Controllable preparation, formation mechanism and photocatalytic performance of copper base sulfide nanoparticles

doi:10.1016/j.matchemphys.2020.123504

Materials Chemistry and Physics

Volume 254, 1 November 2020, 123504

https://doi.org/10.1016/j.matchemphys.2020.123504 Get rights and content

Highlights

•
Copper Base Sulfide Nanoparticles were synthesized by a simple and green method.
•
The ratios of precursors determine the composition and morphology of the products.
•
The products exhibit good photocatalytic activity under visible irradiation.
•
The interaction of sulfur with copper ion in PEG was analyzed in detail.

Abstract

In this paper, copper base sulfide nanoparticles (Cu₂S, CuS, CuO/Cu₂O/Cu₂S, Cu₂S/CuS, CuS/S) were synthesized in polyethylene glycol (PEG)-400 by a one-step method and by tuning the molar ratios of Cu:S (1:0.1–1:3) with copper acetate and sublimed sulfur as sources. The interaction of elemental sulfur with copper ion in PEG was analyzed in detail to elucidate the formation mechanism. With the change of the molar ratio of copper to sulfur, the products exhibit a variety of composition, morphology and size. When the molar ratio of copper to sulfur is 1:1, the product is CuS nanoflakes with particle size of 200–300 nm and thickness of 30 nm. The CuS nanoflakes with a smaller band gap value of 2.01eV can photodegrade 96% (48 mg/g) of rhodamine B (RhB) in 5 min in the presence of H₂O₂. This route is simple, environmentally friendly and it offers a more promising way to prepare different morphologies and compositions of Copper Base Sulfide Nanoparticles (CBSN).

Graphical abstract

Introduction

Cu_xS nanomaterials have been extensively investigated because of their outstanding optical, electrical and chemical properties [1,2]. They have been widely used in catalysis [[3], [4], [5], [6]], photovoltaic [7,8], sensors [9,10], tissue imaging [11,12] and cancer treatment [13]. Features of copper chalcogenides vary with their size and shape. Various nanostructures have been prepared, such as nanodisks [14], nanotubes [15], nanoflowers [16], nanoscale hollow spheres [17], nanoplatelets [18], nanoparticles [19]. Hydrothermal, solvothermal, template, sonochemical, microemulsion and solid phase methods have been explored to prepare Cu_xS.

Cu_xS exists in a variety of stoichiometric ratios, such as CuS, Cu_1.75S, Cu_1.8S, Cu_1.95S and Cu₂S(x = 1–2) with forbidden bands (1.2–2.5eV) [20,21]. The stoichiometric ratios, morphology and size of products are often affected by reaction time, temperature, type and proportion of precursors and reaction medium. Han et al. found precursors containing manganese ions induced shape evolution process from monoclinic egg-like Cu_1.94S nanocrystals to hexagonal CuS nanoplates. Dumbbell Cu_1.94S–CuS were obtained by controlling the reaction time during phase transfer [22]. Kundu et al. prepared CuS spheres and CuS nanotubes by controlling the ratio of the precursor, the proportion of the reaction medium, reaction temperature and time. The diameter of CuS nanotubes became larger with the increase of reaction temperature [20]. Jian et al. used solvothermal method to prepare Cu₂S, Cu₂S/CuS and CuS. Different ligands were employed as sulfur sources to get different products [23]. Wang et al. synthesized flower-like CuS using sulfur powder and CuCl₂·2H₂O as precursors and ethylene glycol as medium and reductant [24]. Wang et al. have synthesized Cu_xS nanoparticles with different stoichiometric ratios by adjusting the ratio of copper chloride and sodium sulfide. With the increase of S²⁻, the product changed from CuS to Cu₇S₄, and finally to Cu₉S₅ [21]. However, as a green solvent, PEG was not used as a medium to prepare Cu_xS with different stoichiometric ratios by tuning the molar ratio of copper salt and elemental sulfur and the interaction of sulfur with copper ion was seldom researched. Furthermore, most reported methods were time consuming and complicated. Thus, green, simple, controllable preparation of CBSN is still a challenge.

In this paper, a one-step(one-pot) synthesis was used to obtain CBSN, including Cu₂S, CuS, Cu₂S/CuS, CuS/S, CuO/Cu₂O/Cu₂S nanoparticles, in a PEG-400 medium with Cu(CH₃COO)₂•H₂O and sulfur powder as the copper source and the sulfur source, respectively. The ratio of the precursors was adjusted to regulate the stoichiometric ratios of copper and sulfur in the products. The reaction mechanism was elucidated. In addition, the obtained products can effectively photodegrade RhB in the visible light region with the assistance of hydrogen peroxide. This route is environmentally friendly and it offers a more promising way to prepare different morphologies and compositions of CBSN owing to its low cost, simple operation and good potential for scale-up.

Section snippets

Chemicals

Cu(CH₃COO)₂•H₂O was purchased from Fuchen chemical reagent plant. PEG-400 and sublimed sulfur were purchased from Tianjin Damao chemical reagent factory. RhB and anhydrous ethanol (CH₃CH₂OH) were purchased from Guangzhou chemical reagent plant. All of them are analytical grade.

Characterization

XRD (MSAL XD-2X, Beijing University, China) with Cu Kα radiation (at 48 kV and 25 mA, λ = 1.5406 nm, scanning speed 2°/min) was used to characterize the crystal structure of the CBSN. Samples dispersed in KBr pellets were

XRD analysis

Fig. 1 shows the XRD patterns of the as-synthetic products, indicating that the molar ratio of Cu(CH₃COO)₂•H₂O and S (n_Cu:n_S) determines the composition of the products. The XRD pattern is compared with tenorite copper oxide (CuO) standard card with monoclinic structure (JCPDS No. 80-0076), cuprite cuprous oxide (Cu₂O) standard card with cubic structure (JCPDS No. 78–2076), cuprous sulfide (Cu₂S) standard card with cubic structure (JCPDS No. 84–1770), covellite copper sulfide(CuS) standard card

Conclusion

We synthesized Cu₂S, CuS, CuO/Cu₂O/Cu₂S, Cu₂S/CuS and CuS/S nanoparticles in PEG-400 by a one-step method and by controlling the molar ratios of Cu:S (1:0.1–1:3) with copper acetate and sublimed sulfur as sources. The characterization and photocatalytic properties of the products were studied. The results show that, the sublimed sulfur is a Cu(II) reducing agent, and it disproportionates to produce S²⁻ interacting with Cu (II) and Cu (I), while the excessive sublimed sulfur becomes spherical

CRediT authorship contribution statement

Jiajie Jiang: Methodology, Writing - original draft, Formal analysis. Qing Jiang: Data curation, Validation. Runkang Deng: Formal analysis, Visualization. Xinyuan Xie: Supervision, Project administration, Writing - review & editing, Resources. Jianxin Meng: Resources.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the Postgraduate Research Funds of Department of Chemistry, Jinan University.

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Controllable preparation, formation mechanism and photocatalytic performance of copper base sulfide nanoparticles

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Characterization

XRD analysis

Conclusion

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgments

Powder Technol.

Powder Technol.

Biosens. Bioelectron.

Acta Biomater.

Mater. Lett.

Mater. Lett.

Sol. Energy

Appl. Catal. B Environ.

J. Alloys Compd.

Chem. Eng. J.

Sensor. Actuator. B Chem.

Appl. Surf. Sci.

Mater. Today: Proceedings

J. Alloys Compd.

Mater. Res. Bull.

Compound copper chalcogenide nanocrystals

Chem. Rev.

Nanostructured binary copper chalcogenides: synthesis strategies and common applications

Nanoscale

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Syntheses and energy storage applications of MxSy (M = Cu, Ag, Au) and their composites: rechargeable batteries and supercapacitors

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