Multifunctional Roles of Clathrate Hydrate Nanoreactors for CO₂ Reduction

Abstract

In this study, we explore a possible platform for the CO2 reduction (CO2R) in one of water’s solid phases, namely clathrate hydrates (CHs), by ab initio molecular dynamics and well‐tempered metadynamics simulations with periodic boundary conditions. We find that the stacked H2O nanocages in CHs assist to initialize CO2R by increasing the electron‐binding ability of CO2. The substantial CO2R processes are further influenced by the hydrogen bond (H‐bond) networks in CHs. The first intermediate CO2− in this process can be stabilized through cage structure reorganization into the H‐bonded [CO2−···H‐OHcage] complex. Further cooperative structural dynamics enables the complex to convert into a vital transient [CO22−···H‐OHcage] intermediate via a low‐barrier disproportionation‐like process. Such a highly reactive intermediate spontaneously triggers sequent double proton transfer along its tethering H‐bonds, finally converting it into HCOOH. These hydrogen‐bonded nanoreactors feature multifunction in facilitating CO2R such as confining, tethering, H‐bond catalyzing and proton pump. Our findings have a general interest and extend the knowledge of CO2R into porous aqueous systems.

A two-electron reducing reaction of CO2 to an oxalate anion: a theoretical study of delocalized (presolvated) electrons in Al(CH3)n(NH3)m, n = 0–2 and m = 1–6, clusters

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