Jorge Gascon

Delft University of Technology, Delft, South Holland, Netherlands

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Publications (165)888.65 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Ordered mesoporous silica-NH2-MIL-53(Al) core-shell spheres of about 4 μm in diameter have been synthesized by seeding the corresponding mesoporous silica spheres (MSSs) with crystals of NH2-MIL-53(Al) and subsequent secondary crystal growth into a MOF shell. The morphology of the particles was analyzed by SEM, while TGA, EDX and XRD characterizations gave information on the composition and structure of this material and the activation of the MOF. N2 adsorption analysis revealed that the NH2-MIL-53(Al) shell controlled the access of guest molecules into the hydrophilic silica mesoporous structure, while the breathing behavior of the microporous NH2-MIL-53(Al) shell was confirmed by CO2 adsorption isotherms.
    No preview · Article · May 2016 · Microporous and Mesoporous Materials
  • Sonia Castellanos · Freek Kapteijn · Jorge Gascon
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    ABSTRACT: The ability of modulating the properties of metal-organic frameworks (MOF) on demand by external light-stimuli is a most appealing pathway to enhance their performance in storage and separation and to render novel advanced applications. Photoswitchable linkers of different nature have been inserted in several MOF structures either as integral parts of their scaffolds or as guests in the pores. In this highlight we analyse the different strategies and expose some aspects that should be considered in the design of new generations of photoswitable MOFs.
    No preview · Article · Feb 2016 · CrystEngComm
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    ABSTRACT: A systematic study of the effect of physicochemical properties affecting catalyst deactivation, overall olefin selectivity and ethylene/propylene ratio during the methanol-to-olefins (MTO) reaction is presented for two zeolites with the DDR topology, namely Sigma-1 and ZSM-58. Both catalysts show high selectivity towards light olefins and completely suppress the formation of hydrocarbons bigger than C4, with selectivity to ethane not exceeding 1% and some traces of propane.By applying seeded growth approach, a series of Sigma-1 zeolites with tunable crystal size and acidity was synthesized. For this series the highest methanol throughput at 450 oC before deactivation was found for crystals 0.5 µm in size with an acidity corresponding to 0.5 Al atoms per zeolite cage, and a selectivity to ethylene and propylene reaching 90%. Comparison between ZSM-58 and Sigma-1 catalysts with similar morphologies and acidity under the same reaction conditions revealed a three times higher throughput of methanol in case of ZSM-58. The analysis of functional surface groups, assessed through FT-IR, revealed the presence of silanol defects in Sigma-1 responsible for faster catalyst deactivation. These silanol defects can be selectively removed (confirmed by FT-IR) from the zeolite framework by applying a mild treatment in presence of NaOH/CTAB, leading to an improved catalyst lifetime. Co-feeding experiments with short olefins and water show low reactivity of primary MTO products, which only react at the surface of the catalyst particles. These results demonstrate that migration of the reaction zone in case of DDR catalysts hardly affects catalyst stability, product composition and nature of deactivating species. The nature of these species depends mostly on reaction temperature: at low temperatures deactivation occurs mainly due to the formation of inert adamantane species, while at high temperatures poly-condensed aromatic hydrocarbons play the major role in deactivation.
    No preview · Article · Jan 2016 · Catalysis Science & Technology
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    ABSTRACT: A study of a copper-based metal–organic framework (MOF) synthesized by an electrochemical route is presented. Morphological and adsorption properties of the MOF synthesized as bulk powder and on supported copper surfaces were investigated. Differences in these properties and structural refinement studies indicate that when 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) is used as linker interpenetration can be prevented when the structure is grown on a surface.
    No preview · Article · Jan 2016 · CrystEngComm
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    ABSTRACT: Mesoporous H-ZSM-5 - carbon composites, prepared via tetrapropylammonium hydroxide (TPAOH) post treatment of H-ZSM-5 followed by deposition of pyrolytic carbon, have been used as support for the preparation of Co based Fischer-Tropsch catalysts. The resulting catalysts display an improved performance during Fischer-Tropsch synthesis (FTS), with higher activity, higher selectivity towards C5-C9 (gasoline range) and lower selectivity towards C1 (and C2) than Co/mesoH-ZSM5 (without pyrolytic carbon). This is due to the weaker metal support interaction by the deposited carbon (as revealed by XPS) leading to a higher reducibility of the Co species. Further, the partial deactivation of the Brønsted acid sites by pyrolytic carbon deposition, as was observed by NH3-TPD, allows modifying the zeolite acidity. Both olefin to paraffin (O/P) and isoparaffin to normal paraffin (I/N) ratios decrease with increasing the carbon content, opening the door to further tuning the catalytic performance in multifunctional FTS operation.
    No preview · Article · Jan 2016 · Catalysis Science & Technology
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    ABSTRACT: The synthesis, characterization, sulfonation, and catalytic performance of two new porous aromatic frameworks are presented. The polymers, which were obtained by the Suzuki-Miyaura cross-coupling of the commercially available precursors 1,3,5-tris(4-bromophenyl)benzene or tris(4-bromophenyl)amine and benzene-1 4-diboronic acid, only contain aromatic sp2 C-C and C-N bonds, display excellent thermal and chemical stability, and allow for post-synthetic functionalization under very harsh reaction conditions. Upon post-synthetic treatment at 160°C in 98wt% sulfuric acid, approximately 65% of the benzene rings in the polymers were sulfonated. The materials were characterized by solid-state NMR spectroscopy, X-ray photoelectron spectroscopy, FTIR spectroscopy, and textural analysis. The sulfonated materials display an excellent catalytic performance in the acid-catalyzed esterification of n-butanol and acetic acid and have a similar or even superior performance to that of state-of-the-art Amberlyst-15 over multiple catalytic cycles.
    No preview · Article · Jan 2016 · ChemCatChem
  • Xiaohui Sun · Sina Sartipi · Freek Kapteijn · Jorge Gascon
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    ABSTRACT: The structure and catalytic performance of bifunctional 10 wt% Co/mesoHZSM-5 catalysts pretreated under different conditions, i.e. in stagnant air, or in a flow of air, N2, or 1 vol% NO/Ar, were investigated for the Fischer–Tropsch synthesis (FTS) under fixed operating conditions of T = 513 K, P = 15 bar, H2/CO = 1. The combination of acid sites and FTS functionality leads to the direct formation of gasoline range hydrocarbons and suppresses the formation of C20+ products. The highest activity, C5–C11 selectivity and lowest CH4 selectivity were obtained for Co/mesoHZSM-5 catalyst pretreated in stagnant air. Pretreatment in gas flow resulted in a lower activity and C5–C11 selectivity, and in a higher CH4 selectivity, in particular for samples pretreated with NO. Characterization shows that this underperformance is due to changes in the Co3O4 particle size distribution and cobalt reducibility, and is related to the cobalt loading relative to the mesopore area. Pretreatment in air or N2 flow increased the number of small Co3O4 particles and increased cobalt reducibility by suppressing the formation of highly dispersed cobalt, e.g. cobalt silicates, in strong interaction with mesoHZSM-5. Pretreatment in a 1 vol% NO/Ar flow significantly increased cobalt dispersion further, decreasing the cobalt reducibility due to the strong interaction between cobalt and mesoHZSM-5. Based on both TEM and in situ DRIFTS studies, the optimum performance of Co/mesoHZSM-5 pretreated in stagnant air could be attributed to a lower fraction of small cobalt particles, known to promote the formation of CH4 via hydrogenolysis or direct methanation. Additionally, small cobalt particles are more susceptible to be oxidized under FT conditions, thereby decreasing FT activity and indirectly increasing CH4 selectivity by increasing the H2/CO ratio through the water gas shift reaction.
    No preview · Article · Dec 2015 · New Journal of Chemistry
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    ABSTRACT: FTIR spectra of (12)CO2 and (12)CO2 + (13)CO2 mixtures adsorbed on MIL-53(Al) reveal the formation of highly symmetric dimeric (CO2)2 species connected to two structural OH groups.
    Full-text · Article · Dec 2015 · Chemical Communications
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    ABSTRACT: The ability to control the interplay of materials with low-energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal-organic frameworks (MOFs) were synthesized from the same linker bearing all-visible ortho-fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids. The framework built with Al-based nodes has congested 1D channels that preclude efficient isomerization. As a result, local light-heat conversion can be used to alter the CO2 adsorption capacity of the material on exposure to green light. The second framework, built with Zr nodes, provides enough room for the photoswitches to isomerize, which leads to a unique bistable photochromic MOF that readily responds to blue and green light. The superiority of green over UV irradiation was additionally demonstrated by reflectance spectroscopy and analysis of digested samples. This material offers promising perspectives for liquid-phase applications such as light-controlled catalysis and adsorptive separation.
    No preview · Article · Nov 2015 · Chemistry - A European Journal
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    ABSTRACT: Single-ion magnets (SIMs) are the smallest possible magnetic devices and are a controllable, bottom-up approach to nanoscale magnetism with potential applications in quantum computing and high-density information storage. In this work, we take advantage of the promising, but yet insufficiently explored, solid-state chemistry of metal-organic frameworks (MOFs) to report the single-crystal to single-crystal inclusion of such molecular nanomagnets within the pores of a magnetic MOF. The resulting host-guest supramolecular aggregate is used as a playground in the first in-depth study on the interplay between the internal magnetic field created by the long-range magnetic ordering of the structured MOF and the slow magnetic relaxation of the SIM.
    Full-text · Article · Nov 2015 · Chemistry - A European Journal
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    ABSTRACT: A large fraction of global energy is consumed for heating and cooling. Adsorption driven heat pumps and chillers could be employed to reduce this consumption. MOFs are often considered as ideal adsorbents for heat pumps and chillers. While most published works to date on this topic have focused on the use of water as working fluid, the instability of many MOFs to water together with the fact that water cannot be used at sub-zero temperatures pose certain drawbacks. The potential of using alcohol-MOF pairs in adsorption driven heat pumps and chillers is investigated. To this end, eighteen different selected MOF structures in combination with either methanol or ethanol as working fluid are considered, and their potential is assessed based on adsorption measurements and thermodynamic efficiencies. If alcohols are used instead of water (1) Adsorption occurs at lower relative pressures for methanol and even lower for ethanol, (2) larger pores can be utilized efficiently, as hysteresis is absent for pores smaller than 3.4 nm (2 nm for water), (3) larger pore sizes need to be employed to ensure the desired step-wise adsorption, (4) the effect of (polar/apolar) functional groups in the MOF is far less pronounced, (5) the energy released or taken up per cycle is lower, but heat and mass transfer may be enhanced, (6) Stability of MOFs seems less of an issue and (7) cryogenic applications (e.g. ice-making) become feasible. From a thermodynamic perspective, UiO-67, CAU-3 and ZIF-8 seem to be the most promising MOFs, for both methanol and ethanol as working fluid. Although UiO-67 might not be completely stable, both CAU-3 and ZIF-8 have potential to be applied, especially in subzero temperature adsorption chillers (AC).
    No preview · Article · Nov 2015 · Langmuir

  • No preview · Article · Oct 2015 · Chemical Reviews
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    ABSTRACT: We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.
    Full-text · Article · Oct 2015 · Inorganic Chemistry
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    ABSTRACT: Bonding in six-coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition-metal analogues. We herein demonstrate through sophisticated electronic-structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron-rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex.
    No preview · Article · Oct 2015 · Angewandte Chemie International Edition
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    ABSTRACT: The latest advances in the field of zeolitic membranes for gas separation are critically reviewed with special emphasis on new synthetic protocols. After introducing the most relevant aspects to membrane performance, including adsorption trends, permeation mechanisms and support effects, we review recent achievements in membrane synthesis and discuss in detail the effect of zeolite topology and chemical composition on membrane gas separation. We pay special attention to promising 8MR high-silica structures. As the formation of defects during synthesis remains one of the major challenges for large-scale production of such membranes, we review various approaches to either limit defect formation or decrease their adverse effect by post-synthesis modification. Finally, the current challenges for this field of research are summarized and an outlook is offered on approaches to decrease fabrication costs, improve reproducibility and rational design of zeolite membranes.
    No preview · Article · Oct 2015 · Journal of Membrane Science
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    ABSTRACT: Incorporation of new functionalities into metal–organic frameworks (MOFs) by post-synthetic modification is a most attractive strategy for attaining the desired properties without risking destruction of the crystalline structure chosen for the aimed application. In this work the amine group in NH2-MIL-53(Al) was used as anchoring point for the diphenylphosphinyl (Ph2PO–) moiety. The success of the derivatization was confirmed by 31P MAS NMR and DRIFT spectroscopic studies. A newly synthesized reference linker bearing the same phosphinic amide functional group was used to assist in the MOF characterization. The introduction of the bulky diphenylphosphinyl group stabilizes the large-pore form of the MOF and leads to changes in the optical properties as a consequence of the electronic influence of the PO group. The approach described here is relevant for the preparation of novel phosphorus-containing MOFs.
    No preview · Article · Aug 2015 · Berichte der deutschen chemischen Gesellschaft
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    ABSTRACT: Bonding in six-coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition-metal analogues. We herein demonstrate through sophisticated electronic-structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron-rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    No preview · Article · Aug 2015 · Angewandte Chemie
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    ABSTRACT: Thermal treatment of phosphotungstic acid (PTA)-MIL-101(Cr) composites in the presence of hydroformylation catalyst RhH(CO)(PPh3)3 leads to immobilization of the homogeneous Rh complex within the metal–organic framework (MOF) scaffold by coordination of PTA-Rh. The Rh complex-containing MOFs are tested in the hydroformylation of 1-octene in which PTA competes with CO during ligand association. In the presence of the carbonyl ligand, the Rh complex is released from the MOF and behaves as a homogeneous catalyst. Therefore, the product spectra and selectivities of the Rh complex-containing MOFs are similar to those of RhH(CO)(PPh3)3. Upon CO evacuation, Rh recoordinates to PTA, allowing for easy recycling of this new pseudo-heterogeneous catalyst.
    No preview · Article · Aug 2015 · ChemCatChem
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    ABSTRACT: A new hydrothermally stable Al polycarboxylate metal-organic framework (MOF) based on a heteroatom bio-derived aromatic spacer has been designed through a template-free green synthesis process. It appears that in some test conditions this MOF outperforms the heat reallocation performances of the commercial SAPO-34. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Full-text · Article · Jul 2015 · Advanced Materials
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    ABSTRACT: During the last decade the number of publications related to the synthesis of new metal-organic frameworks or coordination polymers has grown almost exponentially. Many of them are devoted to the study of the correlation between the molecular components (linkers and metal nodes or clusters) and the final properties of the resulting structure. Withal, the field of metal-organic frameworks has also witnessed important advances in the development of synthetic tools to control the particle size and shape and to obtain secondary porosity by applying knowledge from three disciplines: crystallography, coordination chemistry and chemical engineering. These tools allow for crystal engineering beyond the molecular scale extending over the meso and macro scales, so that certain degree of multi-scale design is already possible. In this manner, MOFs’ performance have been improved in certain applications by choosing the optimal particle morphology and dimensions that enhance the materials’ properties and/or facilitate their implementation on functional devices. This review highlights the latest advances on MOF crystal engineering, with special emphasis on the meso and macro scales. After discussing some general considerations on the fundamentals of MOF crystallization, we examine different synthetic approaches developed in order to tune the MOF particle size, shape and textural properties and the impact this multi-scale MOF crystal engineering has shown so far in different applications. Finally, our view on possible future research directions is outlined.
    Full-text · Article · Jul 2015 · Coordination Chemistry Reviews

Publication Stats

5k Citations
888.65 Total Impact Points

Institutions

  • 2008-2016
    • Delft University of Technology
      • • Department of Chemical Engineering
      • • Catalysis Engineering Group
      Delft, South Holland, Netherlands
  • 2012-2014
    • University of Valencia
      • • Inorganic Chemistry
      • • Instituto de Ciencia Molecular (ICMol)
      Valenza, Valencia, Spain
  • 2013
    • Cambridge Eco
      Cambridge, England, United Kingdom
  • 2004-2008
    • University of Zaragoza
      • Department of Chemical Engineering and Environmental Technology
      Caesaraugusta, Aragon, Spain