Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe3O4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

Tubular Monolayer Superlattices of Hollow Mn3O4 Nanocrystals and Their Oxygen Reduction Activity.

Self-assembled nanocrystal (NC) superlattices are emerging as an important class of materials with rationally modulated properties. Engineering the nanoscale structure of constituent building blocks as well as the mesoscale morphology of NC superlattices is a crucial step in widening their range of applications. Here, we report a template-assisted epitaxial assembly strategy, enabling growth of freestanding, carbon-coated tubular monolayer superlattices (TMSLs). Specifically, we design and construct TMSLs of hollow Mn3O4 NCs (h-Mn3O4-TMSLs) by exploiting structural evolution of MnO NCs. The tubular superlattices obtained possess a number of unique and advantageous structural features unavailable in conventional NC superlattices, rendering them particularly attractive for energy conversion applications. We demonstrate this by employing h-Mn3O4-TMSLs as electrocatalysts for oxygen reduction, the catalytic performance of which is comparable to that of state-of-the-art Pt/C catalysts and superior to that of most manganese oxide-based catalysts reported.

Fine-Tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals.

Because of their unique physical properties, three-dimensional (3D) graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG). By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with their 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites arising from the thin wall thickness and high surface area.