Transforming crystal structures of cobalt molybdate to generate electron-rich sites for electrochemical detection of...

Most of the investigations on distinct crystal structures of catalysts are individually focused on the difference of surface functional groups or adsorption properties, but rarely explore the changes of active sites to affect the electrocatalytic performance. Catalysts with diverse crystal structures had been applied to modified electrodes in different electrocatalytic reactions. However, there is currently a lack of an essential understanding for the role of real active sites in catalysts with crystalline structures in electroanalysis, which is crucial for designing highly sensitive sensing interfaces.

Herein, cobalt molybdate with divergent crystal structures (α-CoMoO₄ and β-CoMoO₄) were synthesized by adjusting the calcination temperature, indicating that α-CoMoO₄ (800 °C) (60.00 μA μM^-1) had the highest catalytic ability than β-CoMoO₄ (700 °C) (38.68 μA μM^-1) and α-CoMoO₄ (900 °C) (29.55 μA μM^-1) for the catalysis of Pb(II). It was proved that the proportion of Co(II) and Mo(IV) as electron-rich sites in α-CoMoO₄ (800 °C) were higher than β-CoMoO₄ (700 °C) and α-CoMoO₄ (900 °C), possessing more electrons to participate in the valence cycles of Co(II)/Co(III) and Mo(IV)/Mo(VI) to boost the catalytic reduction of Pb(II). Specifically, Co(II) transferred a part of electrons to Mo(VI), promoting the formation of Mo(IV). Co(II) and Mo(IV), as the electron-rich sites, providing electrons to Pb(II), further accelerating the conversion of Pb(II) into Pb(0).

In the process of detecting Pb(II), the CoMoO₄ structures under different temperatures have distinct content of electron-rich sites Co(II) and Mo(IV). α-CoMoO₄ (800 °C), with the highest content are benefited to detect Pb(II). This work is conducive to understanding the effect of the changes of active sites resulting from crystal transformation on the electrocatalytic performance, and provides a way to construct sensitive electrochemical interfaces of distinct active sites.