Quaternary Chalcohalides CdSnSX₂ (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties

Abstract

Inorganic chalcohalides are attracting a tremendous amount of attention because of their remarkable structural variety and desirable physical properties. Although great advances have been made in recent years, functional inorganic chalcohalides with two-dimensional neutral layers are still rare. Herein, two novel chalcohalides CdSnSX 2 (X = Cl or Br) with high yields were obtained by reacting CdX 2 with SnS using a traditional solid-state method at 823 K. Both of these chalcohalides adopt orthorhombic space group Cmcm (No. 63) with the following structural values: a = 4.014(4)−4.064(2) Å, b = 12.996(2)−13.746(3) Å, c = 9.471(2)−9.621(2) Å, V = 494.1(8)−537.5(2) Å 3 , and Z = 4. The prominent architectural feature is the unique two-dimensional [CdSnSX 2 ] neutral layer consisting of composite [CdX 2 ] and [SnS] sublattices that are connected alternately through the Cd−S−Sn bonds along the ac plane. The [CdX 2 ] sublattice consists of a single octahedral chain of Cd-centered [CdX 4S 2 ] groups sharing cis-X edges, while the [SnS] sublattice consists of a bend-shaped chain of unusual [SnS 2 X 2 ] units sharing vertices of S atoms. Significantly, each CdSnSX 2 form (X = Cl or Br) shows high visible-light-induced photocatalytic activity for rhodamine B degradation, which is ∼7.0 times higher than that of nitrogen-doped TiO 2 (TiO 2−x N x ) under the same experimental conditions. This discovery enriches the categories of inorganic chalcohalides and provides more choices of candidate materials for photocatalytic applications.

Interesting dimensional transition through changing cations as the trigger in multinary thioarsenates displaying variable photocurrent response and optical anisotropy

“…In addition, inspired by recent reports that most of the lone-pair-based chalcogenides display intriguing photocatalytic properties, 38–43 the photoelectrochemical experiment was performed through a standard three-electrode system using simulated solar light illumination to study the photoelectric properties of Cs 2 ZnAs 4 S 8 and [(NH 4 )Cs]CdAs 4 S 8 . As illustrated in Fig.…”

“…These values are compared to those of other reported quaternary thioarsenates, such as RbCu 4 AsS 4 (E g = 2.15 eV), 36 Cs 3 CuAs 4 S 8 (E g = 2.26 eV), 30 Rb 8 Cu 6 As 8 S 19 (E g = 2.29 eV), 37 and CsCu 2 AsS 3 (E g = 2.30 eV). 27 In addition, inspired by recent reports that most of the lone-pair-based chalcogenides display intriguing photocatalytic properties, [38][39][40][41][42][43] the photoelectrochemical experiment was performed through a standard three-electrode system using simulated solar light illumination to study the photoelectric properties of Cs 2 ZnAs 4 S 8 and [(NH 4 )Cs]CdAs 4 S 8 . As illustrated in Fig.…”

Nanostructured Metal Chalcohalide Photocatalysts: Crystal Structures, Synthesis, and Applications

“…Chalcohalide − materials are just in the conception stage of this new discipline of multi-anion materials as photocatalysts compared to other multi-element compound semiconductors (Figure ). Chalco­halides are usually denoted as MCH, where M stands for one or more metal ions, C stands for chalcogenide, and H stand for halide ions.…”

Pb3SBrI3: the first Pb-based chalcohalide with multiple halogens features a unique two-dimensional structure composed of diverse Pb-centered polyhedra

“…For example, CdSnSX 2 (X = Cl or Br) features neutral layers composed of mixed [CdX 2 ] and [SnS] sublattices and show a good photocatalytic performance. 27 AIn 4 S 6 Cl (A = Rb, Cs) displays layer structures formed by InS 6 octahedra and InS 3 Cl units, and has a great photocurrent effect and may be used for potential applications in electrochemical devices. 28 The 0D Ba 3 FeS 4 Br 8 and 2D Cs 2 [Mn 2 Ga 3 S 7 Cl] 29 have unusual magnetic properties.…”