Hierarchical Cu₃BiS₃ Nanostructures with Thermally Controlled Morphology for Photoconductive, Photothermal, and Catalytic Applications

Abstract

Studies and development of morphology-controlled synthesis of I−V−VI ternary semiconductor chalcogenide nanostructures with the use of earth-abundant, less toxic, and more environmentally friendly metals are in the forefront of current research due to their remarkable physical, chemical, and optoelectronic properties. Herein, we report the solvothermal synthesis of a ternary metal chalcogenide nanostructured material, wittichenite (Cu 3 BiS 3 ) with 1D, 2D, and 1D−2D morphologies at three different temperatures, using the deep eutectic solvent (DES) of choline chloride/thiourea (ChCl/TU). The unique advantages of DES are that it acts as a safer solvent, an in situ source of sulfur, and a nonaqueous soft template for making the reaction system much simpler. The synthesis temperature plays a key role in the morphological evolution and anisotropic growth of copper-bismuthsulfide nanostructures via oriented attachment, self-assembly, and Ostwald ripening mechanisms. The as-synthesized nanostructures of Cu 3 BiS 3 exhibit multifunctional features, including photoconductivity, photothermal and catalytic activity for 4-nitrophenol reduction. This work provides a unique strategy for the design and synthesis of morphology-controlled metal chalcogenide nanostructures using DES as an "all-in-one" reactant, template, and green reaction medium.

Synergistic effect of a bamboo-like Bi2S3 covered Sm2O3 nanocomposite (Bi2S3–Sm2O3) for enhanced alkaline OER

“…The larger doublet positioned at 158.4 eV and 163.8 eV is ascribed to Bi4f 7/2 and Bi4f 5/2 orbitals and Bi 3+ states in an oxidized environment. 33 The second doublet located at 158.3 eV and 167.7 eV is attributed to Bi4f 7/2 and Bi4f 5/2 orbitals and Bi 3+ chemical states in a sulfate environment. 49 The third doublet positioned at 160.5 eV and 162 eV corresponds to S2p 3/2 and S2p 1/2 orbitals in a sulfate environment and the S 2− chemical state, while two singlets are also observed positioned at 160.1 eV and 165.5 eV corresponding to S2p 3/2 and S 2 2− states caused by sulfur radicals contaminated by carbon owing to air exposure or other environmental effects during synthesis.…”

“…30,31 Bi 2 S 3 has a lamellar structure, where Bi and S atoms are interlinked with each other by strong covalent bonds in a plane, while outside the plane they are interlinked by weak bonds along the preferred growth orientation. 32,33 This unique design of Bi 2 S 3 coupled with Sm 2 O 3 offers a channel for charge transport that favors the OER activity. In this unique structure, bismuth plays the role of a mediator to shuttle the charges between Bi 2 S 3 and Sm 2 O 3 and promotes the separation and transfer of charge carriers at the electrode surface.…”

Deciphering the mechanistic insights of 4-nitrophenol reduction catalyzed by a 1D–2D Bi2S3 nanostructured catalyst

“…Furthermore, the reflectance data were converted into corresponding absorption spectra using the Kubelka–Munk function (eqn (7) and (8)). 13 The Kubelka–Munk function is expressed as follows:( hνF ( R )) n = A ( hν − E g )where R is the percentage of reflectance, E g is the material's band gap, hν is the photon energy in eV, F ( R ) is the Kubelka–Munk coefficient, and the exponent n designates the nature of the optical transition. The n = 1/2 and 2 are for indirect and direct allowed transitions, respectively.…”

“…2,3 Due to their good water solubility, non-biodegradability, and other carcinogenic effects, breaking them down or transforming them into less harmful compounds is a vital and significant topic of widespread concern. 4–6 Several techniques, including adsorption, 7 microbial degradation, 8 photocatalytic degradation, 9 ozonation, 10 electrochemical methods, 11,12 and chemical reduction, 13,14 have already been established to eliminate 4-NP from water. A thorough examination of the chosen 4-NP removal methods reveals that the chemical reduction method using heterogeneous catalysts is the most effective for removing nitrophenols from the aqueous matrix due to its eco-friendliness, simplicity in use, and high efficiency.…”

Deep eutectic solvents as an emerging green platform for the synthesis of functional materials

“…14f). While the above-mentioned team utilized a DES as a solvent and structural guide, Mahto et al 125 explored a new approach of using a deep eutectic solvent (DES) of choline chloride/thiourea (ChCl/TU) to perform the multiple functions of solvent, in situ sulfur source and non-aqueous soft template to synthesize ternary metal–sulfur nanomaterial wafers (Cu 3 BiS 3 ) in 1D, 2D, and 1D–2D morphologies (Fig. 14g).…”