15 research outputs found
Designed synthesis and structural investigation of novel zeolites in the ABC-6 family
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Designed synthesis of STA-30 : a small pore zeolite catalyst with topology type SWY
R.G.C. thanks the University of St Andrews and Johnson Matthey for funding. P.A.W. thanks the EPSRC (Designed Synthesis of Zeolites: EP/S016201/1) and the Royal Society (Industry Fellowship INF\R2\192052) for support. A.M. acknowledges the Spanish Ministry of Science and Innovation through the Ramon y Cajal programme (RYC2018-024561-I), the Regional government of Aragon (DGA E13_20R), and to the National Natural Science Foundation of China (NFSC-21850410448; NSFC-21835002).Small-pore aluminosilicate zeolites are attractive targets for synthesis because of their activity as catalysts in important reactions, including ammonia-mediated selective catalytic reduction (SCR) of NOx in auto-exhaust emissions. Such a zeolite with SWY framework type, previously observed as a silicoaluminophosphate, has been prepared with high crystallinity via designed syntheses employing organic 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl (diDABCO-C8) and K+ cations as templates. STA-30 (St Andrews microporous material 30) is an ABC-6 structure in the erionite-offretite family of zeolites that exhibits the 12-layer stacking sequence AABAABAACAAC. The framework, which can be prepared with a controllable Si/Al ratio, possesses columns of alternating d6r units and can cages, of which the latter are oriented to give an inter-column pore space comprising gme cages and swy cages connected via 8Rs. DiDABCO-C8 cations fill the swy cages of as-prepared STA-30, while K+ cations display high occupancy in the can cages. Removal of the template by calcination, followed by ammonium ion exchange of K+ cations residing outside the can cages and subsequent deammoniation, gives a highly crystalline zeolite (K3H6Al9Si72O144, P63/mmc, a = 12.9922(9) Å, c = 29.9624(12) Å) with solid acidity shown by solid-state 1H MAS NMR. Upon hydration, a portion of the Al adopts octahedral geometry, as demonstrated by two sharp resonances at −2.0 and −3.1 ppm in the 27Al MAS NMR. These octahedral species can be converted back to tetrahedral Al by ammonium exchange and are interpreted as distinct hydrated framework Al sites. The activated K,H-STA-30 is a small-pore solid acid with a three-dimensionally connected micropore volume of 0.31 cm3 g–1. In the copper-loaded form, it is an active catalyst for the SCR of NO by ammonia.PostprintPostprintPeer reviewe
Synthetic control of defect structure and hierarchical extra-large/small-pore microporosity in aluminosilicate zeolite SWY
R.G.C. thanks the University of St. Andrews and Johnson Matthey for funding. P.A.W. thanks the Royal Society (Industrial Fellowship INF\R2\192052) for support. R.G.C. acknowledges the support of the EPSRC Light Element Analysis Facility grant EP/T019298/1 and the EPSRC Strategic Equipment Resource grant EP/R023751/1 for the use of the Jeol JSM-IT800 electron microscope at the University of St Andrews. A.M. acknowledges the Spanish Ministry of Science (RYC2018-024561-I) and the Gobierno of Aragon (Nanomidas group, code E13_23R).The SWY-type aluminosilicate zeolite, STA-30, has been synthesized via different routes to understand its defect chemistry and solid acidity. The synthetic parameters varied were the gel aging, the Al source, and the organic structure directing agent. All syntheses give crystalline materials with similar Si/Al ratios (6–7) that are stable in the activated K,H-form and closely similar by powder X-ray diffraction. However, they exhibit major differences in the crystal morphology and in their intracrystalline porosity and silanol concentrations. The diDABCO-C82+ (1,1′-(octane-1,8-diyl)bis(1,4-diazabicyclo[2.2.2]octan)-1-ium)-templated STA-30 samples (but not those templated by bisquinuclidinium octane, diQuin-C82+) possess hierarchical microporosity, consisting of noncrystallographic extra-large micropores (13 Å) that connect with the characteristic swy and gme cages of the SWY structure. This results in pore volumes up to 30% greater than those measured in activated diQuin-C8_STA-30 as well as higher concentrations of silanols and fewer Brønsted acid sites (BASs). The hierarchical porosity is demonstrated by isopentane adsorption and the FTIR of adsorbed pyridine, which shows that up to 77% of the BASs are accessible (remarkable for a zeolite that has a small-pore crystal structure). A structural model of single can/d6r column vacancies is proposed for the extra-large micropores, which is revealed unambiguously by high-resolution scanning transmission electron microscopy. STA-30 can therefore be prepared as a hierarchically porous zeolite via direct synthesis. The additional noncrystallographic porosity and, subsequently, the amount of SiOHs in the zeolites can be enhanced or strongly reduced by the choice of crystallization conditions.Publisher PDFPeer reviewe
Cation control of cooperative CO2 adsorption in Li-containing mixed cation forms of the flexible zeolite merlinoite
The authors thank the EPSRC for funding (Cation-Controlled Gating for Selective Gas Adsorption over Adaptable Zeolites: EP/N032942/1, V.M.G., P.A.W. and an NPIF Ph.D. scholarship for E.L.B.: EP/R512199/1). We acknowledge Diamond Light Source for time on Beamline I11 under Proposal CY22322-1. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation RB2090052-1 from the Science and Technology Facilities Council. The raw data accompanying this publication are directly available at https://doi.org/10.17630/cac904b4-3c07-4159-913f80ff53b13bb7 [reference 59] and, for the neutron powder diffraction data, https://doi.org/10.5286/ISIS.E.RB2090052-1The lithium-exchanged form of a merlinoite zeolite (MER) with Si/Al = 4.2 (unit cell composition Li6.2Al6.2Si25.8O64) possesses a strongly contracted framework when dehydrated (the unit cell volume decreases by 12.9% from the hydrated ‘wide-pore’ form to the dehydrated ‘narrow-pore’ form). It shows cooperative adsorption behaviour for CO2, leading to two-step isotherms with the second step at elevated pressure (>2.5 bar at 298 K). Partially exchanging Na and K cations to give single phase Li,Na- and Li,K-MER materials reduces the pressure of this second adsorption step because the transition from narrow- to wide-pore forms upon CO2 adsorption occurs at lower partial pressures compared to that in Li-MER: partial exchange with Cs does not reduce the pressure of this transition. Exsolution effects are also seen at K cation contents >2.2 per unit cell. The phase transitions proceed via intermediate structures, by complex phase behaviour rarely seen for zeolitic materials. The strongly distorted narrow-pore structures adopted upon dehydration give one dimensional channel structures in which the percolation of CO2 through the material requires cation migration from their locations in ste sites. This is slow in Li3.4Cs2.8-MER where Cs cations occupy these critical ste cavities in the channels, causing very slow adsorption kinetics. As the partial pressure of CO2 increases, a threshold pressure is reached where cooperative adsorption and Cs cation migration occur and the wide-pore form results, with a three dimensionally connected pore system, leading to a sharp increase in uptake. This is far in excess of the increase of unit cell volume because more of the pore space becomes accessible. Strong hysteretic effects occur upon desorption, leading to CO2 encapsulation. CO2 remaining within the material after repeated adsorption/desorption cycles without heated activation improves sorption kinetics and modifies the stepped isotherms.PostprintPostprintPeer reviewe
Following the unusual breathing behaviour of 17O-enriched mixed-metal (Al,Ga)-MIL-53 using NMR crystallography
The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 EXONMR and Advanced Grant 787073 ADOR), and EPSRC (EP/N509759/1) for a studentship for CMR. SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography (CCP-NC) funded by EPSRC (EP/M022501/1) and the UKCP consortium funded by EPSRC (EP/K013564/1). For computational resources we are grateful to the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1) and the UK HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). The research data (and/or materials) supporting this publication can be accessed at DOI: https://doi.org/10.17630/31529c8b-f197-484c-929b-ef993a5bea68.69The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al- MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming.Publisher PDFPeer reviewe
Designed synthesis and structural investigation of novel zeolites in the ABC-6 family (thesis data)
The data files are embargoed until 02/11/202
Designed synthesis of STA-30:a small pore zeolite catalyst with topology type SWY
Small-pore aluminosilicate zeolites are attractive targets for synthesis because of their activity as catalysts in important reactions, including ammonia-mediated selective catalytic reduction (SCR) of NOx in auto-exhaust emissions. Such a zeolite with SWY framework type, previously observed as a silicoaluminophosphate, has been prepared with high crystallinity via designed syntheses employing organic 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl (diDABCO-C8) and K+ cations as templates. STA-30 (St Andrews microporous material 30) is an ABC-6 structure in the erionite-offretite family of zeolites that exhibits the 12-layer stacking sequence AABAABAACAAC. The framework, which can be prepared with a controllable Si/Al ratio, possesses columns of alternating d6r units and can cages, of which the latter are oriented to give an inter-column pore space comprising gme cages and swy cages connected via 8Rs. DiDABCO-C8 cations fill the swy cages of as-prepared STA-30, while K+ cations display high occupancy in the can cages. Removal of the template by calcination, followed by ammonium ion exchange of K+ cations residing outside the can cages and subsequent deammoniation, gives a highly crystalline zeolite (K3H6Al9Si72O144, P63/mmc, a = 12.9922(9) Å, c = 29.9624(12) Å) with solid acidity shown by solid-state 1H MAS NMR. Upon hydration, a portion of the Al adopts octahedral geometry, as demonstrated by two sharp resonances at −2.0 and −3.1 ppm in the 27Al MAS NMR. These octahedral species can be converted back to tetrahedral Al by ammonium exchange and are interpreted as distinct hydrated framework Al sites. The activated K,H-STA-30 is a small-pore solid acid with a three-dimensionally connected micropore volume of 0.31 cm3 g–1. In the copper-loaded form, it is an active catalyst for the SCR of NO by ammonia.</p
Understanding the anion-templated, OSDA-free, interzeolite conversion synthesis of high silica zeolite ZK-5
Funding: Engineering and Physical Sciences Research Council (Grant Number(s): EP/S016201/1, Grant recipient(s): Paul A. Wright, Magdalena M. Lozinska; EP/L017008/1, EP/T019298/1, EP/R023751/1). Engineering and Physical Sciences Research Council (Grant Number(s): EP/S016147/1; Grant recipient(s): James Mattock, Paul A. Cox). Royal Society (Grant Number(s): INF\R2\192052; Grant recipient(s): Paul A. Wright).High silica zeolite ZK-5 (framework Si/Al=4.8) has been prepared by interzeolite conversion from ultrastable zeolite Y via a co-templating route using alkali metal cations and nitrate anions but without organic structure directing agents. The mechanism, which involves zeolite framework – alkali metal cation – nitrate anion ordering, has been established by a combination of chemical and thermal analyses, Raman spectroscopy, computational modelling, and X-ray powder diffraction. Ammonium exchange gives ZK-5 with occluded ammonium nitrate and subsequent heating gives microporous zeolite ZK-5.Publisher PDFPeer reviewe