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/CoO_x 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 CoO_x retaining the microarchitecture of chloroplasts. The abundant active CoNC sites are protected by circumjacent biocarbon and CoO_x to avoid leakage and agglomeration, and at the same time can overcome the poor conductivity weakness of CoO_x 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.