Abstract
The bismuth-rich strategy, which involves increasing the bismuth content within the BiOCl structure, offers an effective approach for tailoring the physicochemical and optoelectrical properties of BiOCl photocatalysts for enhanced photocatalytic performance. In this study, BiOCl, Bi12O15Cl6, and Bi12O17Cl2 were selectively synthesized using the ethylene glycol (EG)-assisted microwave irradiation method by regulating the pH of the reaction solution. Photocatalytic performance was evaluated by studying bisphenol A (BPA) degradation and arsenite (As(III)) oxidation under visible-light irradiation. The energy structures and bandgaps of the materials were tuned according to their chemical compositions, affecting their photocatalytic activity. Bi12O17Cl2 (EG-pH 9) exhibited superior photo-efficiency: 85.4 % of BPA and 97.6 % of As(III) were removed by Bi12O17Cl2 (EG-pH 9) at rates 17.7 and 18.4 times higher than those of BiOCl (EG-initial pH 3), respectively. This superior performance attributed to the synergistic effect between the bismuth-rich nature and oxygen vacancies (OVs) induced by EG, along with the presence of OH− ions in the reaction solution. The increased number of OVs in Bi12O17Cl2 led to enhanced photocurrent density and charge transfer efficiency. Trapping experiments, DMPO-ESR spin-trapping, nitroblue tetrazolium transformation, terephthalic acid photoluminescence probing, and o-tolidine oxidation experiments identified holes (h+), superoxide radicals (•O2−), superoxide radicals (•OH) and electrons (e−) as the reactive species. Density functional theory calculations further highlight the OV of Bi12O17Cl2 as the active site for O2 adsorption. This study not only developed an effective method for fabricating bismuth-rich oxychlorides with OVs but also demonstrated the potential of these photocatalysts for wastewater treatment.
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