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

Heterometallic Titanium-Organic Frameworks as Dual Metal Catalysts for Synergistic Non-Buffered Hydrolysis of Nerve Agent Simulants

Heterometallic metal-organic frameworks (MOFs) can offer important advantages over their homometallic counterparts to enable targeted modification of their adsorption, structural response, electronic structure, or chemical reactivity. However, controlling metal distribution in these solids still remains a challenge. The family of mesoporous titanium-organic frameworks, MUV-101(M), displays heterometallic TiM2 nodes assembled from direct reaction of Ti(IV) and M(II) salts. We use the degradation of nerve agent simulants to demonstrate that only TiFe2 nodes are capable of catalytic degradation in non-buffered conditions. By using an integrative experimental-computational approach, we rationalize how the two metals influence each other, in this case, for a synergistic mechanism reminiscent of bimetallic enzymes. Our results highlight the importance of controlling metal distribution at an atomic level to span the interest of heterometallic MOFs to a broad scope of cascade or tandem reactions. Summary Mixed-metal or heterometallic metal-organic frameworks (MOFs) are gaining importance as a route to produce materials with increasing chemical and functional complexities. We report a family of heterometallic titanium frameworks, MUV-101(M), and use them to exemplify the advantages of controlling metal distribution across the framework in heterogeneous catalysis by exploring their activity toward the degradation of a nerve agent simulant of Sarin gas. MUV-101(Fe) is the only pristine MOF capable of catalytic degradation of diisopropyl-fluorophosphate (DIFP) in non-buffered aqueous media. This activity cannot be explained only by the association of two metals, but to their synergistic cooperation, to create a whole that is more efficient than the simple sum of its parts. Our simulations suggest a dual-metal mechanism reminiscent of bimetallic enzymes, where the combination of Ti(IV) Lewis acid and Fe(III)–OH Brönsted base sites leads to a lower energy barrier for more efficient degradation of DIFP in absence of a base.Financial support for this work was provided by the Marie Skłodowska-Curie Global Fellowships (749359-EnanSET, N.M.P) within the European Union research and innovation framework programme (2014-2020

Search for High-energy Neutrinos from Binary Neutron Star Merger GW170817 with ANTARES IceCube and the Pierre Auger Observatory

The Advanced LIGO and Advanced Virgo observatories recently discovered gravitational waves from a binary neutron star inspiral. A short gamma-ray burst (GRB) that followed the merger of this binary was also recorded by the Fermi Gamma-ray Burst Monitor (Fermi-GBM), and the Anti-Coincidence Shield for the Spectrometer for the International Gamma-Ray Astrophysics Laboratory (INTEGRAL), indicating particle acceleration by the source. The precise location of the event was determined by optical detections of emission following the merger. We searched for high-energy neutrinos from the merger in the GeV-EeV energy range using the Antares, IceCube, and Pierre Auger Observatories. No neutrinos directionally coincident with the source were detected within ± 500 s around the merger time. Additionally, no MeV neutrino burst signal was detected coincident with the merger. We further carried out an extended search in the direction of the source for high-energy neutrinos within the 14 day period following the merger, but found no evidence of emission. We used these results to probe dissipation mechanisms in relativistic outflows driven by the binary neutron star merger. The non-detection is consistent with model predictions of short GRBs observed at a large off-axis angle

High-energy neutrino follow-up search of gravitational wave event GW150914 with ANTARES and IceCube

We present the high-energy-neutrino follow-up observations of the first gravitational wave transient GW150914 observed by the Advanced LIGO detectors on September 14, 2015. We search for coincident neutrino candidates within the data recorded by the IceCube and Antares neutrino detectors. A possible joint detection could be used in targeted electromagnetic follow-up observations, given the significantly better angular resolution of neutrino events compared to gravitational waves. We find no neutrino candidates in both temporal and spatial coincidence with the gravitational wave event. Within ±500 s of the gravitational wave event, the number of neutrino candidates detected by IceCube and Antares were three and zero, respectively. This is consistent with the expected atmospheric background, and none of the neutrino candidates were directionally coincident with GW150914. We use this nondetection to constrain neutrino emission from the gravitational-wave event

Search for high-energy neutrinos from gravitational wave event GW151226 and candidate LVT151012 with ANTARES and IceCube

The Advanced LIGO observatories detected gravitational waves from two binary black hole mergers during their first observation run (O1). We present a high-energy neutrino follow-up search for the second gravitational wave event, GW151226, as well as for gravitational wave candidate LVT151012. We find two and four neutrino candidates detected by IceCube, and one and zero detected by Antares, within ±500 s around the respective gravitational wave signals, consistent with the expected background rate. None of these neutrino candidates are found to be directionally coincident with GW151226 or LVT151012. We use nondetection to constrain isotropic-equivalent high-energy neutrino emission from GW151226, adopting the GW event\u27s 3D localization, to less than 2×1051-2×1054 erg

The Antares Collaboration : Contributions to the 34th International Cosmic Ray Conference (ICRC 2015, The Hague)

The ANTARES detector, completed in 2008, is the largest neutrino telescope in the Northern hemisphere. Located at a depth of 2.5 km in the Mediterranean Sea, 40 km off the Toulon shore, its main goal is the search for astrophysical high energy neutrinos. In this paper we collect the 21 contributions of the ANTARES collaboration to the 34th International Cosmic Ray Conference (ICRC 2015). The scientific output is very rich and the contributions included in these proceedings cover the main physics results, ranging from steady point sources, diffuse searches, multi-messenger analyses to exotic physics