Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

For most metal-containing CO(2) reduction reaction (CO(2)RR) electrocatalysts, the unavoidable self-reduction to zero-valence metal will promote hydrogen evolution, hence lowering the CO(2)RR selectivity. Thus it is challenging to design a stable phase with resistance to electrochemical self-reduction as well as high CO(2)RR activity. Herein, we report a scenario to develop hydrocerussite as a stable and active electrocatalyst via in situ conversion of a complex precursor, tannin-lead(II) (TA-Pb) complex. A comprehensive characterization reveals the in situ transformation of TA-Pb to cerussite (PbCO(3)), and sequentially to hydrocerussite (Pb(3)(CO(3))(2)(OH)(2)), which finally serves as a stable and active phase under CO(2)RR condition. Both experiments and theoretical calculations confirm the high activity and selectivity over hydrocerussite. This work not only offers a new approach of enhancing the selectivity in CO(2)RR by suppressing the self-reduction of electrode materials, but also provides a strategy for studying the reaction mechanism and active phases of electrocatalysts.