Towards molecular control of elementary reactions in zeolite catalysis by advanced molecular simulations mimicking operating conditions

Zeolites are the workhorses of today's chemical industry. For decades they have been successfully applied, however many features of zeolite catalysis are only superficially understood and in particular the kinetics and mechanism of individual reaction steps at operating conditions. Herein we use state-of-the-art advanced ab initio molecular dynamics techniques to study the influence of catalyst topology and acidity, reaction temperature and the presence of additional guest molecules on elementary reactions. Such advanced modeling techniques provide complementary insight to experimental knowledge as the impact of individual factors on the reaction mechanism and kinetics of zeolite-catalyzed reactions may be unraveled. We study key reaction steps in the conversion of methanol to hydrocarbons, namely benzene and propene methylation. These reactions may occur either in a concerted or stepwise fashion, i.e. methanol directly transfers its methyl group to a hydrocarbon or the reaction goes through a framework-bound methoxide intermediate. The DFT-based dynamical approach enables mimicking reaction conditions as close as possible and studying the competition between two methylation mechanisms in an integrated fashion. The reactions are studied in the unidirectional AFI-structured H-SSZ-24, H-SAPO-5 and TON-structured H-ZSM-22 materials. We show that varying the temperature, topology, acidity and number of protic molecules surrounding the active site may tune the reaction mechanism at the molecular level. Obtaining molecular control is crucial in optimizing current zeolite processes and designing emerging new technologies bearing alternative feedstocks

Effect of pH on ciprofloxacin ozonation in hospital WWTP effluent

A bubble column was used for ozonation of the quinolone antibiotic ciprofloxacin and the effect of pH was tested. Degradation at pH 7 increased the ciprofloxacin half life time to 29.1 min compared to pH 3 (26.8 min) and pH 10 (18.7 min), possibly due to increased sorption at neutral pH. Degradation product identification revealed strongest degradation at the piperazinyl substituent at pH 10 while degradation at the quinolone moiety seems promising at pH 7. For P. fluorescens and E. coli, reduction in antibacterial activity, monitored by agar diffusion tests, was in correlation with the ciprofloxacin degradation rate. For B. coagulans, however, no differences in residual antibacterial activity were found in function of pH, indicating that degradation products also affect antibacterial activity of ozonated samples

Toward Computing Accurate Free Energies in Heterogeneous Catalysis: a Case Study for Adsorbed Isobutene in H-ZSM-5

Herein, we propose a novel computational protocol that enables calculating free energies with improved accuracy by combining the best available techniques for enthalpy and entropy calculation. While the entropy is described by enhanced sampling molecular dynamics techniques, the energy is calculated using ab initio methods. We apply the method to assess the stability of isobutene adsorption intermediates in the zeolite H-SSZ-13, a prototypical problem that is computationally extremely challenging in terms of calculating enthalpy and entropy. We find that at typical operating conditions for zeolite catalysis (400 °C), the physisorbed π-complex, and not the tertiary carbenium ion as often reported, is the most stable intermediate. This method paves the way for sampling-based techniques to calculate the accurate free energies in a broad range of chemistry-related disciplines, thus presenting a big step forward toward predictive modeling

Effect of temperature and branching on the nature and stability of alkene cracking intermediates in H-ZSM-5

Catalytic cracking of alkenes takes place at elevated temperatures in the order of 773–833 K. In this work, the nature of the reactive intermediates at typical reaction conditions is studied in H-ZSM-5 using a complementary set of modeling tools. Ab initio static and molecular dynamics simulations are performed on different C4single bond C5 alkene cracking intermediates to identify the reactive species in terms of temperature. At 323 K, the prevalent intermediates are linear alkoxides, alkene π-complexes and tertiary carbenium ions. At a typical cracking temperature of 773 K, however, both secondary and tertiary alkoxides are unlikely to exist in the zeolite channels. Instead, more stable carbenium ion intermediates are found. Branched tertiary carbenium ions are very stable, while linear carbenium ions are predicted to be metastable at high temperature. Our findings confirm that carbenium ions, rather than alkoxides, are reactive intermediates in catalytic alkene cracking at 773 K

Complete low-barrier side-chain route for olefin formation during methanol conversion in H-SAPO-34

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