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Updated: Jun 10, 2026

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions
Published on: June 16, 2014
Breaking the activity-selectivity trade-off in Fenton-like catalysis by d-orbital modulation of single-atom sites
Yuxin Chen1, Xing Xu1, Jianrong Zeng2,3
1Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao, P. R. China.
Abstract:
Direct electron transfer (ETP) during peroxymonosulfate (PMS) activation enables selective, matrix-resistant organic contaminants oxidation, yet its precise control over competing radical pathways remains elusive. Here we report a nano-island-like single-atom catalyst- carbon nitride islands immobilize cobalt single atoms on reduced graphene oxide (CoN3C/rGO)- that leverages an island-sea architecture to direct PMS activation toward ETP. Experimental and density functional theory (DFT) analyses show an rGO induced elevation of the Co d-band center and a sharpened dz2 orbital near the Fermi level, promoting directional hybridization with PMS p orbitals and suppressing antibonding occupation. Consequently, CoN3C/rGO/PMS degrade bisphenol A (BPA) completely within 5 min, with ~94% contribution from ETP. Furthermore, catalytic membrane coatings enable stable 100 h continuous operation in diverse real water matrices with minimal Co leaching. Our results demonstrate a design principle-orbital-level modulation via island-sea architectures to reconcile activity and selectivity in Fenton-like systems and advance translating practical water treatment technologies based on single-atom electronic control.
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To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...