Oriented generation of 1O2 from peroxymonosulfate via Co3O4 facet engineering
Huan Wang, Dashuai Wang, Chen Sun, Xuesong Zhao, Cong Xu, Zhongjian Li, Yang Hou, Lecheng Lei, Bin Yang, Xiaoguang Duan
Abstract
In this study, we synthesized Co 3 O 4 nanoparticles with distinct morphologies, including nanocube, nanotruncated octahedron, and nanopolyhedron with featured exposure of (001), (111), and (112) facets, respectively. The Co 3 O 4 -NC/CNTs-PMS (peroxymonosulfate) system demonstrated a significantly higher steady-state 1 O 2 concentration of 8.84×10⁻¹⁰ M with 99.5 % selectivity, marking a 462-fold increase compared to Co 3 O 4 -NP/CNTs-PMS. Density Functional Theory (DFT) calculations revealed that the (001) facet facilitates 1 O 2 production by lowering the energy barrier for the rate-determining step from *OH to *O. Furthermore, we introduced the sum of Hammett sigma-para constants (∑σ p ) as a predictive descriptor, capable of estimating degradation rates with 87 % accuracy. This study systematically elucidates the influence of Co 3 O 4 crystal facets on 1 O 2 generation, providing valuable insights into the design of catalysts and optimization of PMS activation strategies for the efficient degradation of recalcitrant pollutants in complex water matrices. • Co 3 O 4 with different morphologies were successfully loaded on carbon nanotubes. • Nanocube structured Co 3 O 4 exhibited best catalytic performance for PMS activation. • 1 O 2 production selectivity was tuned by Co 3 O 4 facet engineering. • DFT calculations revealed (001) facet of Co 3 O 4 showed lowest energy barrier.