CdS nanocrystallites sensitized ZnO nanosheets for visible light induced sonophotocatalytic/photocatalytic degradation of tetracycline: From experimental results to a generalized model based on machine learning methods

Abstract

CdS/ZnO nanosheets heterostructures ((x)CdS/ZNs) with different mole ratios of Cd/Zn ((x) = 0.2, 0.4, and 0.6) were synthesized by the impregnation-calcination method. PXRD patterns showed that the (100) diffraction of ZNs was the most significant in the (x)CdS/ZNs heterostructures, and it confirmed that CdS nanoparticles (in cubic phase) occupied the (101) and (002) crystal facets of ZNs with hexagonal wurtzite crystal phase. UV–Vis DRS results indicated that CdS nanoparticles decreased the band gap energy of ZNs (2.80–2.11 eV) and extended the photoactivity of ZNs to the visible light region. The vibrations of ZNs were not observed clearly in the Raman spectra of (x)CdS/ZNs due to the extensive coverage of CdS nanoparticles shielding the deeper-laying ZNs from Raman response. The photocurrent of (0.4) CdS/ZNs photoelectrode reached 33 μA, about 82 times higher than that for ZNs (0.4 μA, 0.1 V vs Ag/AgCl). The formation of an n-n junction at the (0.4) CdS/ZNs reduced the recombination of electron-hole pairs and increased the degradation performance of the as-prepared (0.4) CdS/ZNs heterostructure. The highest percentage removal of tetracycline (TC) in the sonophotocatalytic/photocatalytic processes was obtained by (0.4) CdS/ZNs under visible light. The quenching tests showed that O2•-, h+, and OH• were the main active species in the degradation process. The degradation percentage decreased negligibly in the sonophotocatalytic (84%–79%) compared to the photocatalytic (90%–72%) process after four re-using runs due to the presence of ultrasonic waves. For the estimation of degradation behavior, two machine learning methods were applied. The comparison between the ANN and GBRT models evidenced that both models had high prediction accuracy and could be used for predicting and fitting the experimental data of the %removal of TC. The excellent sonophotocatalytic/photocatalytic performance and stability of the fabricated (x)CdS/ZNs catalysts made them promising candidates for wastewater purification.