Hybrid organic-inorganic structured materials as single-site heterogeneous catalysts

Catalyst selectivity is associated with well-defined homogeneous active sites. Transition metal complexes and organocatalysts are highly active and selective in the homogeneous phase, and their heterogenization by incorporating them into inorganic solid materials allows combining their excellent catalytic activity with improved separation, recovering and recycling properties. In this article, we present the structural characteristics and catalytic properties of hybrid organic inorganic materials in which the molecular catalysts are part of the inorganic structure, emphasizing the possibilities of periodic mesoporous hybrid materials and coordination polymers as single-site solid catalysts.We thank Spanish MICINN (Consolider Ingenio 2010-MULTICAT (CSD2009-00050) and MAT2011-29020-C02-01) and Generalitat Valenciana (PROMETEO project 2088/130) for financial support.Díaz Morales, UM.; Boronat Zaragoza, M.; Corma Canós, A. (2012). Hybrid organic-inorganic structured materials as single-site heterogeneous catalysts. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences. 468(2143):1927-1954. https://doi.org/10.1098/rspa.2012.0066S19271954468214

Metal Ion Detection by Luminescent Metal Organic Frameworks

abstract: Metal Organic Frameworks(MOFs) have been used in various applications, including sensors. The unique crystalline structure of MOFs in addition to controllability of their pore size and their intake selectivity makes them a promising method of detection. Detection of metal ions in water using a binary mixture of luminescent MOFs has been reported. 3 MOFs(ZrPDA, UiO-66 and UiO-66-NH2) as detectors and 4 metal ions(Pb2+, Ni2+, Ba2+ and Cu2+) as the target species were chosen based on cost, water stability, application and end goals. It is possible to detect metal ions such as Pb2+ at concentrations at low as 0.005 molar using MOFs. Also, based on the luminescence responses, a method of distinguishing between similar metal ions has been proposed. It is shown that using a mixture of MOFs with dierent reaction to metal ions can lead to unique and specic 3D luminescence maps, which can be used to identify the present metal ions in water and their amount. In addition to the response of a single MOF to addition of a single metal ion, luminescence response of ZrPDA + UiO-66 mixture to increasing concentration of each of 4 metal ions was studied, and summarized. A new peak is observed in the mixture, that did not exist before, and it is proposed that this peak requires metal ions to activateDissertation/ThesisMasters Thesis Materials Science and Engineering 201

Growing modulator agents for the synthesis of Al-MOF-type materials based on assembled 1D structural sub-domains

[EN] Novel aluminium MOF-type materials structured by 1D subdomains, such as organic-inorganic nanoribbons, were synthesized by modifying the conditions of solvothermal synthesis and the nature of the solvents in the presence of aryl monocarboxylate linkers with long alkyl chains, which acted as growth-modulating agents. Specifically, three different families of materials were prepared with various morphological characteristics: (i) isoreticular MIL-53(Al)-type materials, (ii) mesoscopic metalorganic structures and (iii) lamellar aluminium MOFs. The length of the alkyl chain in the aryl linker and the hydrophobic/hydrophilic nature of the solvothermal synthesis media determined the structuration level that was achieved. The derived Al-MOFs are active and stable catalysts for the synthesis of fine chemicals. This was illustrated by the efficient synthesis of 2,3-dihydro-2,2,4-trimethyl-1H-1,5-benzodiazepine.The authors are grateful for financial support from the Spanish Government under MAT2014-52085-C2-1-P, MAT2017-82288-C2-1-P and Severo Ochoa Excellence Program SEV-2016-0683. J. M. M. thanks predoctoral fellowships from MINECO for economic support. The European Union is also acknowledged for ERC-AdG-2014-671093-SynCatMatchMoreno, JM.; Velty, A.; Vidal Moya, JA.; Díaz Morales, UM.; Corma Canós, A. (2018). Growing modulator agents for the synthesis of Al-MOF-type materials based on assembled 1D structural sub-domains. Dalton Transactions. 47(15):5492-5502. https://doi.org/10.1039/C8DT00394GS549255024715Li, B., Wen, H.-M., Wang, H., Wu, H., Tyagi, M., Yildirim, T., … Chen, B. (2014). A Porous Metal–Organic Framework with Dynamic Pyrimidine Groups Exhibiting Record High Methane Storage Working Capacity. 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Vinylene-Linked Covalent Organic Frameworks by Base-Catalyzed Aldol Condensation

Two 2D covalent organic frameworks (COFs) linked by vinylene (−CH=CH−) groups (V‐COF‐1 and V‐COF‐2) are synthesized by exploiting the electron deficient nature of the aromatic s‐triazine unit of C3‐symmetric 2,4,6‐trimethyl‐s‐triazine (TMT). The acidic terminal methyl hydrogens of TMT can easily be abstracted by a base, resulting in a stabilized carbanion, which further undergoes aldol condensation with multitopic aryl aldehydes to be reticulated into extended crystalline frameworks (V‐COFs). Both V‐COF‐1 (with terepthalaldehyde (TA)) and V‐COF‐2 (with 1,3,5‐tris(p‐formylphenyl)benzene (TFPB)) are polycrystalline and exhibit permanent porosity and BET surface areas of 1341 m2 g−1 and 627 m2 g−1, respectively. Owing to the close proximity (3.52 Å) of the pre‐organized vinylene linkages within adjacent 2D layers stacked in eclipsed fashion, [2+2] photo‐cycloadditon in V‐COF‐1 formed covalent crosslinks between the COF layers.TU Berlin, Open-Access-Mittel - 2019DFG, 390540038, EXC 2008: UniSysCa