Hierarchically Porous Three-Dimensional (3D) Carbon Nanorod Networks with a High Content of FeNx Sites for Efficient Oxygen Reduction Reaction.

Efficient, durable, and inexpensive electrocatalysts are recommendable for accelerating the kinetics of oxygen reduction reaction and achieving high performance. Herein, with predesigned hierarchically porous silica nanorods as a hard template, hierarchically macro-bimodal meso/microporous 3D carbon interwoven nanorod networks containing a high content of single-atom FeNx species (Fe/RNC) were prepared by melting of precursors and confined pyrolysis within the pores of the hard template. What distinguishes the use of silica nanorods as a hard template is that it not only provides a porous texture for confined pyrolysis of the precursors but also the interwoven texture of the nanorods gives rise to a macroporous mesh-like morphology. Benefiting from the ultrahigh iron content (5.69 wt %) of the FeNx sites, a 3D porous network configuration with high accessibility of active centers, as well as a high specific surface area of 793 m2g-1, the as-prepared Fe/RNC exhibited superior activity and durability for ORR and zinc-air batteries. For comparison, the catalyst Fe/NC-MCM, which was prepared with a similar procedure but with unimodal mesoporous silica MCM-41 nanoparticles as the hard template, possesses a less porous structure and active accessibility and thus exhibits inferior ORR activity. This work provides an effective design/nanoengineering for electrocatalysts in ORR and zinc-air batteries and will inspire more research on accessibility of active sites in non-noble carbon-based electrocatalysts.

In-situ growth of cobalt manganate spinel nanodots on carbon black toward high-performance zinc-air battery: Dual functions of 3-aminopropyltriethoxysilane.

Developing cost-effective and stable non-noble electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is now the critical issue for large-scale application of zinc-air batteries. Here, we presented a simple method to synthesize highly dispersed cobalt manganate spinel nanodots in-situ embedded in amine-functionalized carbon black. Silane coupling agent 3-aminopropyltriethoxysilane (APTES) played dual roles in the preparation: (1) to achieve amine-functionalization of carbon support; (2) as weak alkali to precipitate metal hydroxides which were then converted to spinel nanodots after mild calcination. The hydrophilicity of the carbon substrate was enhanced by amine modification from APTES to disperse metal oxide evenly, and the electrochemical activity was promoted through the strong interface interaction between embedded spinel nanodots and carbon substrate during the calcination process. As expected, the CoMn2O4/C-NH2-300 catalyst exhibited satisfactory bifunctional catalytic performance for both ORR and OER with an ΔE (E1/2-Ej10) = 0.75 V, which was lower than most state-of-the-art catalysts. In addition, CoMn2O4/C-NH2-300 as a cathode also exhibited remarkable zinc-air battery performance in alkaline solution. This strategy of APTES as a bifunctional coupling agent provided a novel way to design and explore highly active, durable, and cost-effective catalysts for renewable energy conversion and storage.