ZIF-derived in situ nitrogen-doped porous carbons as efficient metal-free electrocatalysts for oxygen reduction reaction

We have successfully prepared nanoporous Carbon-L and -S materials by using ZIF-7 as a precursor and glucose as an additional carbon source. Results indicate that Carbon-L and -S show an appropriate nitrogen content, high surface area, robust pore structure and excellent graphitization degree. The addition of an environmentally friendly carbon source – glucose – not only improves the graphitization degree of samples, but also plays a key role in removing residual Zn metal and zinc compound impurities, which makes the resulting materials metal-free in situ nitrogen-doped porous carbons. By further investigating the electrocatalytic performance of these nitrogen-doped porous carbons for oxygen reduction reaction (ORR), we find that Carbon-L, as a metal-free electrocatalyst, shows excellent electrocatalytic activity (the onset and half-wave potentials are 0.86 and 0.70 V vs. RHE, respectively) and nearly four electron selectivity (the electron transfer number is 3.68 at 0.3 V), which is close to commercial 20% Pt/C. Moreover, when methanol was added, the Pt/C catalyst would be poisoned while the Carbon-L and -S would be unaffected. By exploring the current-time chronoamperometric response in 25 000 s, we found that the duration stability of Carbon-L is much better than the commercial 20% Pt/C. Thus, both Carbon-L and -S exhibit excellent ability to avoid methanol crossover effects, and long-term operation stability superior to the Pt/C catalyst. This work provides a new strategy for in situ synthesis of N-doped porous carbons as metal-free electrocatalysts for ORR in fuel cells.