Interface catalytic regulation via electron rearrangement and hydroxyl radicals triggered by oxygen vacancies and heavy metal ions

Abstract

Although the enhanced intrinsic activities of some nano-metal oxides are obtained by manufacturing oxygen vacancies (OVs), the effect of multiple roles of OVs is ambiguous. Herein, an interface catalytic regulation via electron rearrangement and hydroxyl radicals (˙OH) was proposed with the designed ZrO₂ hollow sphere rich in OVs (V_o-rich ZrO₂). Surprisingly, it was shown that the catalytic ability of V_o-rich ZrO₂ was 9.9 times higher than that of ZrO₂ with little OVs in electrochemical catalytic reduction of Pb(II). It was found that the generation of Zr²⁺ and Zr³⁺ caused by OVs results in the rearrangement of abundant free electrons to facilitate the catalytic reaction rates. The longer bond length between V_o-rich ZrO₂ and reactants, and the lower adsorption energy are beneficial for reactants to desorb, improving the conversion rates. Besides, the produced ˙OH were captured which were induced by OVs and trace divalent heavy metal ions in in situ electron paramagnetic resonance (EPR) experiments, contributing to lowering the energy barriers. This study not only revealed the enhanced interface catalytic effect of electron rearrangement and generated ˙OH triggered by OVs, but also provided unique insights into interface catalytic regulation on nano-metal oxides simulated by OVs.