Novel electrochemical route to cleaner fuel dimethyl ether

Abstract

Methanol, the simplest alcohol, and dimethyl ether, the simplest ether, are central compounds in the search for alternative “green” combustion fuels. In fact, they are generally considered as the cornerstones of the envisaged “Methanol Economy” scenario, as they are able to efficiently produce energy in an environmentally friendly manner. However, despite a massive amount of research in this field, the synthesis of dimethyl ether from liquid methanol has never so far been reported. Here we present a computational study, based on ab initio Molecular Dynamics, which suggests a novel synthesis route to methanol dehydration – leading thus to the dimethyl ether synthesis – through the application of strong electric fields. Besides proving the impressive catalytic effects afforded by the field, our calculations indicate that the obtained dimethyl ether is stable and that it can be progressively accumulated thanks to the peculiar chemical pathways characterising the methanol reaction network under electric field. These results suggest that the experimental synthesis of dimethyl ether from liquid methanol could be achieved, possibly in the proximity of field emitter tips.

Ab Initio Molecular Dynamics Study of Methanol-Water Mixtures under External Electric Fields

“…They observed both enhanced structuring of water as the methanol mole fraction increases and revealed the existence of separate H-bonded water and methanol networks, in agreement with neutron diffraction experiments [4,6]. The application of static electric fields is able to modify the H-bond structure of neat methanol [27,28] and of pure water [29][30][31][32] leading to crucial implications in electrochemistry [33][34][35][36][37] and in biology [38]. Also for this reason, in a recent article, He et al have investigated the structure of methanol-water mixtures showing that, at high methanol concentrations, the application of the field affects the structural evolution of the H-bond network, in that the field creates a "hollow channel" in the intermolecular interactions [39].…”

“…In fact, electric fields are able to strongly influence redox-and electron-transfer reactions [69,70], to affect covalent and intermolecular bonds [71][72][73][74], to produce the well-known Stark effect [75] as well as the so-called vibrational Stark effect [76,77]. Besides, the field-enhanced chemical reactivity of neat methanol has been described only a few years ago [36,37]. However, the effects produced by intense electric fields on methanol-water mixtures, have not been reported so far.…”

HNCO-based synthesis of formamide in planetary atmospheres

“…This value is again in fairly good agreement with the available data stemming from static quantum chemistry calculations, i.e., 63.1 kcal mol −1 (Nguyen et al 2011). Besides these thermodynamic considerations, the employed technique (Pietrucci & Saitta 2015;Cassone et al 2017b) fully characterizes the reaction pathway. This way, the mechanistic picture of the hydrogenation process of isocyanic acid -leading thus to the formamide synthesis -has been identified, as shown in Fig.…”

Synthesis of RNA Nucleotides in Plausible Prebiotic Conditions from ab Initio Computer Simulations

“…In addition, we used the topological metric of Ref., 41 accurately tracking changes in the chemical bond network passing from reactants, through intermediates, until the products, particularly suited to chemical reactions in solution. [42][43][44] This metric comparing structure R(t) with reference…”

“…To overcome the latter obstacle, we exploited a new general approach able to simulate complex reaction mechanisms in solution, combining enhanced sampling techniques (such as metadynamics and umbrella sampling [37][38][39][40] ) with topological coordinates capable of tracking changes in the chemical bond network. 41 This recent approach proved effective in the simulation of chemical reactions fully accounting for the role of temperature and solvent, including the decomposition 42 and dimerization 43 of amino acids and the synthesis of erythrose, 44 among others. In the present work, we significantly step-up the complexity of the system by tackling the challenging ab initio simulation of nucleotide synthetic pathways.…”