Synthesis of porous Cu2FeSnS4 particles via solvothermal process for removal of organic acid fuchsin dye pollutant from wastewater

https://doi.org/10.1016/j.nanoso.2021.100697Get rights and content

Highlights

  • Porous CFTS particles demonstrate efficient adsorbent for removal of organic AF dye.

  • Highest adsorption capacity and 98% AF dye removal when porous CFTS as adsorbent.

  • Adsorption isotherm and kinetic studies exhibit that pseudo-second-order model.

  • Better stability and reusability performance were obtained when porous CFTS.

Abstract

Herein, solvothermal synthesized Cu2FeSnS4 (CFTS) particles are reported as an efficient adsorbent for removing acid fuchsin (AF) dye pollutants from the wastewater. Variation in synthesis reaction time led to have a porous sphere, sheet-flakes, and intermixed flower-sheet morphologies of CFTS particles synthesized at 200 °C for 6 h, 12 h and 18 h, respectively. The effect of surface morphologies of the CFTS particles on dye adsorption capability is examined. The porous spheres of CFTS particles have shown approximately (89.25 ± 2.21)% of AF dye adsorption within 10 min, and the value reaches (97.12 ± 0.76)% in 60 min. The high adsorption capacity i.e (123.12 ± 2.09) mg/g is obtained for porous spherical CFTS particles. The adsorption isotherm and kinetic studies reveal that the dye adsorption can be explained by the Langmuir isotherm and pseudo-second-order kinetic model. Further, the porous CFTS particles exhibit good stability and reusability of the adsorbent for wastewater purification. The present study results indicate that porous earth-abundant and non-toxic quaternary chalcogenide particles can be low cost, highly efficient adsorbent for removing organic acid fuchsin (AF) dye pollutants from wastewater.

Introduction

Acid fuchsin (AF) dye is broadly used in textile fabrics, silk, nylon, wool, and leather [1], [2]. The water pollution due to the synthetic dye pollutants (for example, AF dye) releases from textiles, paper, rubber, and plastic production which has a direct effect on the environment and human health [3], [4]. The industry’s wastewater release should be purified to reduce the adverse effects before mixing into natural resources [3], [4]. Water purification has been performed using several techniques such as electrochemical reactions [5], biodegradation [6], [7], adsorption [8], and other methods [4], [8]. Among these processes, the adsorption technique for water purification is gaining popularity due to a smooth, less energy consumption, economically feasible process. It does not need any light source with reasonable efficiency [8]. For efficient removal of pollutants from water, the adsorbents should have a large surface area, porosity, hollow and layered structures [4], [8]. Numerous materials such as carbon (carbon nanotubes and graphene/magnetite) [9], [10], [11], graphene–TiO2  [12], metal–organic frameworks (MOFs) [13], inorganic materials (oxides such as Fe3O4, Al2O3, ZnO [14], [15], [16], [17]) and chalcogenides (MoS2 [18], NiS [19], Cu3SnS4@C [20] and Cu2FeSnS4 [21]) and biomaterials (chitosan and peat) have been reported as an adsorbent for the extract of dyes from the aqueous solution/industrial wastewater [22], [23], [24]. Among these materials, earth-abundant and non-toxic quaternary chalcogenide Cu2FeSnS4 (CFTS) has received great attention owing to outstanding physicochemical and optoelectronic properties such as non-toxicity nature of constituent elements, large absorption coefficient (>104 cm−1), suitable bandgap (1.0 eV–1.5 eV), and excellent electrical properties [25], [26], [27], [28]. It has been explored in numerous applications such as solar cells, gas sensors, optical devices, and photocatalysis [26], [27], [28]. Hierarchical porous hollow CFTS microspheres exhibited superior capability to remove methyl orange dye pollutants in water via the adsorption process [21]. CFTS particles have also been investigated for photodegradation of rhodamine (RhB) and methyl orange (MO) under visible light [29], [30]. However, the removal of acid fuchsin (AF) dye pollutant from the water solution with CFTS adsorbent is not yet reported in the literature. Thus, it will be exciting to synthesis porous CFTS particles and utilize them to remove acid fuchsin (AF) dye pollutants from the aqueous solution.

Non-toxic quaternary chalcogenide CFTS particles have been synthesized in various methods such as thermal decomposition [26], microwave [21], solvothermal/hydrothermal method [25], [27], hot injection method, and others [27]. Among them, the solvothermal process is facile, high yield and has good control over crystal phase, morphology, and chemical composition of CFTS particles while varying process parameters such as reaction temperature, time, surfactants, and an initial precursor and their concentrations [29], [31], [32]. It is essential to the synthesis of porous CFTS particles and their application towards efficient dye adsorbent. In this article, solvothermal synthesis of CFTS particles and their application towards adsorbent for the adsorption (degradation) of acid fusion (AF) dye from the aqueous solution are reported. The role of surface morphology of CFTS particles on dye adsorption properties is studied. (97.12 ± 0.76)% of AF dye is adsorbed by the porous spheres of CFTS particles within 60 min. The CFTS particles have shown recyclable nature and can be repeatably used for adsorption of dye. The obtained results indicate that porous CFTS particles have a higher adsorption capacity.

Section snippets

Materials

The following chemicals were used for experimental work: ethylene glycol (EG, Merck), copper acetate monohydrate (CH3 CO2)2Cu. H2O, SRL, AR grade), ferric nitrate (Fe(NO3)3, Lobachemie), stannite chloride (SnCl2), SRL) and thiourea (CH4N2S, Loba Chemie).

Synthesis of CFTS particles

Cu2FeSnS4 particles were synthesized at 200 °C for 6 h, 12 h, and 18 h via solvothermal method. A typical synthesis, 2 mmol copper acetate monohydrate, 1 mmol ferric nitrate, 1 mmol stannite chloride, and 8 mmol thiourea were added into 40 ml

Physical characteristics of synthesized CFTS particles

The structural properties of synthesized samples are analysed using XRD and Raman measurements. The measured XRD patterns (Fig. 1a) of the prepared samples exhibit various diffraction peaks, such as (101), (112), (200), (220), (222), and (312) matches with the tetragonal structure of CFTS phase (ICDD No: 44-1476). The CFTS particles synthesized in 6 h reaction time have a slightly lower intensity and broader peaks (for example: (112) peak). The peak intensities in XRD patterns increase with an

Conclusions

The change in solvothermal reaction time successfully prepares different surface morphologies of CFTS particles. The reaction time has a clear impact on the chemical composition and surface morphology of synthesized CFTS particles. The porous spherical CFTS particles have a higher adsorption capacity and more dye adsorption properties than other sheet-flake and intermixed of the flower-sheet morphologies. The obtained experimental results concluded that the earth-abundant and non-toxic

CRediT authorship contribution statement

Nagaraju Mukurala: Conceptualization, Methodology, Validation, Investigation, Data curation, Formal analysis, Writing - original draft, Writing - review & editing, Visualization. Krishnaiah Mokurala: Formal analysis, Writing - review & editing. Siddhartha Suman: Formal analysis, Writing - review & editing. Ajay K. Kushwaha: Conceptualization, Methodology, Supervision, Resources, Writing - review & editing, Funding acquisition, Project administration.

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.

Acknowledgements

This work is supported by the department of science and technology, government of India , under Inspire Faculty Award (INSPIRE/04/2015/002498). The authors gratefully acknowledge the SIC-IIT Indore and MEMS department for providing the XRD and FE-SEM, EDX, BET, and UV–visible facilities. We would like to thank the Department of Physics in IIT Indore supported for Raman analysis.

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