De novo synthesis of mesoporous photoactive titanium(IV)-organic frameworks with MIL-100 topology
[EN] Most developments in the chemistry and applications of metal-organic frameworks (MOFs) have been made possible thanks to the value of reticular chemistry in guiding the unlimited combination of organic connectors and secondary building units (SBUs) into targeted architectures. However, the development of new titanium-frameworks still remains limited by the difficulties in controlling the formation of persistent Ti-SBUs with predetermined directionality amenable to the isoreticular approach. Here we report the synthesis of a mesoporous Ti-MOF displaying a MIL-100 topology. MIL-100(Ti) combines excellent chemical stability and mesoporosity, intrinsic to this archetypical family of porous…
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 methodologi…
111 oriented gold nanoplatelets on multilayer graphene as visible light photocatalyst for overall water splitting
[EN] Development of renewable fuels from solar light appears as one of the main current challenges in energy science. A plethora of photocatalysts have been investigated to obtain hydrogen and oxygen from water and solar light in the last decades. However, the photon-to-hydrogen molecule conversion is still far from allowing real implementation of solar fuels. Here we show that 111 facet-oriented gold nanoplatelets on multilayer graphene films deposited on quartz is a highly active photocatalyst for simulated sunlight overall water splitting into hydrogen and oxygen in the absence of sacrificial electron donors, achieving hydrogen production rate of 1.2 molH2 per gcomposite per h. This phot…
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 near 4.000 m·g-1 ,with excellent stability in water, and conductivities at room temperature of 4·10-2 S·cm-1 even at very low carbon weight contents (2.3 wt%).
Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping
[EN] We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationa…
Tuning the Photocatalytic Activity of Ti-Based Metal-Organic Frameworks through Modulator Defect-Engineered Functionalization.
Defect engineering is a valuable tool to tune the photocatalytic activity of metal–organic frameworks (MOFs). Inducing defects through the attachment of functionalized modulators can introduce cooperative units that can tune the bandgap of the material and enhance their chemical, thermal, and photostabilities among other properties. However, the majority of defect engineering studies for photocatalytic applications are limited to Zr-based MOFs, and there is still a lack of interrelation between synthetic variables, the resultant MOF properties, and their effect on their photocatalytic performance. We report a comprehensive study on the defect engineering of the titanium heterometallic MOF M…
CCDC 1819267: Experimental Crystal Structure Determination
Related Article: Javier Castells‐Gil, Natalia M. Padial, Neyvis Almora‐Barrios, Josep Albero, A. Rabdel Ruiz‐Salvador, Javier González‐Platas, Hermenegildo García, Carlos Martí‐Gastaldo|2018|Angew.Chem.,Int.Ed.|57|8453|doi:10.1002/anie.201802089
CCDC 2023345: Experimental Crystal Structure Determination
Related Article: Belén Lerma-Berlanga, Carolina R. Ganivet, Neyvis Almora-Barrios, Sergio Tatay, Yong Peng, Josep Albero, Oscar Fabelo, Javier González-Platas, Hermenegildo García, Natalia M. Padial, Carlos Martí-Gastaldo|2021|J.Am.Chem.Soc.|143|1798|doi:10.1021/jacs.0c09015
CCDC 2023346: Experimental Crystal Structure Determination
Related Article: Bel��n Lerma-Berlanga, Carolina R. Ganivet, Neyvis Almora-Barrios, Sergio Tatay, Yong Peng, Josep Albero, Oscar Fabelo, Javier Gonz��lez-Platas, Hermenegildo Garc��a, Natalia M. Padial, Carlos Mart��-Gastaldo|2021|J.Am.Chem.Soc.|143|1798|doi:10.1021/jacs.0c09015
CCDC 1871195: Experimental Crystal Structure Determination
Related Article: Javier Castells-Gil, Natalia M. Padial, Neyvis Almora-Barrios, Ivan da Silva, Diego Mateo, Josep Albero, Hermenegildo García, Carlos Martí-Gastaldo|2019|Chemical Science|10|4313|doi:10.1039/C8SC05218B