Biomorphic CoNC/CoOx Composite Derived from Natural Chloroplasts as Efficient Electrocatalyst for Oxygen Reduction Reaction.

Natural chloroplasts containing big amounts of chlorophylls (magnesium porphyrin, Mg-Chl) are employed both as template and porphyrin source to synthesize biomorphic CoNC/CoOx composite as electrocatalyst for the oxygen reduction reaction (ORR). Cobalt-substituted chlorophyll derivative (Co-Chl) in chloroplasts is first obtained by successively rinsing in hydrochloric acid and cobalt acetate solutions. After calcining in nitrogen to 800 °C, Co-Chl is transferred to CoNC; while other parts of chloroplasts adsorbed with Co ions are transferred to CoOx retaining the microarchitecture of chloroplasts. The abundant active CoNC sites are protected by circumjacent biocarbon and CoOx to avoid leakage and agglomeration, and at the same time can overcome the poor conductivity weakness of CoOx by directly transporting electrons to the carbonaceous skeleton. This unique synergistic effect, together with efficient bioarchitecture, leads to good electrocatalytical performance for the ORR. The onset and half-wave potentials are 0.89 and 0.82 V versus reversible hydrogen electrode, respectively, with better durability and methanol tolerance than that of commercial Pt/C. Different from the traditional concept of biomorphic materials which simply utilize bioarchitectures, this work provides a new example of coupling bioderivative components with bioarchitectures into one integrated system to achieve good comprehensive performance for electrocatalysts.