Nafion-Mediated Proton Transfer Facilitates the Electroreduction of SO 2 to H 2 S.

The electrocatalytic reduction of SO 2 to produce H 2 S is a critical approach for achieving the efficient utilization of sulfur resources. At the core of this approach for commercial applications lies the imperative need to elevate current density. However, the challenges posed by high current density manifest in the rapid depletion of protons, leading to a decrease in SO 2 partial pressure, consequently hampering the generation and separation of H 2 S. Here, we demonstrate an effective solution to alleviate the problem of insufficient supply of protons by employing Nafion polymer as the proton conductor to modified Cu catalysts surface, creating a proton-enriched layer to boost H 2 S generation. It was observed that Nafion shortens the hydrogen bonds with water molecules in the electrolyte via its sulfonic acid groups, benefiting the proton transfer and consequently increasing the proton density on the electrode surface by 5-fold. With the Nafion-modified catalyst, the H 2 S partial current density and separation efficiency reached 205.9 mA·cm -2 (1.01 mmol·cm -2 ·h -1 ) and 87.8%, which were 1.34 and 1.22 times that on unmodified Cu, respectively. This work highlights the practicality of fabricating a proton conductor via ionic polymer for the control over product selectivity in pH-sensitive reactions under high current density.