Electronic tuning of confined sub-nanometer cobalt oxide clusters boosting oxygen catalysis and rechargeable Zn-air batteries

Reasonable design of robust bifunctional oxygen catalysts from an electronic structure perspective is intriguing and challenging for the development of high active rechargeable zinc-air batteries (ZABs). In this study, the favorable regulation of the electronic structure of the cobalt oxide nanoclusters was firstly predicted by density functional theory (DFT) simulation, and then experimentally verified by confining sub-nanometer CoOx clusters (0.86 nm) into the small pore of ZIF-8 derived N-doped nanomaterials (PNC) using a microporous MOFs confinement strategy. The confined effect of the MOF micropores not only enhanced the stability of the subnanometer cobalt oxide clusters, but also make it coupled with Co-Nx to further regulate the electronic structure of the former, synergistic resulting in enhanced ORR/OER actives. As a result, the optimized 0.05CoOx@PNC catalyst demonstrates outstanding bifunctional oxygen performance with a smaller potential gap of 0.67 V. Moreover, the rechargeable Zn-air batteries integrated 0.05CoOx@PNC air cathode displays encouraging performance with a peak power density of 157.1 mW cm(-2), a specific capacity of 887 mAh g(Zn)(-1)at 10 mA cm(-2) and long-term cyclability for over 200 h, significantly outperforming the benchmark electrode couple consisted of Pt/C/RuO2. DFT calculation further revealed that reducing particle size and coupling with Co-N could effectively regulate the charge distribution of CoOx nanoclusters and downshift the D-band center of Co adsorption sites in CoOx nanoclusters, which reduced the reaction barrier of intermediate O-2* and OH* and ORR/ OER overpotential, thus accelerating the overall ORR/OER kinetic process. This work offers a novel reference for the construction of a robust sub-nanometer cluster catalysts in the field of ZABs.

Automated summary

This study predicted the electronic structure regulation of cobalt oxide nanoclusters using DFT simulation, and experimentally verified the enhancement of bifunctional oxygen performance through microporous MOFs confinement strategy. The optimized catalyst demonstrated outstanding performance in rechargeable Zn-air batteries, outperforming benchmark electrodes. DFT calculations showed that reducing particle size and coupling with Co-N can effectively regulate the charge distribution of CoOx nanoclusters and accelerate the overall ORR/OER kinetic process.