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Peroxidase-like reaction process involving o-phenylenediamine (OPD) and silver nanoprisms in the presence of hydrogen peroxide (H2O2) was monitored using time-resolved ultraviolet-visible (UV-Vis) absorption spectroscopy. The oxidation of OPD and etching of silver nanoprisms were investigated by analyzing the dynamic spectral data. Two-dimensional correlation spectroscopy (2D-COS) and principal component analysis (PCA) were employed to gain insights into the correlation between catalytic oxidation of OPD and etching of silver nanoprisms. It was foun