| 1. |
- Bello, Estefania, et al.
(författare)
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NH3-SCR catalysts for heavy-duty diesel vehicles : Preparation of CHA-type zeolites with low-cost templates
- 2022
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Ingår i: Applied Catalysis B. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 303
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Tidskriftsartikel (refereegranskat)abstract
- Computer-assistance allows selecting the most adequate low-cost organic structure directing agents (OSDAs) for the crystallization of Al-rich CHA-type zeolites. The host-guest stabilization energies of tetraethylammonium (TEA), methyltriethylammonium (MTEA) and dimethyldiethylammonium (DMDEA), in combination with Na, were first theoretically evaluated. This ab-initio analysis reveals that two TEA show a serious steric hindrance in a cha cavity, whereas two MTEA would present excellent host-guest confinements. The synthesis of Al-rich CHA-type zeolites has been accomplished using TEA and MTEA. Electron diffraction and high-resolution transmission electron microscopy reveal large CHA-domains with narrow faulted GME-domains in the CHAtype material synthesized with TEA, confirming the better OSDA-directing roles of MTEA cations towards the cha cavity, in good agreement with DFT calculations. Cu-exchanged Al-rich CHA-type samples achieved with MTEA and TEA show excellent catalytic activity and hydrothermal stability for the selective catalytic reduction (SCR) of NOx with ammonia under conditions relevant for future heavy duty diesel conditions.
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| 2. |
- Bello-Jurado, Estefanía, et al.
(författare)
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Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure-Directing Agents : Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:28
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Tidskriftsartikel (refereegranskat)abstract
- A novel ab initio methodology based on high-throughput simulations has permitted designing unique biselective organic structure-directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well-established commercial CHA-type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.
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| 3. |
- Campbell, Charles, et al.
(författare)
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Bridging model and real catalysts: general discussion
- 2016
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Ingår i: Faraday Discussions. - 1359-6640 .- 1364-5498. ; 188, s. 565-589
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Charles Campbell opened the discussion of the paper by Hans-JoachimFreund: If you have a 3D gold particle and it spreads out to be a 2D particle whenyou adsorb CO2, it must gain energy stability. Did you estimate the energy changeof the overall process to do that?
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| 4. |
- Campbell, Charles, et al.
(författare)
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Catalyst design from theory to practice: general discussion
- 2016
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Ingår i: Faraday Discussions. - 1359-6640 .- 1364-5498. ; 188, s. 279-307
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Hans-Joachim Freund opened the discussion of the paper by Alberto Roldan:How is the atomic hydrogen produced on the greigite surface? In the paper (DOI:10.1039/C5FD00186B) there is no comment whether you studied dissociatehydrogen adsorption.
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| 5. |
- Jiang, Jiuxing, et al.
(författare)
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ITQ-54 : a multi-dimensional extra-large pore zeolite with 20 [times] 14 [times] 12-ring channels
- 2015
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Ingår i: Chemical Science. - 2041-6520 .- 2041-6539. ; 6, s. 480-485
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Tidskriftsartikel (refereegranskat)abstract
- A multi-dimensional extra-large pore silicogermanate zeolite, named ITQ-54, has been synthesised by in situ decomposition of the N,N-dicyclohexylisoindolinium cation into the N-cyclohexylisoindolinium cation. Its structure was solved by 3D rotation electron diffraction (RED) from crystals of ca. 1 [small mu ]m in size. The structure of ITQ-54 contains straight intersecting 20 [times] 14 [times] 12-ring channels along the three crystallographic axes and it is one of the few zeolites with extra-large channels in more than one direction. ITQ-54 has a framework density of 11.1 T atoms per 1000 A3, which is one of the lowest among the known zeolites. ITQ-54 was obtained together with GeO2 as an impurity. A heavy liquid separation method was developed and successfully applied to remove this impurity from the zeolite. ITQ-54 is stable up to 600 [degree]C and exhibits permanent porosity. The structure was further refined using powder X-ray diffraction (PXRD) data for both as-made and calcined samples.
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| 6. |
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| 7. |
- Kapaca, Elina, et al.
(författare)
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Synthesis and Structure of a 22 x 12 x 12 Extra-Large Pore Zeolite ITQ-56 Determined by 3D Electron Diffraction
- 2021
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 143:23, s. 8713-8719
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Tidskriftsartikel (refereegranskat)abstract
- A multidimensional extra-large pore germanosilicate, denoted ITQ-56, has been synthesized by using modified memantine as an organic structure-directing agent. ITQ-56 crystallizes as plate-like nanocrystals. Its structure was determined by 3D electron diffraction/MicroED. The structure of ITQ-56 contains extra-large 22-ring channels intersecting with straight 12-ring channels. ITQ-56 is the first zeolite with 22-ring pores, which is a result of ordered vacancies of double 4-ring (d4r) units in a fully connected zeolite framework. The framework density is as low as 12.4 T atoms/1000 angstrom(3). The discovery of the ITQ-56 structure not only fills the missing member of extra-large pore zeolite with 22-ring channels but also creates a new approach of making extra-large pore zeolites by introducing ordered vacancies in zeolite frameworks.
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| 8. |
- Kwon, Soonhyoung, et al.
(författare)
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One-Pot Synthesis of CHA/ERI-Type Zeolite Intergrowth from a Single Multiselective Organic Structure-Directing Agent
- 2024
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Ingår i: ACS Applied Materials and Interfaces. - 1944-8244 .- 1944-8252. ; 16:12, s. 14661-14668
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Tidskriftsartikel (refereegranskat)abstract
- We report the one-pot synthesis of a chabazite (CHA)/erionite (ERI)-type zeolite intergrowth structure characterized by adjustable extents of intergrowth enrichment and Si/Al molar ratios. This method utilizes readily synthesizable 6-azaspiro[5.6]dodecan-6-ium as the exclusive organic structure-directing agent (OSDA) within a potassium-dominant environment. High-throughput simulations were used to accurately determine the templating energy and molecular shape, facilitating the selection of an optimally biselective OSDA from among thousands of prospective candidates. The coexistence of the crystal phases, forming a distinct structure comprising disk-like CHA regions bridged by ERI-rich pillars, was corroborated via rigorous powder X-ray diffraction and integrated differential-phase contrast scanning transmission electron microscopy (iDPC S/TEM) analyses. iDPC S/TEM imaging further revealed the presence of single offretite layers dispersed within the ERI phase. The ratio of crystal phases between CHA and ERI in this type of intergrowth could be varied systematically by changing both the OSDA/Si and K/Si ratios. Two intergrown zeolite samples with different Si/Al molar ratios were tested for the selective catalytic reduction (SCR) of NOx with NH3, showing competitive catalytic performance and hydrothermal stability compared to that of the industry-standard commercial NH3-SCR catalyst, Cu-SSZ-13, prevalent in automotive applications. Collectively, this work underscores the potential of our approach for the synthesis and optimization of adjustable intergrown zeolite structures, offering competitive alternatives for key industrial processes.
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| 9. |
- Lofstedt, Joakim, et al.
(författare)
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Green Diesel from Kraft Lignin in Three Steps
- 2016
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 9:12, s. 1392-1396
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Tidskriftsartikel (refereegranskat)abstract
- Precipitated kraft lignin from black liquor was converted into green diesel in three steps. A mild Ni-catalyzed transfer hydrogenation/hydrogenolysis using 2-propanol generated a lignin residue in which the ethers, carbonyls, and olefins were reduced. An organocatalyzed esterification of the lignin residue with an insitu prepared tall oil fatty acid anhydride gave an esterified lignin residue that was soluble in light gas oil. The esterified lignin residue was coprocessed with light gas oil in a continous hydrotreater to produce a green diesel. This approach will enable the development of new techniques to process commercial lignin in existing oil refinery infrastructures to standardized transportation fuels in the future.
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| 10. |
- Martinez-Franco, Raquel, et al.
(författare)
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Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes
- 2014
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Ingår i: Proceedings of the Royal Society. Mathematical, Physical and Engineering Sciences. - : The Royal Society. - 1364-5021 .- 1471-2946. ; 470:2166
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Tidskriftsartikel (refereegranskat)abstract
- The combination of different experimental techniques, such as solid C-13 and H-1 magic-angle spinning NMR spectroscopy, fluorescence spectroscopy and powder X-ray diffraction, together with theoretical calculations allows the determination of the unique structure directing the role of the bulky aromatic proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) towards the extra-large-pore ITQ-51 zeolite through supra-molecular assemblies of those organic molecules.
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| 11. |
- Martinez-Franco, Raquel, et al.
(författare)
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Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents
- 2013
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 110:10, s. 3749-3754
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of crystalline microporous materials containing large pores is in high demand by industry, especially for the use of these materials as catalysts in chemical processes involving bulky molecules. An extra-large-pore silicoaluminophosphate with 16-ring openings, ITQ-51, has been synthesized by the use of bulky aromatic proton sponges as organic structure-directing agents. Proton sponges show exceptional properties for directing extra-large zeolites because of their unusually high basicity combined with their large size and rigidity. This extra-large-pore material is stable after calcination, being one of the very few examples of hydrothermally stable molecular sieves containing extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals using the rotation electron diffraction method. Finally, several hypothetical zeolites related to ITQ-51 have been proposed.
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| 12. |
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| 13. |
- Moliner, Manuel, et al.
(författare)
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A New Aluminosilicate Molecular Sieve with a System of Pores between Those of ZSM-5 and Beta Zeolite
- 2011
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 133:24, s. 9497-9505
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Tidskriftsartikel (refereegranskat)abstract
- A new aluminosilicate zeolite (ITQ-39) has been synthesized. This is an extensively faulted structure with very small domains that makes the structure elucidation very difficult. However, a combination of adsorption spectroscopy and reactivity studies with selected probe molecules suggests that the pore structure of ITQ-39 is related to that of Beta zeolite, with a three-directional channel system with large pores (12-MR), but with an effective pore diameter between those of Beta and ZSM-5, or a three-directional channel system with interconnected large (12-MR) and medium pores (10-MR). The pore topology of ITQ-39 is very attractive for catalysis and shows excellent results for the preparation of cumene by alkylation of benzene, while it can be a promising additive for FCC.
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| 14. |
- Moliner, Manuel, et al.
(författare)
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Synthesis Design and Structure of a Multipore Zeolite with Interconnected 12-and 10-MR Channels
- 2012
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 134:14, s. 6473-6478
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Tidskriftsartikel (refereegranskat)abstract
- A new molecular sieve, ITQ-38, containing interconnected large and medium pores in its structure has been synthesized. The rational combination of dicationic piperidine-derivative molecules as organic structure directing agents (OSDAs) with germanium and boron atoms in alkaline media has allowed the synthesis of ITQ-38 zeolite. High-resolution transmission electron microscopy (HRTEM) has been used to elucidate the framework topology of ITQ-38, revealing the presence of domains of perfect ITQ-38 crystals as well as very small areas containing nanosized ITQ-38/ITQ-22 intergrowths. The structure of ITQ-38 is highly related to ITQ-22 and the recently described polymorph C of ITQ-39 zeolite. It shares a common building layer with ITQ-22 and contains the same building unit as the polymorph C of ITQ-39. All three structures present similar framework density, 16.1 T atoms/1000 angstrom(3).
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| 15. |
- Schwalbe-Koda, Daniel, et al.
(författare)
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A priori control of zeolite phase competition and intergrowth with high-throughput simulations
- 2021
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 374:6565, s. 308-315
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Tidskriftsartikel (refereegranskat)abstract
- Zeolites are versatile catalysts and molecular sieves with large topological diversity, but managing phase competition in zeolite synthesis is an empirical, labor-intensive task. In this work, we controlled phase selectivity in templated zeolite synthesis from first principles by combining high-throughput atomistic simulations, literature mining, human-computer interaction, synthesis, and characterization. Proposed binding metrics distilled from more than 586,000 zeolite-molecule simulations reproduced the extracted literature and rationalized framework competition in the design of organic structure-directing agents. Energetic, geometric, and electrostatic descriptors of template molecules were found to regulate synthetic accessibility windows and aluminum distributions in pure-phase zeolites. Furthermore, these parameters allowed us to realize an intergrowth zeolite through a single bi-selective template. The computation-first approach enables control of both zeolite synthesis and structure composition using a priori theoretical descriptors.
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| 16. |
- Subbotina, Elena, 1990-, et al.
(författare)
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Zeolite-assisted lignin-first fractionation of lignocellulose : Overcoming lignin recondensation via shape-selective catalysis
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Organosolv pulping releases reactive monomers from both lignin and hemicellulose via the cleavage of weak C–O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C–C bonds. Different strategies have been developed to prevent this process by stabilising the reactive monomers (i.e., lignin-first approaches). To date, all reported approaches rely on the addition of capping agents or metal-catalysed stabilisation reactions, which usually require high pressures of hydrogen gas. Herein, we report a metal- and additive-free approach that uses zeolites as acid catalysts to convert the reactive monomers into more stable derivatives under organosolv pulping conditions. Experiments with model lignin compounds showed that the recondensation of aldehydes and allylic alcohols produced by the cleavage of β-O-4′ bonds was efficiently inhibited by the use of protonic BETA zeolite. By applying a zeolite with a preferred pore size, the bimolecular reactions of reactive monomers were effectively inhibited, resulting in stable and valuable monophenolics. The developed methodology was further extended to birch wood to yield monophenolic compounds and value-added products from carbohydrates.
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| 17. |
- Subbotina, Elena, et al.
(författare)
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Zeolite-Assisted Lignin-First Fractionation of Lignocellulose : Overcoming Lignin Recondensation through Shape-Selective Catalysis
- 2020
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 13:17, s. 4528-4536
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Tidskriftsartikel (refereegranskat)abstract
- Organosolv pulping releases reactive monomers from both lignin and hemicellulose by the cleavage of weak C-O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C-C bonds. Different strategies have been developed to prevent this process by stabilizing the reactive monomers (i.e., lignin-first approaches). To date, all reported approaches rely on the addition of capping agents or metal-catalyzed stabilization reactions, which usually require high pressures of hydrogen gas. Herein, a metal- and additive-free approach is reported that uses zeolites as acid catalysts to convert the reactive monomers into more stable derivatives under organosolv pulping conditions. Experiments with model lignin compounds showed that the recondensation of aldehydes and allylic alcohols produced by the cleavage of beta-O-4 ' bonds was efficiently inhibited by the use of protonic beta zeolite. By applying a zeolite with a preferred pore size, the bimolecular reactions of reactive monomers were effectively inhibited, resulting in stable and valuable monophenolics. The developed methodology was further extended to birch wood to yield monophenolic compounds and value-added products from carbohydrates.
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| 18. |
- Willhammar, Tom, et al.
(författare)
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Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography
- 2012
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Ingår i: Nature Chemistry. - : Springer Science and Business Media LLC. - 1755-4330 .- 1755-4349. ; 4, s. 188-194
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Tidskriftsartikel (refereegranskat)abstract
- Porous materials such as zeolites contain well-defined pores in molecular dimensions and have important industrial applications in catalysis, sorption and separation. Aluminosilicates with intersecting 10- and 12-ring channels are particularly interesting as selective catalysts. Many porous materials, especially zeolites, form only nanosized powders and some are intergrowths of different structures, making structure determination very challenging. Here, we report the atomic structures of an aluminosilicate zeolite family, ITQ-39, solved from nanocrystals only a few unit cells in size by electron crystallography. ITQ-39 is an intergrowth of three different polymorphs, built from the same layer but with different stacking sequences. ITQ-39 contains stacking faults and twinning with nano-sized domains, being the most complex zeolite ever solved. The unique structure of ITQ-39, with a three-dimensional intersecting pairwise 12-ring and 10-ring pore system, makes it a promising catalyst for converting naphtha into diesel fuel, a process of emerging interest for the petrochemical industry.
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| 19. |
- Yun, Yifeng, et al.
(författare)
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The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- A new germanosilicate zeolite (denoted as ITQ-53) with extra-large 14-ring pores has been synthesized using tri-tertbutylmethylphosphonium cation as the organic structure directing agent (OSDA). The new rotation electron diffraction (RED) method was used to both identify and solve the structure of ITQ-53 from an initially synthesized sample containing impurities, which facilitated the synthesis optimization that led to pure ITQ-53. The structure was refined against PXRD data. ITQ-53 is the first example of extra-large pore zeolites with tri-directional interconnected 14 × 14 × 14-ring channels. It is built from double 3-rings (D3Rs), double 4-rings (D4Rs), and a new composite building unit [42.54.63]. D3Rs are very rare, previously only found in two zeolitic silicogermanates. ITQ-53 is stable up to at least 450 °C. The structure of ITQ-53 was changed from monoclinic to orthorhombic up on calcination.
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| 20. |
- Yun, Yifeng, et al.
(författare)
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The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule
- 2015
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 51:36, s. 7602-7605
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Tidskriftsartikel (refereegranskat)abstract
- A new germanosilicate zeolite (denoted as ITQ-53) with extra-large pores has been synthesised using tri-tertbutylmethylphosphonium cation as the organic structure directing agent (OSDA). Rotation electron diffraction (RED) was used to identify ITQ-53 from an initially-synthesised sample containing impurities, and to solve its structure. The structure was refined against PXRD data of pure ITQ-53 samples obtained after synthesis optimisation. ITQ-53 is the first example of extra-large pore zeolites with tri-directional interconnected 14 x 14 x 14-ring channels. It is stable up to at least 650 degrees C. The structure of ITQ-53 changes from monoclinic to orthorhombic upon calcination.
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