Synthesis of highly efficient novel two-step spatial 2D photocatalyst material WS2/ZnIn2S4 for degradation/reduction of various toxic pollutants

Abstract

In this article, we report the synthesis, characterization of novel biofriendly 2D/2D heterostructure WS2/ZnIn2S4 material in which 2D WS2 nanosheets are uniformly distributed spatially onto the spherically arranged 2D leaves of ZnIn2S4. We then studied the in-depth photocatalytic degradation activity of this novel nanocomposite and its pristine component materials on cationic dye: malachite green, anionic dye: congo red and reduction of heavy metal: chromium(VI) and the degradation efficiency of composite material was also tested on rhodamine-B, methylene blue, methyl orange dyes and acetaminophen/paracetamol drug. Form factor, structure factor and shape factor analysis has been carried out using X-ray diffractometry (XRD). Bond vibrations, functional groups and phonon vibration mode analysis has been done based on Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. Morphological and compositional analysis has been done using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM). Surface area and pore size/distribution was characterized using Brunauer–Emmett–Teller (BET) method and Barrett-Joyner-Halenda Model. Degradation pathways and intermediate products are proposed using the high-performance liquid chromatography (HPLC). Photocatalytic activity of the nanocomposite WS2/ZnIn2S4 is compared with pristine ZnIn2S4 and pristine WS2, which shows more than 50% enhancement in both efficiency and rate of degradation/reduction for all the pollutants. A scavenger study was carried out to get insight of primary and secondary reactive oxygen species (ROS) taking part in degradation. Exciton lifetime, surface charge and stability, and flat band positions were studied based on time-correlated single photon counting (TCSPC) also known as time-resolved photoluminescence (TRPL), zeta potential, and Mott-Schottky respectively. Rate kinetics study was performed to analyze the physical and chemical behaviour of the nanocomposite with pollutants in consideration. Results show ∼100%, ∼90%, and ∼95% degradation efficiency by the heterostructure for malachite green (MG), congo red (CR), and reduction of heavy metal chromium (Cr(VI)) respectively within 5 min, which is a huge improvement as compared to pristine WS2 and pristine ZnIn2S4, both of which show the efficiencies of only ∼25% to∼75% in all the cases.