‐like nature, which would greatly promote MOF photocatalysis.