One-step electric-field driven methane and formaldehyde synthesis from liquid methanol

Cassone, Giuseppe; Pietrucci, Fabio; Saija, Franz; Guyot, F.; Saitta, A. Marco

doi:10.1039/c6sc04269d

Cited by 58 publications

(48 citation statements)

References 55 publications

(55 reference statements)

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“…Their introduction in the toolbox of synthetic chemists could potentially be a game changer, opening new (and more sustainable) routes toward chemical synthesis . At the same time, an increasing understanding of the role played by electrostatics in (bio)chemistry could offer new fundamental insights into a variety of phenomena associated to chemical reactivity …”

Section: Introductionmentioning

confidence: 99%

TITAN: A Code for Modeling and Generating Electric Fields—Features and Applications to Enzymatic Reactivity

et al. 2019

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We present here a versatile computational code named “elecTric fIeld generaTion And maNipulation (TITAN),” capable of generating various types of external electric fields, as well as quantifying the local (or intrinsic) electric fields present in proteins and other biological systems according to Coulomb's Law. The generated electric fields can be coupled with quantum mechanics (QM), molecular mechanics (MM), QM/MM, and molecular dynamics calculations in most available software packages. The capabilities of the TITAN code are illustrated throughout the text with the help of examples. We end by presenting an application, in which the effects of the local electric field on the hydrogen transfer reaction in cytochrome P450 OleTJE enzyme and the modifications induced by the application of an oriented external electric field are examined. We find that the protein matrix in P450 OleTJE acts as a moderate catalyst and that orienting an external electric field along the Fe─O bond of compound I has the biggest impact on the reaction barrier. The induced catalysis/inhibition correlates with the calculated spin density on the O‐atom. © 2019 Wiley Periodicals, Inc.

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Section: Introductionmentioning

confidence: 99%

TITAN: A Code for Modeling and Generating Electric Fields—Features and Applications to Enzymatic Reactivity

et al. 2019

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“…In addition, external field strengths of the order of 0.50 V/Å have been also employed in order to reproduce in silico the historical Miller experiment 19 . By exploiting similar computational approaches, we have recently shown 20 the feasibility of formaldehyde and methane synthesis through the application of electric fields to liquid methanol. Similarly, with an equivalent AIMD setup, methanol reactivity in proximity of electrified interfaces has been probed in order to characterise the first steps of the electro-oxidation of the simplest alcohol 21 .…”

Section: Introductionmentioning

confidence: 99%

“…Here we present a set of so far unreported chemical reactions which occur when a sample of pure liquid methanol is exposed to the effect of static and homogeneous electric fields, besides the mentioned observation of the one-step formation of formaldehyde and methane 20 . Anticipating our results, we observe that other relevant chemical species, such as DME and formaldehyde monohydrate, are formed at high field intensities.…”

Section: Introductionmentioning

confidence: 99%

Novel electrochemical route to cleaner fuel dimethyl ether

Cassone

Pietrucci

Saija

et al. 2017

Sci Rep

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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.

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“…Up to now, some endeavors had been done to develop a new methodology in accordance with green chemistry principles . An emerging greener catalyst is coming into one's sight, which is the external electric field (EEF), as a smart reagent to catalyze reactions had been reported by theory and experiment . Especially, the experiment of EEF by Aragonés et al paved the way for the development of EEF in catalyzing chemistry reactions.…”

Section: Introductionmentioning

confidence: 99%

A greener catalyst for hydroboration of imines—external electric field modify the reaction mechanism

Zhang

2019

J Comput Chem

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Usually, an extra catalyst (for example, the transition metal complexes) need to be used in catalyzing hydroboration, which involved the cost, environment, and so forth. Here, a greener and controllable catalyst—external electric field (EEF) was used to study its effect on hydroboration of N‐(4‐methylbenzyl)aniline (PhN═CHPhMe) with pinacolboane (HBPin). The results demonstrated that EEF could affect the barrier heights of both two pathways of this reaction. More significantly, flipping the direction of EEF could modify the reaction mechanism to induce a dominant inverse hydroboration at some field strength. That is to say, oriented EEF is a controlling switch for the anti‐ or Markovnikov hydroboration reaction of imines. This investigation is meaningful for the exploration of greener catalyst for chemistry reaction and guide a new method for the Markovnikov hydroboration addition. © 2019 Wiley Periodicals, Inc.

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One-step electric-field driven methane and formaldehyde synthesis from liquid methanol

Abstract: By means of state-of-the-art computational approaches, a new fundamental chemical reaction, involving formaldehyde and methane, has been observed when an electric field is applied to liquid methanol.

Cited by 58 publications

References 55 publications

TITAN: A Code for Modeling and Generating Electric Fields—Features and Applications to Enzymatic Reactivity

TITAN: A Code for Modeling and Generating Electric Fields—Features and Applications to Enzymatic Reactivity

Novel electrochemical route to cleaner fuel dimethyl ether

A greener catalyst for hydroboration of imines—external electric field modify the reaction mechanism

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