A new Titanium Metal Organic Framework with visible-light responsive photocatalytic activity.

We report the one step synthesis and characterization of a new and robust titanium-based Metal Organic Framework, ACM-1 . In this new structure, based on infinite Ti-O chains and 4,4',4″,4″'-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge separation lifetimes. The suitable energies for band gap and CBM offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.

[1]  Hong Yang,et al.  A novel BODIPY-based MOF photocatalyst for efficient visible-light-driven hydrogen evolution , 2019, Journal of Materials Chemistry A.

[2]  H. García,et al.  De novo synthesis of mesoporous photoactive titanium(iv)–organic frameworks with MIL-100 topology , 2019, Chemical science.

[3]  Wenbin Lin,et al.  Titanium-Based Nanoscale Metal-Organic Framework for Type I Photodynamic Therapy. , 2019, Journal of the American Chemical Society.

[4]  Lei Shi,et al.  Pyrene-Based Covalent Organic Polymers for Enhanced Photovoltaic Performance and Solar-Driven Hydrogen Production , 2018, ACS Applied Energy Materials.

[5]  Jared B. DeCoste,et al.  Synthesis and functionalization of phase-pure NU-901 for enhanced CO2 adsorption: the influence of a zirconium salt and modulator on the topology and phase purity , 2018 .

[6]  Jinhee Park,et al.  Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster , 2018, Angewandte Chemie.

[7]  Jinhee Park,et al.  Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster. , 2018, Angewandte Chemie.

[8]  Can Li,et al.  Visible‐Light‐Responsive 2D Cadmium–Organic Framework Single Crystals with Dual Functions of Water Reduction and Oxidation , 2018, Advanced materials.

[9]  Jiaxing Jiang,et al.  The effect of molecular structure and fluorination on the properties of pyrene-benzothiadiazole-based conjugated polymers for visible-light-driven hydrogen evolution , 2018 .

[10]  Huanting Wang,et al.  Modified metal-organic frameworks as photocatalysts , 2018, Applied Catalysis B: Environmental.

[11]  Guo Wang,et al.  A Methylthio-Functionalized-MOF Photocatalyst with High Performance for Visible-Light-Driven H2 Evolution , 2018, Angewandte Chemie.

[12]  Yang Tian,et al.  A Methylthio-Functionalized-MOF Photocatalyst with High Performance for Visible-Light-Driven H2 Evolution. , 2018, Angewandte Chemie.

[13]  C. Ochsenfeld,et al.  Tailor‐Made Photoconductive Pyrene‐Based Covalent Organic Frameworks for Visible‐Light Driven Hydrogen Generation , 2018, Advanced Energy Materials.

[14]  H. García,et al.  Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping , 2018, Angewandte Chemie.

[15]  H. García,et al.  Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping. , 2018, Angewandte Chemie.

[16]  C. Serre,et al.  A phase transformable ultrastable titanium-carboxylate framework for photoconduction , 2018, Nature Communications.

[17]  Hai‐Long Jiang,et al.  Direct evidence of charge separation in a metal–organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer , 2018, Chemical science.

[18]  K. Takanabe,et al.  Insights on Measuring and Reporting Heterogeneous Photocatalysis: Efficiency Definitions and Setup Examples , 2017 .

[19]  Kieron Burke,et al.  Understanding band gaps of solids in generalized Kohn–Sham theory , 2016, Proceedings of the National Academy of Sciences.

[20]  Aron Walsh,et al.  Electronic origins of photocatalytic activity in d0 metal organic frameworks , 2016, Scientific Reports.

[21]  Rob Ameloot,et al.  A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti(IV)3(μ3-O)(O)2(COO)6] Cluster. , 2015, Angewandte Chemie.

[22]  Qiang Zhang,et al.  A single crystalline porphyrinic titanium metal–organic framework† †Electronic supplementary information (ESI) available. CCDC [1036868]. For ESI and crystallographic data in CIF or other electronic format. See DOI: 10.1039/c5sc00916b Click here for additional data file. Click here for additional da , 2015, Chemical science.

[23]  Reiner Sebastian Sprick,et al.  Tunable organic photocatalysts for visible-light-driven hydrogen evolution. , 2015, Journal of the American Chemical Society.

[24]  F. Kapteijn,et al.  Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production , 2015 .

[25]  Y. Horiuchi,et al.  Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation. , 2014, Chemical communications.

[26]  Xiao‐Ping Zhou,et al.  A highly stable MOF with a rod SBU and a tetracarboxylate linker: unusual topology and CO2 adsorption behaviour under ambient conditions. , 2014, Chemical communications.

[27]  Bin Liu,et al.  A p-type Ti(IV)-based metal-organic framework with visible-light photo-response. , 2014, Chemical communications.

[28]  J. Fraser Stoddart,et al.  Metal-organic framework thin films composed of free-standing acicular nanorods exhibiting reversible electrochromism , 2013 .

[29]  A. Borgna,et al.  Post-synthesis modification of a metal–organic framework to construct a bifunctional photocatalyst for hydrogen production , 2013, Energy & Environmental Science.

[30]  Aron Walsh,et al.  Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization. , 2013, Journal of the American Chemical Society.

[31]  Y. Horiuchi,et al.  Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst , 2013 .

[32]  David Fairen-Jimenez,et al.  Vapor-phase metalation by atomic layer deposition in a metal-organic framework. , 2013, Journal of the American Chemical Society.

[33]  Can Li,et al.  Roles of cocatalysts in photocatalysis and photoelectrocatalysis. , 2013, Accounts of chemical research.

[34]  Seth M. Cohen,et al.  Postsynthetic ligand and cation exchange in robust metal-organic frameworks. , 2012, Journal of the American Chemical Society.

[35]  Masakazu Saito,et al.  Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework , 2012 .

[36]  Yongtao Lu,et al.  Photocatalytic hydrogen evolution without an electron mediator using a porphyrin–pyrene conjugate functionalized Pt nanocomposite as a photocatalyst , 2011 .

[37]  S. Chong,et al.  A guest-responsive fluorescent 3D microporous metal-organic framework derived from a long-lifetime pyrene core. , 2010, Journal of the American Chemical Society.

[38]  Gérard Férey,et al.  A new photoactive crystalline highly porous titanium(IV) dicarboxylate. , 2009, Journal of the American Chemical Society.

[39]  Eva Navas,et al.  Accepted Manuscript , 2022 .

[40]  Armel Le Bail,et al.  Whole powder pattern decomposition methods and applications: A retrospection , 2005, Powder Diffraction.

[41]  Daniel Louër,et al.  Powder pattern indexing with the dichotomy method , 2004 .

[42]  M. Mazur,et al.  Photochemical and Electrochemical Oxidation Reactions of Surface-Bound Polycyclic Aromatic Hydrocarbons , 2004 .

[43]  Akira Fujishima,et al.  Titanium dioxide photocatalysis , 2000 .

[44]  Su-Moon Park,et al.  Studies on electroreduction mechanisms of selected aromatic hydrocarbons in tetrahydrofuran , 1983 .