Direct Z-scheme of n-type CuS/p-type ZnS@electrospun PVP nanofiber for the highly efficient catalytic reduction of 4-nitrophenol and mixed dyes

Abstract

Environmental pollution has been the most critical issue on earth due to many factors, particularly the industrial chemical waste, which can be detoxified by photocatalytic methods. In this study, we demonstrate the fabrication of an electrospun composite nanofiber embedded with n-type CuS and p-type ZnS in partially carbonized-PVP nanofibers, so-called Z-type-CuS/ZnS@PVP nanofibers, to reduce 4-nitrophenol to 4-aminophenol and degrade the mixed dyes of methylene blue, rhodamine B, and methyl orange. The Z-type-CuS/ZnS@PVP nanofibers were prepared by an electrospinning method, followed by annealing at 180 °C and 400 °C under N₂ atmosphere. As-prepared CuS/ZnS@PVP nanofibrous mats were characterized by SEM, XRD, PL, DRS, TPC, and EIS analyses. The results revealed that Z-type CuS/ZnS@PVP nanofibers have enhanced optical and electrochemical properties as compared with the CuS@PVP and ZnS@PVP nanofibers. Likewise, the Z-scheme was more beneficial for promoting the electron transfer as well as for delaying the photocarrier recombination. For the applications of CuS/ZnS@PVP nanofibers, the reduction of 4-nitrophenol to 4-aminophenol occurred within 2 h and the mixed-dye degradation occurred in 90 min in 5% MeOH aqueous solution under solar light irradiation. The CuS/ZnS@PVP nanofibers also possessed excellent stability, with more than 95% remaining after five recycle runs. The photocatalytic mechanism reaction is proposed, in which the mechanism was initiated by the adsorption of organic pollutants on the nanofiber matrix, followed by the photoreaction due to e⁻ and h⁺ in CuS/ZnS after light irradiation as well as from the generated radical species. Lastly, the inorganic photocatalyst embedded in the nanofiber matrix offered an easy recovery process with excellent degradation performance as well.