Zirconia (ZrO₂) Embedded in Carbon Nanowires via Electrospinning for Efficient Arsenic Removal from Water Combined with DFT Studies

To use zirconia (ZrO2) as an efficient environmental adsorbent, it can be impregnated on a support to improve its physical properties and lower the overall cost. In this study, ZrO2 embedded in carbon nanowires (ZCNs) is fabricated via an electrospinning method to remove arsenic (As) from water. The maximum adsorption capacity values of As(III) and As(V) on the ZCNs are 28.61 and 106.57 mg/g, respectively, at 40 °C. These capacities are considerably higher than those of pure ZrO2 (2.56 and 3.65 mg/g for As(III) and As(V), respectively) created using the same procedure as for the ZCNs. Meanwhile, the adsorption behaviors of As(III) and As(V) on the ZCNs are endothermic and pH dependent and follow the Freundlich isotherm model and pseudo-first-order kinetic model. Both As(III) and As(V) are chemisorbed onto the ZCNs, which is confirmed by a partial density of state (PDOS) analysis and Dubinin-Radushkevich (D-R) model calculations. Furthermore, the ZCNs also possess the capability to enhance or catalyze the oxidation process of As(III) to As(V) using dissolved oxygen. This result is confirmed by a batch experiment, XPS analysis and Mulliken net charge analysis. Density functional theory (DFT) calculations indicate the different configurations of As(III) and As(V) complexes on the tetragonal ZrO2 (t-ZrO2)(111) and monoclinic ZrO2 (m-ZrO2)(111) planes, respectively. The adsorption energy (Ead) of As(V) is higher than that of As(III) on both the t-ZrO2(111) and m-ZrO2 (111) planes (3.38 and 1.90 eV, respectively, for As(V) and 0.37 and 0.12 eV, respectively, for As(III)).