Abstract
Two types of hierarchical mesoporous CuS nanospheres, i.e., solid spheres (SSs) and hollow spheres (HSs), were controllably synthesized by a facile and green microwave-assisted wet chemical process, using copper acetate and thiourea aqueous solutions as precursors without a surfactant or template. The crystal structures, morphologies and photocatalytic properties of the products were characterized by various techniques. The results indicated that CuS SSs of 150 ± 50 nm in diameter are made of nanograins of about 10 nm in size, whereas CuS HSs of 400 ± 100 nm in outer-diameter are the assembly of ultrathin nanosheets in thickness of about 6 nm. The as-obtained both CuS architectures exhibit far superior dye degradation properties than commercial CuS powder for the decomposition of organic dyes including rhodamine B, methylene blue and malachite green with the help of hydrogen peroxide under visible light. Specially, using CuS HSs as catalyst, the decoloring rates of three organic dyes catalyst reach above 90% after just 1 min of irradiation and are approaching 100% after 20 min of irradiation, suggesting a fast and efficient photocatalytic activity and a promising application in industrial wastewater purification.
Similar content being viewed by others
References
Zou Z, Ye J, Sayama K, Arakawa H (2001) Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst. Nature 414:625–627
Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y (2001) Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293:269–271
Jin X, Ye L, Xie H (2017) Bismuth-rich bismuth oxyhalides for environmental and energy photocatalysis. Coord Chem Rev 349:84–101
Liu Q, Zhou Y, Kou J, Chen X, Tian Z, Gao J, Yan S, Zou Z (2010) High-yield synthesis of ultralong and ultrathin Zn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 into renewable hydrocarbon fuel. J Am Chem Soc 132:14385–14387
Basu M, Sinha AK, Pradhan M, Sarkar S, Negishi Y, Govind Pal T (2010) Evolution of hierarchical hexagonal stacked plates of CuS from liquid-liquid interface and its photocatalytic application for oxidative degradation of different dyes under indoor lighting. Environ Sci Technol 44:6313–6318
Liu S-Q, Wen H-R, Ying G, Zhu Y-W, Fu X-Z, Sun R, Wong C-P (2018) Amorphous Ni(OH) 2 encounter with crystalline CuS in hollow spheres: a mesoporous nano-shelled heterostructure for hydrogen evolution electrocatalysis. Nano Energy 44:7–14
Venkadesh A, Radhakrishnan S, Mathiyarasu J (2017) Eco-friendly synthesis and morphology-dependent superior electrocatalytic properties of CuS nanostructures. Electrochim Acta 246:544–552
Deng C, Hu H, Ge X, Han C, Zhao D, Shao G (2011) One-pot sonochemical fabrication of hierarchical hollow CuO submicrospheres. Ultrason Sonochem 18:932–937
Deng C, Ge X, Hu H, Yao L, Han C, Zhao D (2014) Template-free and green sonochemical synthesis of hierarchically structured CuS hollow microspheres displaying excellent Fenton-like catalytic activities. CrystEngComm 16:2738–2745
Deng C, Hu H, Shao G, Han C (2010) Facile template-free sonochemical fabrication of hollow ZnO spherical structures. Mater Lett 64:852–855
Han C, Zhao D, Deng C, Hu K (2012) A facile hydrothermal synthesis of porous magnetite microspheres. Mater Lett 70:70–72
Deng C, Guan H (2013) Fabrication of hollow inorganic fullerene-like BiOBr eggshells with highly efficient visible light photocatalytic activity. Mater Lett 107:119–122
Hu H, Xu J, Deng C, Ge X (2014) Hierarchical mesoporous MoO2 hollow microspheres: synthesis, mechanism and application in removing Cr(VI) from wastewater. Mater Res Bull 51:402–410
Huang Y, Xiao H, Chen S, Wang C (2009) Preparation and characterization of CuS hollow spheres. Ceram Int 35:905–907
Qi H, Huang J, Cao L, Wu J, Li J (2012) Controlled synthesis and optical properties of doughnut-aggregated hollow sphere-like CuS. Ceram Int 38:6659–6664
Heydari H, Moosavifard SE, Elyasi S, Shahraki M (2017) Nanoporous CuS nano-hollow spheres as advanced material for high-performance supercapacitors. Appl Surf Sci 394:425–430
Liu J, Xue D (2009) Solvothermal synthesis of CuS semiconductor hollow spheres based on a bubble template route. J Cryst Growth 311:500–503
Jiang D, Hu W, Wang H, Shen B, Deng Y (2011) Microemulsion template synthesis of copper sulfide hollow spheres at room temperature. Colloids Surf, A 384:228–232
Jiang D, Hu W, Wang H, Shen B, Deng Y (2011) A microemulsion-template-interfacial-reaction route to copper sulfide hollow spheres. J Colloid Interface Sci 357:317–321
Liu X, Ai L, Jiang J (2015) Interconnected porous hollow CuS microspheres derived from metal-organic frameworks for efficient adsorption and electrochemical biosensing. Powder Technol 283:539–548
Feng F, Li K, Li Y, Ma Z (2017) Synthesis of hollow CuS and PdS via microwave-assisted cation exchange. J Nanosci Nanotechnol 17:3615–3619
He Y, Yu X, Zhao X (2007) Synthesis of hollow CuS nanostructured microspheres with novel surface morphologies. Mater Lett 61:3014–3016
Thongtem T, Phuruangrat A, Thongtem S (2009) Formation of CuS with flower-like, hollow spherical, and tubular structures using the solvothermal-microwave process. Curr Appl Phys 9:195–200
Hu H, Deng C, Zhang K, Yin P (2012) Facile microwave-assisted synthesis of PbS nanotubes. Micro Nano Lett 7:464–466
Deng C, Tian X (2013) Facile microwave-assisted aqueous synthesis of CdS nanocrystals with their photocatalytic activities under visible lighting. Mater Res Bull 48:4344–4350
Deng C, Guan H, Tian X (2013) Novel Bi19S27Br 3 superstructures: facile microwave-assisted aqueous synthesis and their visible light photocatalytic performance. Mater Lett 108:17–20
Hu H, Chen G, Deng C, Qian Y, Wang M, Zheng Q (2016) Green microwave-assisted synthesis of hierarchical NiO architectures displaying a fast and high adsorption behavior for Congo red. Mater Lett 170:139–141
Rahmani A, Rahmani H, Zonouzi A (2017) Synthesis of copper sulfides with different morphologies in DMF and water: catalytic activity for methyl orange reduction. Mater Res Express 4:125024
Li H, Wang Y, Jiang J, Zhang Y, Peng Y, Zhao J (2017) CuS microspheres as high-performance anode material for Na-ion batteries. Electrochim Acta 247:851–859
Li H, Wang Y, Huang J, Zhang Y, Zhao J (2017) Microwave-assisted synthesis of CuS/graphene composite for enhanced lithium storage properties. Electrochim Acta 225:443–451
Chen X, Wang Z, Wang X, Zhang R, Liu X, Lin W, Qian Y (2004) Synthesis of novel copper sulfide hollow spheres generated from copper (II)–thiourea complex. J Cryst Growth 263:570–574
He W, Jia H, Li X, Lei Y, Li J, Zhao H, Mi L, Zhang L, Zheng Z (2012) Understanding the formation of CuS concave superstructures with peroxidase-like activity. Nanoscale 4:3501–3506
Basu M, Sinha AK, Pradhan M, Sarkar S, Negishi Y, Pal T (2010) Evolution of hierarchical hexagonal stacked plates of CuS from liquid—liquid interface and its photocatalytic application for oxidative degradation of different dyes under indoor lighting. Environ Sci Technol 44:6313–6318
Liu B, Xu W, Sun T, Chen M, Tian L, Wang J (2014) Efficient visible light photocatalytic activity of CdS on (001) facets exposed to BiOCl. New J Chem 38:2273
He S, Wang GS, Lu C, Luo X, Wen B, Cao L, Guo MS (2013) Controllable fabrication of CuS hierarchical nanostructures and their optical, photocatalytic, and wave absorption properties. ChemPlusChem 78:250–258
Hu H, Wang M, Deng C, Chen J, Wang A, Le H (2018) Satellite-like CdS nanoparticles anchoring onto porous NiO nanoplates for enhanced visible-light photocatalytic properties. Mater Lett 224:75–77
Sakthivel S, Kisch H (2003) Daylight photocatalysis by carbon-modified titanium dioxide. Angew Chem Int Ed 42:4908–4911
Mi L, Wei W, Zheng Z, Gao Y, Liu Y, Chen W, Guan X (2013) Tunable properties induced by ion exchange in multilayer intertwined CuS microflowers with hierarchal structures. Nanoscale 5:6589–6598
Li Z, Mi L, Chen W, Hou H, Liu C, Wang H, Zheng Z, Shen C (2012) Three-dimensional CuS hierarchical architectures as recyclable catalysts for dye decolorization. CrystEngComm 14:3965–3971
Jiang D, Hu W, Wang H, Shen B, Deng Y (2012) Controlled synthesis of hierarchical CuS architectures by a recrystallization growth process in a microemulsion system. J Mater Sci 47:4972–4980. https://doi.org/10.1007/s10853-012-6372-8
Wei T-Y, Wang Y-Y, Wan C-C (1990) Photocatalytic oxidation of phenol in the presence of hydrogen peroxide and titanium dioxide powders. J Photochem Photobiol A 55:115–126
Wong C, Chu W (2003) The hydrogen peroxide-assisted photocatalytic degradation of alachlor in TiO2 suspensions. Environ Sci Technol 37:2310–2316
Acknowledgements
This work was supported by the Natural Science Foundation of Anhui Province (1808085MB40), the Program of Study Abroad for Excellent Young Scholar of Anhui Province (gxfxZD2016221), the Key Projects of Support Program for Outstanding Young Talents of Anhui Province (gxyqZD2016151), the Natural Science Foundation of Anhui Province Educational Committee (KJ2018A0511, KJ2015A145) and the Special Foundation for Scientists of Hefei University (15RC06).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Hu, H., Wang, J., Deng, C. et al. Microwave-assisted controllable synthesis of hierarchical CuS nanospheres displaying fast and efficient photocatalytic activities. J Mater Sci 53, 14250–14261 (2018). https://doi.org/10.1007/s10853-018-2669-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-018-2669-6