Catalyst-Free Hydrogen Synthesis from Liquid Ethanol: An ab Initio Molecular Dynamics Study

Abstract

Hydrogen is the simplest, oldest, and most widespread molecule in Nature. Nevertheless, the vast majority of the hydrogen industrial production stems from steam reforming of methane performed at high temperatures or pressures. Albeit other chemical routes to the hydrogen synthesis-involving, e.g., water electrolysis and novel photocatalysts-have recently been explored, no catalyst-free reaction pathways have been identified, seriously limiting the large-scale deployment of hydrogen. Based on state-of-the-art ab initio molecular dynamics simulations, here we present a study revealing a novel synthesis route to hydrogen from neat liquid ethanol, which has been achieved at room temperature and in absence of any catalyst, upon electric field exposure. This result paves the way to the unprecedented catalyst-free experimental synthesis of hydrogen from liquid ethanol by exploiting commonly employed field emitter tips apparatus. 2

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

“…When a static and homogeneous electric field is switched on, polarization effects are induced [ 46 ]. Similarly to other H-bonded systems [ 59 ], when field strengths larger than V/Å are applied on samples of liquid methanol or liquid water, a detectable fraction of molecules aligns toward the field direction [ 31 , 60 ]. The application of an external electrostatic potential gradient forces, indeed, dipole vectors to align along the field direction.…”

“…Fast neutralization of the latter counterions culminates in the formation of formaldehyde and molecular hydrogen, with the consequent release of a methanol molecule, as shown in Figure 5 d. The same mechanism has also been detected to occur in the 75:25 methanol-water mixture. Incidentally, synthesis of molecular hydrogen has recently been reported also for liquid neat ethanol exposed to static electric fields [ 59 ].…”

“…The same mechanism has also been detected to occur in the 75:25 methanol-water mixture. Incidentally, synthesis of molecular hydrogen has recently been reported also for liquid neat ethanol exposed to static electric fields [59]. Notwithstanding the relevance of the reaction pathways connecting CH 3 OH to H 2 CO via the formation of CH 4 , on the one hand, and of H 2 , on the other, another reaction route governs the electrochemical response of liquid methanol to strong electric fields.…”

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

“…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 …”

“…[1][2][3][4][5] Their introduction in the toolbox of synthetic chemists could potentially be a game changer, opening new (and more sustainable) routes toward chemical synthesis . [6][7][8][9][10][11] 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. [12][13][14][15][16][17] The hypothesis that the local electric fields (LEFs), induced by the charged functional groups scattered throughout any (asymmetric) protein matrix, have a profound impact on the catalytic function of enzymes, was originally put forward by Warshel in the 1970s.…”