Phosphorous-Nitrogen-Codoped Carbon Materials Derived from Metal-Organic Frameworks as Efficient Electrocatalysts for Oxygen Reduction Reactions

Despite the impressive progress in the development of doped carbon catalysts for the oxygen reduction reaction (ORR), the current mono-heteroatom-doped carbon-based catalysts are still far from satisfactory for large-scale applications in fuel cells. The development of dual-heteroatom-doped nanoporous carbon electrocatalysts for the ORR is particularly attractive as a feasible solution for the commercialization of fuel-cell technology. Herein, a series of UiO-66-NH2-derived phosphorus-nitrogen-codoped porous carbon materials (P-N-carbons) are prepared from phosphorus-doped UiO-66-NH2 through postsynthetic modification (PSM) followed by one-step pyrolysis at various temperatures. The newly developed P-N-carbons exhibit high catalytic activity that is nearly equal to those of commercial Pt/C catalysts along with superior long-term stability and excellent methanol tolerance. This work shows not only that UiO-66-NH2 can be considered as a self-sacrificial precursor and nitrogen source but also that metal-organic frameworks (MOFs) with active functional groups may be developed as efficient alternative precursors. Owing to the versatility of MOF structures, the MOF-derived porous carbon materials would broaden the family of nanoporous carbon materials significantly and provide new structures and multifunctional properties for use in electrocatalysts, sensors, supercapacitors, and batteries, for example.