Suchergebnisse

Three different conducting polymers, polythiophene (PT), polypirrol (PPY) and polyaniline (PANI) have been synthesized via oxidative chemical polymerization in aqueous media, in such a way that the synthesis protocol did not involve any toxic solvents. They have been tested in the abatement of nitrates from an aqueous solution without the need of any metal catalyst. The N-containing polymers (PANI and PPy) were able to remove nitrates to a level that accomplishes the European legislation requirements; however, the nature of each polymer greatly influenced the process mechanism. Whereas ion exchange between Cl- and SO42- counter-ions in the polymer and NO3- from water is the main responsible for the effective nitrate removal in PANI, as assessed by FTIR and XPS analyses, the nitrate removal mechanism on PPy is based in an electron transfer from the polymer to nitrate through N sites located in the pyrrolic ring. On the other hand, PT was not able to exchange nitrate unless it was synthesized with FeCl3 as oxidant/dopant and an anionic surfactant (sodium dodecyl sulfate -SDS-) is used. In that case, the electrostatic attraction between sulfate (OSO3-) groups from the surfactant and Fe3+ ions from FeCl3 produced the anchoring of Cl- to the oxidized PT growing chain, this favoring ion exchange with nitrate in the aqueous solution, followed by a redox process. ; Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) is gratefully acknowledged.

The hydrogenation of nitroarenes to produce the corresponding amines using dihydrogen as reducing agent has an important industrial role, since it allows to obtain important added-value products. This reaction needs the help of a catalyst to proceed. Many catalysts have been already tested and studied. Most of them are based on noble metals supported on metal oxides. These catalysts perform well, but they are expensive and thus, alternative systems are needed. In this context, cobalt-based catalysts have emerged as adequate alternatives, despite cobalt nanoparticles per se are not very active for this reaction. A way to improve the catalytic activity of cobalt nanoparticles is by supporting them on a support with functional groups that are able to change their intrinsic properties and to enhance their catalytic properties. In this sense, N-containing carbons are promising candidates to be used as support, since nitrogen functionalities may modify the catalytic properties of cobalt. In this work, cobalt nanoparticles supported on N-doped activated carbons have been prepared and studied as catalysts for the hydrogenation of 1-chloro-4-nitrobencene to the corresponding chloro-aniline. It is demonstrated that the catalytic activity is enhanced by the presence of nitrogen species in the support. When the temperature of the catalyst activation treatment (reduction under flowing hydrogen) is increased, the catalytic activity increases drastically in the presence of nitrogen functionalities on the support. The catalysts have been characterised by transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction, X-ray photoelectron spectroscopi (XPS) and N2 adsorption at 77 K. It has been found that the enhanced catalytic activity was due to two different factors, namely the interaction of the cobalt particles with the nitrogen functional groups (forming Co4N), and the development of mesopores in the support during the activation process that increases the accessibility of reactants to the active sites. ; Authors acknowledge financial support by MINECO (Spain) through the projects MAT2017-86992-R and MAT2016-80285-P and the European Union for the project "eForFuel", grant agreement 763911. J. C. S. R. would like to thank the Spanish Ministry of Science and Innovation for financial support through the Ramón y Cajal Program, Grant: RYC-2015-19230 J. C. S. R. would also like to thank Junta de Andalucía for financial support through the projects PY18-RE-0012 and IE18_0047_FUNDACIÓN LOYOLA.

Understanding/visualizing the established interactions between gases and adsorbents is mandatory to implement better performance materials in adsorption/separation processes. Here we report the unique behavior of a rare example of a hemilabile chiral three-dimensional metal–organic framework (MOF) with an unprecedented qtz-e-type topology, with formula CuII2(S,S)-hismox·5H2O (1) (hismox = bis[(S)-histidine]oxalyl diamide). 1 exhibits a continuous and reversible breathing behavior, based on the hemilability of carboxylate groups from l-histidine. In situ powder (PXRD) and single crystal X-ray diffraction (SCXRD) using synchrotron radiation allowed us to unveil the crystal structures of four different host–guest adsorbates (Ar@1, N2@1, CO2@1, and C3H6@1), rationalize the breathing motion, and unravel the mechanisms governing the adsorption of these gases. Then this information was transferred to implement efficient separations of mixtures of industrial and environmental relevance, CO2/N2, CO2/CH4, and C3H8/C3H6, using 1 in packed columns as the stationary phase and dispersed in a mixed matrix membrane. ; This work was supported by the MINECO (Spain) (projects CTQ2016-75671-P, MAT2017-86992-R, and MAT-80285-P and Excellence Unit "Maria de Maeztu" MDM-2015-0538) and the Ministero dell'Istruzione, dell'Università e della Ricerca (Italy). M.M. and E.T. thank the MINECO, and R.B. thanks the MIUR (project PON R&I FSE-FESR 2014-2020) for predoctoral grants. Thanks are also extended to the "Programa post-Ramón y Cajal de la Universidad de Valencia (E.P.)", the "Fondo per il finanziamento delle attivita base di ricerca" (D.A.), and the "Atracció de talent-contractes postdoctorals de la Universitat de Valencia" and "Juan de la Cierva-Incorporación-2017" programs (J.F.-S.). E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme/ERC grant agreement no. 814804, MOF-reactors.

Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions. ; S. M. J. Rogge, J. Hajek, and V. Van Speybroeck acknowledge the Fund for Scientific Research – Flanders (FWO), the Research Board of Ghent University (BOF) and BELSPO in the frame of IAP/7/05 for financial support. V. Van Speybroeck acknowledges funding from the European Union's Horizon 2020 research and innovation programme (consolidator ERC grant agreement no. 647755 – DYNPOR (2015–2020)). This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 641887 (project acronym: DEFNET). W. Dewitte and C. Caratelli are acknowledged for technical support with the figures. J. Gascon acknowledges funding from the European Union's 2020 research and innovation programme (ERC grant agreement no. 335746 – CrystEng-MOF-MMM) and from the Dutch Organization for Scientific Research (NWO, VIDI grant agreement 723.012.107 – MetMOFCat).