Nickel phosphonate MOF as efficient water splitting photocatalyst

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 Pi having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand. Remarkably, this material exhibits coordinatively unsaturated nickel(II) sites, free–PO3H2 and–PO3H acidic groups, a CO2 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 H2 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 H2 per gram using methanol as sacrificial agent, exhibiting stability, maintaining its crystal structure and allowing its recycling. Even more, 170 µmol of H2 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 O2 reduction. The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.

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Acknowledgements

This work was supported by MOFseidon project (Retos project, PID2019-104228RB-I00, MICIU-AEI/FEDER, UE), and the Ramón Areces Foundation project H+MOFs. P. H. acknowledges the Spanish Ramón y Cajal Programme (2014-15039). S. N. thanks financial support by the Fundación Ramón Areces (XVIII Concurso Nacional para la Adjudicación de Ayudas a la Investigatión en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovatión y Universidades RTI2018–099482-A-I00 project and Generalitat Valenciana grupos de investigación consolidables 2019 (AICO/2019/214) project and Agència Valenciana de la Innovació (AVI, INNEST/2020/111) project. H. G. thanks financial support to the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo2017/083). In memory of our dear colleague, Prof. Emilio Morán, who recently passed away.

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Correspondence to Hermenegildo García or Patricia Horcajada.

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Salcedo-Abraira, P., Vilela, S.M.F., Babaryk, A.A. et al. Nickel phosphonate MOF as efficient water splitting photocatalyst. Nano Res. 14, 450–457 (2021). https://doi.org/10.1007/s12274-020-3056-6

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Keywords

  • metal-organic framework
  • phosphonates
  • photocatalysis
  • water splitting