Oxygen-vacancy-linked Co and Zr triadic sites steering C-P cleavage in aminophosphonates

Selective bond activation in heterogeneous oxidation catalysis remains challenging when multiple competitive pathways coexist. In aminophosphonates, oxidative transformation is typically dominated by kinetically favored C-N cleavage, generating refractory intermediates such as aminomethylphosphonic acid (AMPA). Herein, we demonstrated that selective C-P bond activation could be achieved via active-site coordination engineering. A cobalt single-atom catalyst featuring oxygen-vacancy-linked Zr sites (Co-Ov-Zr ensemble) created a dual-anchoring microenvironment that enforces bidentate adsorption of aminotris(methylenephosphonate), elongating the C-P bond and lowering its cleavage barrier. The vacancy-modified electronic structure promoted efficient peroxymonosulfate activation and Co(IV)=O generation. Consequently, the reaction coordinate was reprogrammed, reversing intrinsic selectivity from C-N to C-P cleavage. The optimized Co-Ov-ZrO 2 /PMS system achieved a five-fold enhancement in phosphate release kinetics compared to the vacancy-free analogue while suppressing AMPA formation. This work establishes adsorption-configuration control as a strategy for designing selective single-atom oxidation catalysts.