Chalcogenide Materials in Water Purification: Advances in Adsorptive and Photocatalytic Removal of Organic Pollutants

Abstract

Chalcogenide-based materials, known for their unique physicochemical properties, emerge as promising solutions for the removal of hazardous organic pollutants, such as dyes, pharmaceuticals, pesticides, and herbicides, from water and wastewater. This review examines the latest developments in the synthesis, structural optimization, and application of chalcogenide materials for environmental remediation. The past decade has witnessed remarkable advances in controlling the composition and structure of chalcogenide materials at the atomic level. The development of precise synthetic methods enables the creation of complex hierarchical structures, heterojunctions, and hybrid materials, leading to significant improvements in photocatalytic efficiency, stability, and selectivity for various environmental applications. Key emphasis is placed on adsorption and photocatalysis as green technologies, offering efficient pathways for pollutant removal. Mechanistic insights into the interactions between chalcogenide materials and contaminants are explored, providing a comprehensive understanding of their performance. Furthermore, challenges such as toxicity, scalability, and operational stability are discussed alongside future prospects for integrating these materials into industrial-scale water treatment systems. This review aims to inspire continued innovation in sustainable water purification technologies using chalcogenides.

Keywords: adsorption; metal chalcogenides; organic pollutants; photocatalytic; water/wastewater treatment.

Figure 1

Evolution of Metal Chalcogenides Research.

Figure 2

Electronic Structure and Properties of Metal Chalcogenides.

Figure 3

Ball‐milling synthetic process of unsymmetrical selenides and sulfides. Reproduced with permission.^{[ 106 ]} Copyright 2015, Semantic Scholar.

Figure 4

a) Preparation process of BV powder using balling milling technique, SEM images of b–d) BV and e) BiV samples. Reproduced with permisison.^{[ 115 ]} Copyright 2023, Nature. f) Top depiction of the ball milling jar, g) the path of the balls within the milling jar, and h) a schematic illustration demonstrating the generation of reactive species when SrTiO₃ becomes entrapped between two balls during a collision. Reproduced with permission.^{[ 116 ]} Copyright 2024, RSC.

Figure 5

a) Synthesis and optimization of Cu₂‐xSe on copper foil using the CVD technique. b) XRD illustrating the Cu₂‐xSe on copper foil; c) HRSEM depicting the development of microstructural elements and the formation of Cu₂‐xSe over varying reaction times (5 min to 3 h) between the etched copper foil and elemental selenium. Reproduced with permission.^{[ 122 ]} Copyright 2024, MDPI.

Figure 6

a) Schematic illustration of various morphologies in CdIn₂S₄. Reproduced with permission.^{[ 128 ]} Copyright 2010, RSC. b) Synthetic route of VSe₂@Cu₂Se nanocomposites. Reproduced with permission.^{[ 129 ]} Copyright 2023, Physica Scripta.

Figure 7

a) “Synthesis of Cd_0.5Zn_0.5S/Bi₂WO₆ (CZS/BWO) S‐scheme heterojunction. SEM images of b) BWO and c–e) 1.0CZS/BWO; f–h) TEM images”. Reproduced with permission.^{[ 134 ]} Copyright 2023, Elsevier. i) The synthesis of CuO and CdO nanoparticles, and CuO/CdO nanocomposite j) Photodegradation setup for RhB dye. Reproduced with permission.^{[ 135 ]} Copyright 2023, Elsevier.

Figure 8

A typical example of self‐assembled liquid phase crystal architectures. Reproduced with permission.^{[ 140 ]} Copyright 2014, Elsevier.

Figure 9

Schematic representation of the primary synthesis pathways for mesoporous materials. a–c) Soft template techniques: a) CSA, b) TLCT, and c) EISA. d) Hard‐templating technique. Reproduced with permission.^{[ 145 ]} Copyright 2011, RSC.

Figure 10

Illustration of a scheme demonstrating the hard‐template synthesis process utilizing SBA‐15 as the hard template, aimed at the fabrication of 2D hexagonally orderly mesoporous WS₂. Phosphotungstic acid: H₃PW₁₂O₄₀. Reproduced with permission.^{[ 157} , ^{159 ]} Copyright 2023, Wiley; Copyright 2007, ACS.

Figure 11

Fundamental adsorption method for the elimination of pollutants onto chalcogenide materials.

Figure 12

“Nano‐structured morphology of CoSe₂ nanoflakes viewed using a) FE‐SEM, b) TEM, c) HR‐TEM and d) SAED pattern. e) Typical XRD diffraction pattern of CoSe₂ nanoflakes which were synthesized using 12 mol L⁻¹ KOH matching JCPDS No. 88–1712. f) Percentage change in adsorption with increasing numbers of adsorption and desorption cycles (five) demonstrates the reusability of CoSe₂ nanoflakes for adsorption of RhoB dye.” Reproduced with permission.^{[ 175 ]} Copyright 2018, Wiley.

Figure 13

“SEM images of a) Cu₂MoS₄‐4/g‐C₃N₄ b) Cu₂MoS₄‐2/g‐C₃N. Sorption mechanism of c) Cu₂MoS₄/g‐C₃N₄ and d) the structure of MB and MO.” Reproduced with permission.^{[ 177 ]} Copyright 2019, Elsevier.

Figure 14

a) Schematic preparation route of MoS₂‐EA‐MWCNTs. b) AFM image, matching line profile of thickness obtained along the blue line of a singular nanostructured MoS₂ from MoS₂‐EA‐MWCNTs, and crystal size distribution for vertical and lateral orientations of MoS₂‐EA‐MWCNTs. c) sorption activity and removal efficient, d) sorption kinetics and isotherms.^{[ 178 ]} e) Methodology for synthesizing MoS₂ nanosheet, TiO₂ microtube, and TiO₂@MoS₂ microtube, together with their f) utilization for the elimination of RhB. Reproduced with permission.^{[ 179 ]} Copyright 2020, Elsevier.

Figure 15

Photodegradation of dyes.

Figure 16

a) Schematic representation for the fabrication of a ZnIn₂S₄ modified Sb₂S₃ hybrid heterostructure. Water contact angles of b) ZnIn₂S₄; c) Sb₂S₃; and d) SB‐ZIS‐2. Reporduced with permission.^{[ 215 ]} Copyright 2017, Elsevier.

Figure 17

a) Proposed route and intermediate products for degradation of tetracycline. b) Mechanism for the degradation of tetracycline. Reproduced with permission.^{[ 217 ]} Copyright 2021, Elsevier.

Figure 18

“SEM images of a) ZnIn₂S₄, b) g‐C₃N₄, c) 50% CZ, d) corresponding mapping images. ESR spectra of 50% CZ in dark and under visible light (λ > 420 nm): e) DMPO‐^•OH in aqueous dispersions and f) DMPO‐^•O₂ ⁻ in methanol dispersions. g) Trapping experiment of active species during the photocatalytic breakdown of tetracycline over 50% CZ under visible light irradiation. h) The potential mechanism behind the improved photocatalytic activity of the g‐C₃N₄/ZnIn₂S₄ heterojunction.” Reproduced with permission.^{[ 215 ]} Copyright 2017, Elsevier.

Figure 19

Classes of synthetic insecticides according to pest kinds[218] 2022, Springer

Figure 20

Photoactivity of ZnIn₂S₄ and ZnIn₂S₄/rGO composites for the breakdown of 4‐NP under visible light (a) and simulated solar light (b) irradiation, c) total organic carbon removal efficiency of 4‐NP onto ZnIn₂S₄/rGO–1.5% and ZnIn₂S₄, d) photostability assessment of ZnIn₂S₄/rGO–1.5% and ZnIn₂S₄ for 4‐NP photodegradation. e) Schematic mechanism of 4‐NP photodegradation process. Reproduced with permission.^{[ 232 ]} Copyright 2015, Elsevier.

Figure 21

The framework for LCA.