Electrons in Oxygen Vacancies and Oxygen Atoms Activated by Ce/Ce Promote High-Sensitive Electrochemical Detection of Pb(II) over Ce-Doped α-MoO Catalysts.

Modulating the active sites of oxygen vacancies (OVs) to enhance the catalytic properties of nanomaterials has attracted much research interest in various fields, but its intrinsic catalytic mechanism is always neglected. Herein, we establish an efficient strategy to promote the electrochemical detection of Pb(II) by regulating the concentration of OVs in α-MoO nanorods via doping Ce/Ce ions. α-MoO with the Ce-doped content of 9% (C9M) exhibited the highest detection sensitivity of 106.64 μM μA for Pb(II), which is higher than that achieved by other metal oxides and most precious metal nanomaterials. It is found that C9M possessed the highest concentration of OVs, which trapped some electrons for strong affinity interaction with Pb(II) and provided numerous atomic level interfaces of high surface free energy for catalysis reactions. X-ray absorption fine structure spectra and density functional theory calculation indicate that Pb(II) was bonded with the surface-activated oxygen atoms (Os) around Ce ions and obtained some electrons from Os. Besides, the longer Pb-O bonds on C9M were easier to break, causing a low desorption energy barrier to effectively accelerate Pb(II) desorbing to the electrode surface. This study helps to understand the changes in electronic structure and catalytic performance with heteroatom doping and OVs in chemically inert oxides and provide a reference for designing high-active electrocatalytic interfaces to realize ultrasensitive analysis of environmental contaminants.