A Ferrocene Metal–Organic Framework Solid for Fe-Loaded Carbon Matrices and Nanotubes: High-Yield Synthesis and Oxygen Reduction Electrocatalysis

Using a carbon-rich designer metal-organic framework (MOF), we open a high-yield synthetic strategy for iron-nitrogen-doped carbon (Fe-N-C) nanotube materials that emulate the electrocatalysis performance of commercial Pt/C. The Zr(IV)-based MOF solid boasts multiple key functions: (1) a dense array of alkyne units over the backbone and the side arms, which are primed for extensive graphitization; (2) the open, branched structure helps maintain porosity for absorbing nitrogen dopants; and (3) ferrocene units on the side arms as atomically dispersed precursor catalyst for targeting micropores and for effective iron encapsulation in the carbonized product. As a result, upon pyrolysis, over 89% of the carbon component in the MOF scaffold is successfully converted into carbonized products, thereby contrasting the easily volatilized carbon of most MOFs. Moreover, over 97% of the iron ends up being encased as acid-resistant Fe/Fe3C nanoparticles in carbon nanotubes/carbon matrices.