Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish government (CTQ2017-83486-P, RTI2018-098568-A-I00, RYC-2016-1981, CEX2019-000919-M, PID2019-106383GB-C44/AEI/10.13039/501100011033 and RTI2018-098568-A-I00). B.L.-B. thanks the Spanish government for a FPU (FPU16/04162). S.T. thanks the Spanish government for a Ramón y Cajal Fellowship (RYC-2016-60719817). N.M.P. thanks the European Union for a Marie Skłodowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET). J.G.P. thanks to the SIDIX at Servicios Generales de Apoyo a la Investigación (SEGAI) at La Laguna University. We also thank BSC-RES for computational resources (QS-2020-2-0024) and the University of Valencia for research facilities (Tirant and NANBIOSIS).Peer reviewe

Wrapping up Metal–Organic Framework Crystals with Carbon Nanotubes

The presence of tetrazine units in the organic nodes of UiO-68-TZCD controls the formation of ultrathin coatings of single-wall nanotubes that decorate the surface of the crystal. These crystal hybrids can be prepared straightforwardly in one step and are extraordinarily respectful with the properties of the framework for combination of mesoporosity and surface areas ≈4.000 m g, with excellent stability in water, and conductivities at room temperature of 4 × 10 S cm even at very low carbon weight contents (2.3 wt.%).B.L.-B. and N.M.P. contributed equally to the work. This work was supported by the EU H2020 program (ERC-2021-COG-101043428 & ERC-2016-STG-714122), the Generalitat Valenciana (PROMETEU/2021/054 and SEJIGENT/2021/059) and the Spanish government (CEX2019-000919-M, PID2020-118117RB-I00 & EUR2021-121999). B.L.-B. thanks the Spanish government for an FPU (FPU16/04162). N.M.P. and M.G. thanks La Caixa Foundation for a Postdoctoral Junior Leader–Retaining Fellowship (ID 100010434 & ID 100010434 and fellowship code LCF/BQ/PR20/11770014 & LCF/BQ/PR21/11840011). The authors also thank the University of Valencia for its research facilities (NANBIOSIS). J.A. and H. G. are grateful to the Spanish Ministry of Science and Innovation (RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2021–038) for the financial support