Stabilizing High Density Cu Active Sites with ZrO2 Quantum Dots as Chemical Ligand in N-doped Porous Carbon Nanofibers for Efficient ORR

Abstract

The emerging transition metal-nitrogen-carbon (MNC) materials are considered as a promising oxygen reduction reaction (ORR) catalyst system to substitute expensive Pt/C catalysts due to their high surface area and potential high catalytic activity. However, MNC catalysts are easy to be attacked by the ORR byproducts that easily lead to the deactivation of metal active sites. Moreover, a high metal loading affects the mass transfer and stability, but a low loading delivers inferior catalytic activity. Here, a new strategy of designing ZrO₂ quantum dots and N-complex as dual chemical ligands in N-doped bubble-like porous carbon nanofibers (N-BPCNFs) to stabilize copper (Cu) by forming CuZrO_3-x /ZrO₂ heterostructures and CuN ligands with a high loading of 40.5 wt.% is reported. While the highly porous architecture design of N-BPCNFs builds a large solidelectrolytegas phase interface and promotes mass transfer. The preliminary results show that the half-wave potential of the catalyst reaches 0.856 V, and only decreases 0.026 V after 10 000 cycles, exhibiting excellent stability. The proposed strategy of stabilizing metal active sites with both heterostructures and CuN ligands is feasible and scalable for developing high metal loading ORR catalyst.

Keywords: ZrO 2 quantum dots; active Cu ZrO 3-x structures; bubble-like porous carbon nanofibers; heterostructures; oxygen reduction reaction.