Direct Pyrolysis of a Manganese‐Triazolate Metal–Organic Framework into Air‐Stable Manganese Nitride Nanoparticles

Abstract Although metal–organic frameworks (MOFs) are being widely used to derive functional nanomaterials through pyrolysis, the actual mechanisms involved remain unclear. In the limited studies to date, elemental metallic species are found to be the initial products, which limits the variety of MOF‐derived nanomaterials. Here, the pyrolysis of a manganese triazolate MOF is examined carefully in terms of phase transformation, reaction pathways, and morphology evolution in different conditions. Surprisingly, the formation of metal is not detected when manganese triazolate is pyrolyzed in an oxygen‐free environment. Instead, a direct transformation into nanoparticles of manganese nitride, Mn2Nx embedded in N‐doped graphitic carbon took place. The electrically conductive Mn2Nx nanoparticles show much better air stability than bulk samples and exhibit promising electrocatalytic performance for the oxygen reduction reaction. The findings on pyrolysis mechanisms expand the potential of MOF as a precursor to derive more functional nanomaterials.