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High ion selectivity and permeability, as two contradictory aspects for the membrane design, highly hamper the development of osmotic energy harvesting technologies. Metal-organic frameworks (MOFs) with ultra-small and high-density pores and functional surface groups show great promise in tackling these problems. Here, we propose a facile and mild cathodic deposition method to directly prepare crack-free porphyrin MOF membranes on a porous anodic aluminum oxide for osmotic energy harvesting. The abundant carboxyl groups of the functionalized porphyrin ligands together with the nanoporous structure endows the MOF membrane with high cation selectivity and ion permeability, thus a large output power density of 6.26 W m -2 is achieved. The photoactive porphyrin ligands further lead to an improvement of the power density to 7.74 W m -2 upon light irradiation. This work provides a promising strategy for the design of high-performance osmotic energy harvesting systems., (© 2022 Wiley-VCH GmbH.)

High ion selectivity and permeability, as two contradictory aspects for the membrane design, highly hamper the development of osmotic energy harvesting technologies. Metal–organic frameworks (MOFs) with ultra‐small and high‐density pores and functional surface groups show great promise in tackling these problems. Here, we propose a facile and mild cathodic deposition method to directly prepare crack‐free porphyrin MOF membranes on a porous anodic aluminum oxide for osmotic energy harvesting. The abundant carboxyl groups of the functionalized porphyrin ligands together with the nanoporous structure endows the MOF membrane with high cation selectivity and ion permeability, thus a large output power density of 6.26 W m−2 is achieved. The photoactive porphyrin ligands further lead to an improvement of the power density to 7.74 W m−2 upon light irradiation. This work provides a promising strategy for the design of high‐performance osmotic energy harvesting systems. [ABSTRACT FROM AUTHOR]