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

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 V₂ O₅ ) 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.