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

Intense electric fields applied on H-bonded systems are able to induce molecular dissociations, proton transfers, and complex chemical reactions. Nevertheless, the effects induced in heterogeneous molecular systems such as methanol-water mixtures are still elusive. Here we report on a series of state-of-the-art ab initio molecular dynamics simulations of liquid methanol-water mixtures at different molar ratios exposed to static electric fields. If, on the one hand, the presence of water increases the proton conductivity of methanol-water mixtures, on the other, it hinders the typical enhancement of the chemical reactivity induced by electric fields. In particular, a sudden increase of the protonic conductivity is recorded when the amount of water exceeds that of methanol in the mixtures, suggesting that important structural changes of the H-bond network occur. By contrast, the field-induced multifaceted chemistry leading to the synthesis of e.g., hydrogen, dimethyl ether, formaldehyde, and methane observed in neat methanol, in 75:25, and equimolar methanol-water mixtures, completely disappears in samples containing an excess of water and in pure water. The presence of water strongly inhibits the chemical reactivity of methanol.

No abstract