Modelling metal centres, acid sites and reaction mechanisms in microporous catalysts

We discuss the role of QM/MM (embedded cluster) computational techniques in catalytic science, in particular their application to microporous catalysis. We describe the methodologies employed and illustrate their utility by briefly summarising work on metal centres in zeolites. We then report a detailed investigation into the behaviour of methanol at acidic sites in zeolites H-ZSM-5 and H-Y in the context of the methanol-to-hydrocarbons/olefins process. Studying key initial steps of the reaction (the adsorption and subsequent methoxylation), we probe the effect of framework topology and Brønsted acid site location on the energetics of these initial processes. We find that although methoxylation is endothermic with respect to the adsorbed system (by 17-56 kJ mol(-1) depending on the location), there are intriguing correlations between the adsorption/reaction energies and the geometries of the adsorbed species, of particular significance being the coordination of methyl hydrogens. These observations emphasise the importance of adsorbate coordination with the framework in zeolite catalysed conversions, and how this may vary with framework topology and site location, particularly suited to investigation by QM/MM techniques

Hydrocarbon Dynamics in Microporous Catalysts

The dynamics of hydrocarbons inside microporous zeolite catalysts are studied using neutron scattering methods and complementary molecular simulations, to investigate quantitatively a crucial component of industrial zeolite catalysis. The diffusion of longer n-alkanes in the siliceous analogue of ZSM-5, silicalite is modelled using state-of-the-art molecular dynamics (MD) simulations. The measured diffusivities show far improved agreement with quasielastic neutron scattering (QENS) experiments. Isobutane diffusion in silicalite is also modelled, giving good agreement with diffusion coefficients and jump diffusion parameters obtained by neutron spin-echo experiments. The simulations give interesting insights into preferred siting locations, contradicting previous studies of isobutane dynamics in the MFI structure due to the use of a more accurate framework model. Tandem QENS and MD studies of octane isomer diffusion in zeolite HY show a counterintuitive increase in diffusion with branching, due to alkane clustering in the faujasite supercage. The difference in intermolecular forces (dictated by molecular shape) slow the diffusion of n-octane significantly more than 2,5-dimethyhexane in the faujasite structure. The behaviour contrasts with that in the MFI structure where branching is known to hinder alkane diffusion. Methanol diffusion in commercial HY and H-ZSM-5 samples was studied using QENS, showing free methanol diffusion in HY, but not in H-ZSM-5 due to room temperature methoxylation as confirmed by inelastic neutron scattering (INS) spectroscopy and quantum mechanical calculations of vibrational spectra. QM/MM embedded cluster calculations were also performed to compare the acidity and methanol adsorption energy of HY, and at three locations in the H-ZSM-5 structure. The diffusion component of the recently patented SAPO-37 catalysed Beckmann rearrangement is also studied using QENS to measure cyclohexanone oxime mobility in zeolites HY and SAPO-37, highlighting diffusion differences correlatable to catalytic activity despite sharing the same faujasite structure. This thesis illustrates the power of complementary neutron scattering and computational studies of sorbate dynamics in zeolites, future work aims to incorporate these studies into the design of new microporous catalytic processes

Methanol diffusion and dynamics in zeolite H-ZSM-5 probed by quasi-elastic neutron scattering and classical molecular dynamics simulations

Zeolite ZSM-5 is a key catalyst in commercially relevant processes including the widely studied methanol to hydrocarbon reaction, and molecular diffusion in zeolite pores is known to be a crucial factor in controlling catalytic reactions. Here, we present critical analyses of recent quasi-elastic neutron scattering (QENS) data and complementary molecular dynamics (MD) simulations. The QENS experiments show that the nature of methanol diffusion dynamics in ZSM-5 pores is dependent both on the Si/Al ratio (11, 25, 36, 40 and 140), which determines the Brønsted acid site density of the zeolite, and that the nature of the type of motion observed may vary qualitatively over a relatively small temperature range. At 373 K, on increasing the ratio from 11 to 140, the observed mobile methanol fraction increases and the nature of methanol dynamics changes from rotational (in ZSM-5 with Si/Al of 11) to translational diffusion. The latter is either confined localized diffusion within a pore in zeolites with ratios up to 40 or non-localized, longer-range diffusion in zeolite samples with the ratio of 140. The complementary MD simulations conducted over long time scales (1 ns), which are longer than those measured in the present study by QENS (≈1-440 ps), at 373 K predict the occurrence of long-range translational diffusion of methanol in ZSM-5, independent of the Si/Al ratios (15, 47, 95, 191 and siliceous MFI). The rate of diffusion increases slightly by increasing the ratio from 15 to 95 and thereafter does not depend on zeolite composition. Discrepancies in the observed mobile methanol fraction between the MD simulations (100% methanol mobility in ZSM-5 pores across all Si/Al ratios) and QENS experiments (for example, ≈80% immobile methanol in ZSM-5 with Si/Al of 11) are attributed to the differences in time resolutions of the techniques. This perspective provides comprehensive information on the effect of acid site density on methanol dynamics in ZSM-5 pores and highlights the complementarity of QENS and MD, and their advantages and limitations. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'

How common are vascular injuries in open tibial fractures? A prospective longitudinal cohort study.

BACKGROUND: Tibial fractures have an incidence of 15% of all adult fractures. They have been shown to have the highest incidence of non-union in long bone fractures and the highest incidence of vascular injury. Evidence from the literature suggests that a good vascular supply is important to ensure bone union. The aim of our study was to prospectively assess the incidence of vascular injuries in open tibial fractures and determine whether they were associated with an increased risk of non-union. METHODS: We performed a prospective study to investigate the incidence of arterial injuries with computed tomography angiography (CTA) in patients with Gustilo-Anderson grade I-III open tibial fractures between 2013 and 2015. CTA was performed with the trauma series at acute admission and reported by two independent musculoskeletal radiologists. Patients were followed up with clinical and radiographic assessment for 1 year. RESULTS: We recruited 77 patients into the study, and 56 patients (47 males, 9 females) were available for the final analysis, between 16 and 90 years of age. At the initial assessment, 29% had signs of arterial injury with active extravasation in 5%. The most common site of injury was in the diaphysis (87.5%), and the commonest mechanism was a road traffic accident. We found no significant relation between occult vascular injury and non-union (p > 0.05). CONCLUSION: The incidence of vascular injury in open tibial fractures is 29%, and CTA is therefore a useful test in identifying vascular injuries that may require vascular intervention

Quasielastic Neutron Scattering and Molecular Dynamics Simulation Study on the Molecular Behaviour of Catechol in Zeolite Beta

The dynamics of catechol in zeolite Beta was studied using quesielastic neutron scattering (QENS) experiments and molecular dynamics simulations at 393 K, to understand the behaviour of phenolic monomers relevant in the catalytic conversion of lignin via metal nanoparticles supported on zeolites. Compared to previous work studying phenol, both methods observe that the presence of the second OH group in catechol can hinder mobility significantly, as explained by stronger hydrogen-bonding interactions between catechol and the Brønsted sites of the zeolite. The instrumental timescale of the QENS experiment allows us to probe rotational motion, and the catechol motions are best fit to an isotropic rotation model with a Drot of 2.9 × 1010 s−1. While this Drot is within error of that measured for phenol, the fraction of molecules immobile on the instrumental timescale is found to be significantly higher for catechol. The MD simulations also exhibit this increased in ‘immobility’, showing that the long-range translational diffusion coefficients of catechol are lower than phenol by a factor of 7 in acidic zeolite Beta, and a factor of ∼3 in the siliceous material, further illustrating the significance of Brønsted site H-bonding. Upon reproducing QENS observables from our simulations to probe rotational motions, a combination of two isotropic rotations was found to fit the MD-calculated EISF; one corresponds to the free rotation of catechol in the pore system of the zeolite, while the second rotation is used to approximate a restricted and rapid “rattling”, consistent with molecules anchored to the acid sites through their OH groups, the motion of which is too rapid to be observed by experiment

Amyloid-β nanotubes are associated with prion protein-dependent synaptotoxicity

Growing evidence suggests water-soluble, non-fibrillar forms of amyloid-β protein (Aβ) have important roles in Alzheimer's disease with toxicities mimicked by synthetic Aβ1-42. However, no defined toxic structures acting via specific receptors have been identified and roles of proposed receptors, such as prion protein (PrP), remain controversial. Here we quantify binding to PrP of Aβ1-42 after different durations of aggregation. We show PrP-binding and PrP-dependent inhibition of long-term potentiation (LTP) correlate with the presence of protofibrils. Globular oligomers bind less avidly to PrP and do not inhibit LTP, whereas fibrils inhibit LTP in a PrP-independent manner. That only certain transient Aβ assemblies cause PrP-dependent toxicity explains conflicting reports regarding the involvement of PrP in Aβ-induced impairments. We show that these protofibrils contain a defined nanotubular structure with a previously unidentified triple helical conformation. Blocking the formation of Aβ nanotubes or their interaction with PrP might have a role in treatment of Alzheimer's disease

Comparing ammonia diffusion in NH3-SCR zeolite catalysts: a quasielastic neutron scattering and molecular dynamics simulation study

The diffusion of ammonia in the small pore zeolite and potential commercial NH3-SCR catalyst levynite (LEV) was measured and compared with its mobility in the chabazite (CHA) topology (more established in NOx abatement catalysis), using quasielastic neutron scattering (QENS) and molecular dynamics (MD) simulations at 273, 323 and 373 K. The QENS experiments suggest that mobility in LEV is dominated by jump diffusion through the 8-ring windows between cages (as previously observed in CHA) which takes place at very similar rates in the two zeolites, yielding similar experimental self-diffusion coefficients (Ds). After confirming that the same characteristic motions are observed between the MD simulations and the QENS experiments on the picosecond scale, the simulations suggest that on the nanoscale, the diffusivity is higher by a factor of ∼2 in the CHA framework than in LEV. This difference between zeolites is primarily explained by the CHA cages having six 8-ring windows in the building unit, compared to only three such windows in the LEV cage building unit, thereby doubling the geometric opportunities to perform jump diffusion between cages (as characterised by the QENS experiments) leading to the corresponding increase in the MD calculated Ds. The techniques illustrate the importance of probing both pico- and nanoscale dynamics when studying intracrystalline diffusion in both NH3-SCR catalyst design, and in porous materials generally, where notable consistencies and differences may be found on either scale

Influence of Topology and Brønsted Acid Site Presence on Methanol Diffusion in Zeolites Beta and MFI

Detailed insight into molecular diffusion in zeolite frameworks is crucial for the analysis of the factors governing their catalytic performance in methanol-to-hydrocarbons (MTH) reactions. In this work, we present a molecular dynamics study of the diffusion of methanol in all-silica and acidic zeolite MFI and Beta frameworks over the range of temperatures 373–473 K. Owing to the difference in pore dimensions, methanol diffusion is more hindered in H-MFI, with diffusion coefficients that do not exceed 10×10−10 m2s−1. In comparison, H-Beta shows diffusivities that are one to two orders of magnitude larger. Consequently, the activation energy of translational diffusion can reach 16 kJ·mol−1 in H-MFI, depending on the molecular loading, against a value for H-Beta that remains between 6 and 8 kJ·mol−1. The analysis of the radial distribution functions and the residence time at the Brønsted acid sites shows a greater probability for methylation of the framework in the MFI structure compared to zeolite Beta, with the latter displaying a higher prevalence for methanol clustering. These results contribute to the understanding of the differences in catalytic performance of zeolites with varying micropore dimensions in MTH reactions