Nickel phosphonate MOF as efficient water splitting photocatalyst
Pablo Salcedo‐Abraira, Sérgio M. F. Vilela, Artem A. Babaryk, María Cabrero‐Antonino, Pedro Gil Gregório, Fabrice Salles, Sergio Navalón, Hermenegildo Garcı́a, Patricia Horcajada
Abstract
A novel microporous two-dimensional (2D) Ni-based phosphonate metal-organic framework (MOF; denoted as IEF-13) has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques. Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group P i having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand. Remarkably, this material exhibits coordinatively unsaturated nickel(II) sites, free–PO 3 H 2 and–PO 3 H acidic groups, a CO 2 accessible microporosity, and an exceptional thermal and chemical stability. Further, its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis. In this sense, the photocatalytic activity for challenging H 2 generation and overall water splitting in absence of any co-catalyst using UV–Vis irradiation and simulated sunlight has been evaluated, constituting the first report for a phosphonate-MOF photocatalyst. IEF-13 is able to produce up to 2,200 µmol of H 2 per gram using methanol as sacrificial agent, exhibiting stability, maintaining its crystal structure and allowing its recycling. Even more, 170 µmol of H 2 per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting, being this reaction limited by the O 2 reduction. The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.