Continuous On-Site H2O2 Electrosynthesis via Two-Electron Oxygen Reduction Enabled by an Oxygen-Doped Single-Cobalt Atom Catalyst with Nitrogen Coordination.

Single-Co atom catalysts are suggested as an efficient platinum metal group-free catalyst for promoting the oxygen reduction into water or hydrogen peroxide, while the relevance of the catalyst structure and selectivity is still ambiguous. Here, we propose a thermal evaporation method for modulating the chemical environment of single-Co atom catalysts and unveil the effect on the selectivity and activity. It discloses that nitrogen functional groups prefer to proceed the oxygen reduction via a 4e- pathway and notably improve the intrinsic activity, especially when being coordinated with the Co center, while oxygen doping tempts the electron delocalization around cobalt sites and decreases the binding force toward HOO* intermediates, thereby increasing the 2e- selectivity. Consequently, the well-designed oxygen-doped single-Co atom catalysts with nitrogen coordination deliver an impressive 2e- oxygen reduction performance, approaching the onset potential of 0.78 V vs RHE and selectivity of >90%. As an impressive cathode catalyst of an electrochemical flow cell, it generates H2O2 at a rate of 880 mmol gcat-1 h-1 and faradaic efficiency of 95.2%, in combination with an efficient nickel-iron oxygen evolution anode.