K. Hemelsoet

The conversion of methanol to olefins (MTO) over a heterogeneous nanoporous catalyst material is a highly complex process involving a cascade of elementary reactions. The elucidation of the reaction mechanisms leading to either the desired production of ethene and/or propene or undesired deactivation has challenged researchers for many decades. Clearly, catalyst choice, in particular topology and acidity, as well as the specific process conditions determine the overall MTO activity and selectivity; however, the subtle balances between these factors remain not fully understood. In this review, an overview of proposed reaction mechanisms for the MTO process is given, focusing on the archetypal MTO catalysts, H-ZSM-5 and H-SAPO-34. The presence of organic species, that is, the so-called hydrocarbon pool, in the inorganic framework forms the starting point for the majority of the mechanistic routes. The combination of theory and experiment enables a detailed description of reaction mechanisms and corresponding reaction intermediates. The identification of such intermediates occurs by different spectroscopic techniques, for which theory and experiment also complement each other. Depending on the catalyst topology, reaction mechanisms proposed thus far involve aromatic or aliphatic intermediates. Ab initio simulations taking into account the zeolitic environment can nowadays be used to obtain reliable reaction barriers and chemical kinetics of individual reactions. As a result, computational chemistry and by extension computational spectroscopy have matured to the level at which reliable theoretical data can be obtained, supplying information that is very hard to acquire experimentally. Special emphasis is given to theoretical developments that open new perspectives and possibilities that aid to unravel a process as complex as methanol conversion over an acidic porous material.

Nanofibres functionalised with pH-sensitive dyes could greatly contribute to the development of stimuli-responsive materials. However, the application of biocompatible polymers is vital to allow for their use in (bio)medical applications. Therefore, this paper focuses on the development and characterisation of pH-sensitive polycaprolactone (PCL) nanofibrous structures and PCL/chitosan nanofibrous blends with 20% chitosan. Electrospinning with added Nitrazine Yellow molecules proved to be an excellent method resulting in pH-responsive non-wovens. Unlike the slow and broad response of PCL nanofibres (time lag of more than 3 h), the use of blends with chitosan led to an increased sensitivity and significantly reduced response time (time lag of 5 min). These important effects are attributed to the increased hydrophilic nature of the nanofibres containing chitosan. Computational calculations indicated stronger interactions, mainly based on electrostatic interactions, of the dye with chitosan (ΔG of -132.3 kJ/mol) compared to the long-range interactions with PCL (ΔG of -35.6 kJ/mol), thus underpinning our experimental observations. In conclusion, because of the unique characteristics of chitosan, the use of PCL/chitosan blends in pH-sensitive biocompatible nanofibrous sensors is crucial.

It is of great interest to introduce pH-sensitive dyes into fibrous materials since this may result in flexible sensor systems. However, to date, the effect of a textile matrix on the halochromic properties of dyes is still unknown which severely limits their further development. Therefore, this paper focuses on an in-depth study of the halochromism of the azo pH-indicator dye Nitrazine Yellow in solution and incorporated in polyamide textile matrices with different structures. Based on both experimental spectroscopic data and computational calculations, an azo hydrazone tautomerism was found to be responsible for the halochromism of Nitrazine Yellow in solution. The hydrazone tautomer was most stable in neutral pH while the deprotonated dye molecule was believed to be an azo tautomer, resulting in a bathochromic shift with increasing pH. This tautomerism was, moreover, also present in the polyamide matrices. However, the equilibrium was clearly affected by the polymeric environment resulting in a shift and broadening of the dynamic pH-range. The polyamide type and textile structure influenced the halochromic response due to different interactions and accessibility of the dye. In conclusion, the halochromism of Nitrazine Yellow is present in all studied systems and is always based on an azo hydrazone tautomerism but the polyamide matrix causes distinct alterations in the tautomeric equilibrium.