Cobalt Single Atoms on Tetrapyridomacrocyclic Support for Efficient Peroxymonosulfate Activation

Transition-metal catalysts that can efficiently activate peroxide bonds have been extensively pursued for various applications including environmental remediation, chemical synthesis, and sensing. Here, we present pyridine-coordinated Co single atoms embedded in a polyaromatic macrostructure as a highly efficient peroxide-activation catalyst. The efficient catalytic production of reactive radicals through peroxymonosulfate activation was demonstrated by the rapid removal of model aqueous pollutants of environmental and public health concerns such as bisphenol A, without pH limitation and Co²⁺ leaching. The turnover frequency of the newly synthesized Co single-atom catalyst bound to tetrapyridomacrocyclic ligands was found to be 2 to 4 orders of magnitude greater than that of benchmark homogeneous (Co²⁺) and nanoparticulate (Co₃O₄) catalysts. Experimental results and density functional theory simulation suggest that the abundant π-conjugation in the polyaromatic support and strong metal-support electronic interaction allow the catalysts to effectively adsorb and activate the peroxide precursor. We further loaded the catalysts onto a widely used poly(vinylidene fluoride) microfiltration membrane and demonstrated that the model pollutants were oxidatively removed as they simply passed through the filter, suggesting the promise of utilizing this novel catalyst for realistic applications.