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 com...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-P0_(3)H_(2)and-P0_(3)H acidic groups,a C0_(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 fimol of H_(2)per gram using methanol as sacrificial agent,exhibiting stability,maintaining its crystal structure and allowing its recycling.Even more,170μmol 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 0_(2)reduction.The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.展开更多
基金MOFseidon project(Retos project,PID2019-104228RB-I00,MICIU-AEI/FEDER,UE)and the Ramon Areces Foundation project H+MOFs.P.H.acknowledges the Spanish Ramon y Cajal Programme(2014-15039).S.N.thanks financial support by the Fundacion Ramon Areces(XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigaci6n en Ciencias de la Vida y de la Materia,2016)+1 种基金Ministerio de Ciencia,Innovacion y Universidades RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019(AICO/2019/214)project and A genda Valenciana de la Innovacio(AVI,INNEST/2020/111)project.H.G.thanks financial support to the Spanish Ministry of Science and Innovation(Severo Ochoa and RTI2018-098237-C 021)Generalitat Valenciana(Prometeo2017/083).In memory of our dear colleague,Prof.Emilio Moran,who recently passed away.
文摘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-P0_(3)H_(2)and-P0_(3)H acidic groups,a C0_(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 fimol of H_(2)per gram using methanol as sacrificial agent,exhibiting stability,maintaining its crystal structure and allowing its recycling.Even more,170μmol 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 0_(2)reduction.The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.
