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Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga-2(OH)(2)(L)] (H4L = Biphenyl-3,3 ',5,5 '-tetracarboxylic Acid), MFM-300(Ga-2)

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Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga-2(OH)(2)(L)] (H4L = Biphenyl-3,3 ',5,5 '-tetracarboxylic Acid), MFM-300(Ga-2)

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dc.contributor.author Krap, Cristina P. es_ES
dc.contributor.author Newby, Ruth es_ES
dc.contributor.author Dhakshinamoorthy, Amarajothi es_ES
dc.contributor.author García Gómez, Hermenegildo es_ES
dc.contributor.author Cebula, Izabela es_ES
dc.contributor.author Easun, Timothy L. es_ES
dc.contributor.author Savage, Mathew es_ES
dc.contributor.author Eyley, Jennifer E. es_ES
dc.contributor.author Gao, Shan es_ES
dc.contributor.author Blake, Alexander J. es_ES
dc.contributor.author Lewis, William es_ES
dc.contributor.author Beton, Peter H. es_ES
dc.contributor.author Warren, Mark R. es_ES
dc.contributor.author Allan, David R. es_ES
dc.contributor.author Frogley, Mark D. es_ES
dc.contributor.author Tang, Chiu C. es_ES
dc.contributor.author Cinque, Gianfelice es_ES
dc.contributor.author Yang, Sihai es_ES
dc.contributor.author Schroeder, Martin es_ES
dc.date.accessioned 2017-05-22T09:36:49Z
dc.date.issued 2016-02-01
dc.identifier.issn 0020-1669
dc.identifier.uri http://hdl.handle.net/10251/81567
dc.description.abstract Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga-2(OH)(2)(L)] (H4L = biphenyl-3,3',5,5'-tetracarboxylic acid), designated as MFM-300(Ga-2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)(3) and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga-2) crystallizes in the tetragonal space group I4(1)22, a = b = 15.0174(7) angstrom and c = 11.9111(11) angstrom and is isostructural with the Al(III) analogue MFM-300(Al-2) with pores decorated with -OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga1.87Fe0.13(OH)(2)(L)], MFM-300(Ga1.87Fe0.13), can be prepared under similar conditions to MFM-300(Ga-2) via reaction of a homogeneous mixture of Fe(NO3)(3) and Ga(NO3)(3) with biphenyl-3,3',5,5'-tetracarboxylic acid. An Fe(III)-based material [Fe3O1.5(OH)(HL)(L)(0.5)(H2O)(3.5)], MFM-310(Fe), was synthesized with Fe(NO3)(3) and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn2(1) with a = 10.560(4) angstrom, b = 19.451(8) angstrom, and c = 11.773(5) angstrom and incorporates mu(3)-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe-2(OH)(2)(L)], MFM-300(Fe-2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga-2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga1.87Fe0.13) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g(-1) at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga-2)-solv, MFM-300(Ga-2), MFM-300(Ga-2)center dot 2.35CO(2), MFM-300(Ga1.87Fe0.13)-solv, MFM-300(Ga1.87Fe0.13), and MFM-300(Ga1.87Fe0.13)center dot 2.0CO(2) have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M-OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the -OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga-2), Fe-doped MFM-300(Ga1.87Fe0.13) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the structural integrity of the parent material. es_ES
dc.description.sponsorship We thank the Universities of Nottingham and Manchester for support. M.S. acknowledges receipt of an ERC Advanced Grant and EPSRC Programme Grant. We also thank EPSRC for funding of X-ray equipment. We acknowledge the use of instrumentation within the Nottingham Nanotechnology and Nanoscience Centre, and thank Dr. Christopher Parmenter for assistance. We thank Conacyt, Mexico, for funding to C.P.K. We are especially grateful to Diamond Light Source for access to Beamlines Ill (EE8943), 119 (MT7548, MT8448, MT8937), and B22 (SM11279). en_EN
dc.language Inglés es_ES
dc.publisher American Chemical Society es_ES
dc.relation.ispartof Inorganic Chemistry es_ES
dc.rights Reconocimiento (by) es_ES
dc.subject METAL-ORGANIC FRAMEWORKS es_ES
dc.subject CARBON-DIOXIDE es_ES
dc.subject HYDROGEN ADSORPTION es_ES
dc.subject STRUCTURAL-CHARACTERIZATION es_ES
dc.subject CRYSTAL-STRUCTURE es_ES
dc.subject SOLID-SOLUTIONS es_ES
dc.subject SULFUR-DIOXIDE es_ES
dc.subject POROUS HOST es_ES
dc.subject FLUE-GAS es_ES
dc.subject SITES es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.title Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga-2(OH)(2)(L)] (H4L = Biphenyl-3,3 ',5,5 '-tetracarboxylic Acid), MFM-300(Ga-2) es_ES
dc.type Artículo es_ES
dc.embargo.lift 10000-01-01
dc.embargo.terms forever es_ES
dc.identifier.doi 10.1021/acs.inorgchem.5b02108
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials es_ES
dc.description.bibliographicCitation Krap, CP.; Newby, R.; Dhakshinamoorthy, A.; García Gómez, H.; Cebula, I.; Easun, TL.; Savage, M.... (2016). Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga-2(OH)(2)(L)] (H4L = Biphenyl-3,3 ',5,5 '-tetracarboxylic Acid), MFM-300(Ga-2). Inorganic Chemistry. 55(3):1076-1088. doi:10.1021/acs.inorgchem.5b02108 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://doi.org/10.1021/acs.inorgchem.5b02108 es_ES
dc.description.upvformatpinicio 1076 es_ES
dc.description.upvformatpfin 1088 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 55 es_ES
dc.description.issue 3 es_ES
dc.relation.senia 328549 es_ES
dc.identifier.eissn 1520-510X
dc.identifier.pmid 26757137 en_EN
dc.identifier.pmcid PMC4805307 en_EN
dc.contributor.funder University of Nottingham es_ES
dc.contributor.funder University of Manchester es_ES
dc.contributor.funder Engineering and Physical Sciences Research Council, Reino Unido es_ES
dc.contributor.funder Consejo Nacional de Ciencia y Tecnología, México es_ES
dc.contributor.funder European Research Council es_ES


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