In this study, molybdenum disulfide (MoS2) decorated on graphitic carbon nitride (g-C3N4) heterostructure catalysts at various weight ratios (0.5%, 1%, 3%, 10%, w/w) were successfully prepared via a two-step hydrothermal synthesis preparation method. The properties of the synthesized materials were studied by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FT-IR), UV–Vis diffuse reflection spectroscopy (DRS), scanning electron microscopy (SEM) and N2 porosimetry. MoS2 was successfully loaded on the g-C3N4 forming heterojunction composite materials. N2 porosimetry results showed mesoporous materials, with surface areas up to 93.7 m2g−1, while determined band gaps ranging between 1.31 and 2.66 eV showed absorption over a wide band of solar light. The photocatalytic performance was evaluated towards phenol oxidation and of Cr(VI) reduction in single and binary systems under simulated sunlight irradiation. The optimum mass loading ratio of MoS2 in g-C3N4 was 1%, showing higher photocatalytic activity under simulated solar light in comparison with bare g-C3N4 and MoS2 for both oxidation and reduction processes. Based on scavenging experiments a type-II photocatalytic mechanism is proposed. Finally, the catalysts presented satisfactory stability (7.8% loss) within three catalytic cycles. Such composite materials can receive further applications as well as energy conversion.
The objective of this work was to evaluate the efficiency of a solar photocatalytic process using g-C3N4 as photocatalyst on the degradation of pharmaceutical compounds detected in hospital wastewater treatment plant secondary effluents. A compound parabolic collector pilot plant, established in the secondary effluent stream of the Ioannina city hospital wastewater treatment plant, was used for the photocatalytic experiments. The analysis of the samples before and after the photocatalytic treatment was accomplished using solid phase extraction (SPE), followed by UHPLC-LTQ/Orbitrap HRMS. Initial effluent characterization revealed the presence of ten pharmaceutical compounds. Among these, amisulpride, O-desmethyl venlafaxine, venlafaxine and carbamazepine were detected in all experiments. Initial concentrations ranged from 73 ng L−1 for citalopram to 2924.53 ng L−1 for O-desmethyl venlafaxine. The evolution of BOD5 and COD values were determined before and after the photocatalytic treatment. All detected pharmaceuticals were removed in percentages higher than 54% at an optimum catalyst loading ranging between 200 and 300 mg L−1. The potential of the catalyst to be reused without any treatment for two consecutive cycles was studied, showing a significant efficiency decrease.
Today, the pollution caused by a multitude of pharmaceuticals used by humans has been recognized as a major environmental problem. The objective of this study was to evaluate and compare the photocatalytic degradation of ten target psychiatric drugs in hospital wastewater effluents using g-C3N4 and 1%MoS2/g-C3N4 (1MSCN) as photocatalytic materials. The experiments were performed using real wastewater samples collected from hospital wastewater treatment plant (WWTP) secondary effluent in spiked and inherent pharmaceutical concentration levels. The photocatalytic experiments were performed in a laboratory-scale pilot plant composed of a stainless-steel lamp reactor (46 L) equipped with ten UVA lamps and quartz filters connected in series with a polypropylene recirculation tank (55–100 L). In addition, experiments were carried out in a solar simulator apparatus Atlas Suntest XLS+ at a 500 Wm−2 irradiation intensity. The analysis of the samples was accomplished by solid-phase extraction, followed by liquid chromatography-Orbitrap high-resolution mass spectrometry. Results showed that the photocatalytic degradation of pharmaceutical compounds followed first-order kinetics. In all cases, 1MSCN presented higher photocatalytic performance than g-C3N4. The removal rates of the pharmaceutical compounds were determined above 30% and 54% using g-C3N4 and 1MSCN, respectively. Parallel to kinetic studies, the transformation products (TPs) generated during the treatment were investigated.
In the present study, the photocatalytic degradation of amisulpride using g-C3N4 catalyst under UV-A irradiation was investigated. The photocatalytic process was evaluated in terms of its effectiveness to remove amisulpride from ultrapure and real municipal wastewater. High removal percentages were achieved in both aqueous matrices. However, a slower degradation rate was observed using wastewater as matrix that could be attributed to its complex chemical composition. The transformation products (TPs) were identified with liquid chromatography–mass spectrometry (LC–MS) in both ultrapure and real municipal wastewater. Based on the identified TPs, the photocatalytic degradation pathways of amisulpride are proposed which include mainly oxidation, dealkylation, and cleavage of the methoxy group. Moreover, the contribution of reactive species to the degradation mechanism was studied using well-documented scavengers, and the significant role of h+ and O2•− in the reaction mechanism was proved. The evolution of ecotoxicity was also estimated using microalgae Chlorococcum sp. and Dunaliella tertiolecta. Low toxicity was observed during the overall process without the formation of toxic TPs when ultrapure water was used as matrix. In the case of real municipal wastewater, an increased toxicity was observed at the beginning of the process which is attributed to the composition of the matrix. The application of heterogeneous photocatalysis reduced the toxicity, and almost complete detoxification was achieved at the end of the process. Our results are in accordance with literature data that reported that heterogeneous photocatalysis is effective for the removal of amisulpride from aqueous matrices.