Bicarbonate-mediated proton transfer requires cations

Near-neutral HCO3– aqueous solution plays an essential role in respiratory, mineralization and catalysis, yet the interconversion between hydrated CO2, HCO3– and CO32– and the associated proton transfer under such proton-deficient conditions remain uncovered. Here we reveal that cation enables HCO3– to self-dissociate into OH– and CO2 through a pH-independent process, where CO2 hydration and subsequent proton transfer in acid-base reactions lead to the overall exchange of oxygen isotopes between HCO3– and H2O tracked by oxygen isotope-labeled Raman spectroscopy. Isolating HCO3– from cations with crown ether impedes HCO3– dissociation and the following reactions. Further molecular dynamics simulations demonstrate that the interplay between HCO3– and hydrated cations drives HCO3– dissociation. This study suggests a natural proton channel upon coupling HCO3– with cations. Unlike the traditional views that HCO3- anions transit to either CO2 or CO32- upon suffering pH changes. Here, the authors report that cation enables HCO3- to self-dissociate into OH- and CO2 through a pH independent process, leading to the formation of acid-base encounter pairs for proton transfer.