Abstract

Co-thermal decompositions of equimolar concentrations of thiourea complexes ([Cu(tu)₃]Cl and [Sb(tu)₂]Cl₃) in ethylene glycol and ethanolamine were attempted. Based on the results from powder X-ray diffraction, Raman spectroscopy, and energy dispersive spectral analysis of the products, Cu₃SbS₃ in cubic symmetry emerged from ethylene glycol. In contrast, orthorhombic CuSbS₂ resulted from the ethanolamine medium. The generation of copper-rich and copper-poor sulfides was found to be the major reason behind the formation of these stoichiometries of the Cu-Sb-S system as verified by reacting the preformed Cu-S and Sb-S species in ethanolamine and ethylene glycol. Attempts to include bismuth (up to 50 mol%) for antimony were successful only in ethylene glycol medium. The inclusion of bismuth stabilized the orthorhombic form of Cu₃SbS₃, possibly due to the non-bonded lone pairs present on Bi³⁺ and Sb³⁺-ions. The inclusion of bismuth confirmed from the successful refinement of powder X-ray diffraction pattern by the Rietveld method, Raman spectroscopy, and energy dispersive spectroscopy analysis. CuSbS₂, Cu₃SbS₃ (cubic) and Cu₃Sb_0.50Bi_0.50S₃ showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu₃SbS₃, CuSbS₂, and Cu₃Sb_0.50Bi_0.50S₃, respectively.

Graphic abstract

CuSbS₂, Cu₃SbS₃ (cubic) and Cu₃Sb_0.50Bi_0.50S₃ showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu₃SbS₃, CuSbS₂, and Cu₃Sb_0.50Bi_0.50S₃, respectively.

中文翻译：

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溶剂介质在湿化学合成CuSbS 2，Cu 3 SbS 3和铋取代的Cu 3 SbS 3中的作用

摘要

尝试在乙二醇和乙醇胺中等摩尔浓度的硫脲络合物（[Cu（tu）₃ ] Cl和[Sb（tu）₂ ] Cl ₃））进行共热分解。基于产物的粉末X射线衍射，拉曼光谱和能量色散光谱分析的结果，来自乙二醇的立方对称的Cu ₃ SbS ₃出现了。相反，斜方CuSbS ₂由乙醇胺介质产生。通过在乙醇胺和乙烯中使预先形成的Cu-S和Sb-S物种反应证明，发现富铜和贫铜硫化物的生成是形成Cu-Sb-S系统这些化学计量的背后主要原因。乙二醇。仅在乙二醇介质中尝试加入铋（最高含量为50 mol％）作为锑。铋的掺入稳定了Cu ₃ SbS ₃的正交晶形，可能是由于Bi ³⁺和Sb ^3+离子上存在未结合的孤对。通过Rietveld方法，拉曼光谱和能量色散光谱分析成功地完善了粉末X射线衍射图，证实了铋的存在。硫化铜_{如图2所示}，Cu ₃ SbS ₃（立方晶）和Cu ₃ Sb _0.50 Bi _0.50 S ₃在其UV-可见光谱中显示出宽广的吸收，延伸到可见光区域。通过Tauc曲线分别估计出Cu ₃ SbS ₃，CuSbS ₂和Cu ₃ Sb _0.50 Bi _0.50 S ₃的带隙值分别为1.31、1.40和0.94 eV 。

图形摘要

CuSbS ₂，Cu ₃ SbS ₃（立方）和Cu ₃ Sb _0.50 Bi _0.50 S ₃在其UV-可见光谱中显示出广泛的吸收，延伸到可见光区域。通过Tauc曲线分别估计出Cu ₃ SbS ₃，CuSbS ₂和Cu ₃ Sb _0.50 Bi _0.50 S ₃的带隙值分别为1.31、1.40和0.94 eV 。