Copper(II) sulfide nanostructures and its nanohybrids: recent trends, future perspectives and current challenges

doi:10.1007/s11706-023-0632-1

Front. Mater. Sci.

2023, Vol. 17

Issue (3) : 230632 https://doi.org/10.1007/s11706-023-0632-1

REVIEW ARTICLE

Copper(II) sulfide nanostructures and its nanohybrids: recent trends, future perspectives and current challenges

Narinder Singh^1,²(

)

¹. Department of Physics, Sardar Patel University, Mandi, Himachal Pradesh 175001, India
². Department of Physics, Government College Nadaun, District Hamirpur, Himachal Pradesh 177033, India

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Abstract

Among various metal chalcogenides, metal oxides and phases of copper sulfide, copper(II) sulfide (covellite, CuS) nanostructures have enjoyed special attentiveness from researchers and scientists across the world owing to their complicated structure, peculiar composition and valency, attractive and panoramic morphologies, optical and electrical conductivity, less toxicity, and biocompatibility that can be exploited in advanced and technological applications. This review paper presents a brief idea about crystal structure, composition, and various chemical methods. The mechanism and effect of reaction parameters on the evolution of versatile and attractive morphologies have been described. Physical properties of CuS and its hybrid nanostructures, such as morphology and optical, mechanical, electrical, thermal, and thermoelectrical properties, have been carefully reviewed. A concise account of CuS and its hybrid nanostructures’ diverse applications in emerging and recent applications such as energy storage devices (lithium-ion batteries, supercapacitance), sensors, field emission, photovoltaic cells, organic pollutant removal, electromagnetic wave absorption, and emerging biomedical field (drug delivery, photothermal ablation, deoxyribonucleic acid detection, anti-microbial and theranostic) has also been elucidated. Finally, the prospects, scope, and challenges of CuS nanostructures have been discussed precisely.

Keywords copper sulfide chemical synthesis method morphology electrical property optical property application

Corresponding Author(s): Narinder Singh

Issue Date: 06 September 2023

Cite this article:

Narinder Singh. Copper(II) sulfide nanostructures and its nanohybrids: recent trends, future perspectives and current challenges[J]. Front. Mater. Sci., 2023, 17(3): 230632.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-023-0632-1
https://academic.hep.com.cn/foms/EN/Y2023/V17/I3/230632

Fig.1 Data extracted from Google Scholar using keyword “copper sulfide nano” in abstract only.

Fig.2 (a) Crystal structure of hexagonal CuS unit cell. (b) Space-filling arrangement. (c) Ball-and-stick arrangement. (d) Alternating layers of CuS₄?Cu₃?CuS₄ planes bonded through S?S bond. (e) A typical view of CuS along c-axis. (f) Rietveld refinement of experimental XRD data of CuS. Reproduced with permission from Ref. [73] (Copyright 2018, RSC).

Fig.3 Chemical synthesis methods for CuS nanostructures.

Fig.4 FESEM and TEM images of CuS nanostructures synthesized by different chemical methods: (a) CuS microflowers by the hydrothermal method. Reproduced with permission from Ref. [87] (Copyright 2017, Elsevier). (b) Self-assembled hexagonal CuS nanoplates by solvothermal method. Reproduced with permission from Ref. [88] (Copyright 2013, Elsevier). (c) CuS NPs by chemical co-precipitation method. Reproduced with permission from Ref. [89] (Copyright 2017, Elsevier). (d) CuS NPs by sonochemical method. Reproduced with permission from Ref. [90] (Copyright 2019, Elsevier). (e) CuS hierarchical flowers by the microwave-assisted method. Reproduced with permission from Ref. [91] (Copyright 2010, Elsevier). (f)(g) CuS nanocrystals by sol-gel method. Reproduced with permission from Ref. [79] (Copyright 2014, Elsevier). (h) CuS NPs bychemical co-precipitation method. Reproduced with permission from Ref. [80] (Copyright 2019, Elsevier).

Fig.6 Schematic illustration of properties of CuS nanostructures.

Tab.2 Different morphologies of CuS nanostructures using hydrothermal and solvothermal methods [32–33,35,37,39,81,124–137]

Fig.7 Morphologies of CuS nanostructures. Adapted from Ref. [123].

Fig.8 Schematic illustration of the general mechanism responsible for diverse morphologies.

Fig.9 SEM images of CuS nanostructures synthesized at 20 °C with different reaction times: (a) 0.5 h; (b) 2 h; (c) 10 h; (d) 12 h. SEM images of CuS samples synthesized at different reaction temperatures for 10 h: (e) 20 °C; (f) 70 °C; (g) 120 °C [32]. (h)(i)(j)(k) FESEM images of the V-doped CuS micro skeins. Reproduced with permission from Ref. [37] (Copyright 2020, Elsevier). SEM images of CuS architectures with diverse morphologies at different magnifications: (l)(m) microspheres; (n)(o) hexagonal microsheets; (p)(q) sandwich-like plates; (r)(s) interlaced nanosheets; (t)(u) nanoflowers. Reproduced with permission from Ref. [63] (Copyright 2019, Elsevier).

Fig.11 (a) XRD patterns of CuS NPs suggestinga change in phase with variation in temperature from as-synthesized to 700 °C. SEM images of CuS NPs treated at different temperatures: (b) as-synthesized; (c) 250 °C; (d) 500 °C; (e) 750 °C. (f) TG curves of CuS NPs at 250, 500, and 700 °C. EDX spectra of samples treated at different temperatures: (g) as-synthesized; (h) 250 °C; (i) 500 °C; (j) 750 °C. (k) Atomic percentage analysis of different elements present in the samples. The values are expressed in average ± standard deviation. Reproduced with permission from Ref. [156] (Copyright 2020, Elsevier).

Fig.12 Variation of temperature with (a) Seebeck coefficient and (b) electrical resistivity for Cu_1?xAg_xS NCs when x = 0, 0.1, 0.2, 0.5, and 0.75. (c) Temperature dependent Hall resistivity (ρ_xy) for pristne CuS in presence of 5 T magnetic field at different applied currents of 20 and 51 mA. Variation of temperature with (d) electronic (κ_e) and lattice (κ_l) components of thermal conductivity and with (e) the values of ZT for Cu_1?xAg_xS NCs at x = 0, 0.1, 0.2, 0.5, and 0.75. Reproduced with permission from Ref. [73] (Copyright 2018, RSC).

Fig.13 Schematic representation of alications of CuS nanostructure.

Fig.14 Schematic representation of specific energy vs. specific power for the different electrochemical energy storage devices. Adapted from Ref. [164].

Tab.3 Different CuS nanostructures and its nanohybrids as supercapacitors electrode material [65,113,133,142,168,170–186]

Fig.15 FESEM images of (a)(a₁) CuS-2 h, (b)(b₁) CuS-3 h, and (c)(c₁) CuS-4 h. (d) Galvanostatic charge?discharge curves of CuS electrodes at the current density of 4 A·g^?1 in 2 mol·L^?1 KOH. (e) Galvanostatic charge?discharge curves of CuS-3 h based electrode measured at different current densities. (f)(g) The specific capacitance vs. current density curves of CuS-2 h and CuS-3 h for various current densities ranging from 4 to 13 A·g^?1. (h) Ragone plot and (i) stability performance curves of CuS-2 h and CuS-3 h based electrodes. (j) CV curves of CuS electrodes with different deposition times at scan rate of 15 mV·s^?1 in 2 mol·L^?1 KOH solution. CV curves of (k) CuS-2 h, (l) CuS-3 h, and (m) CuS-4 h at scan rates of 5?45 mV·s^?1. Reproduced with permission from Ref. [113] (Copyright 2017, Elsevier).

Fig.16 SEM images of CuS nanostructures obtained from (a) DMSO as solvent, (b) 3:1 DMSO-EG as solvent, (c) self-assembled CuS NW bundles. (d) 3:7 DMSO-EG as solvent, (e) 1:4 DMSO-EG as solvent, (f) EG as a solvent, and (g) Charge?discharge curves of the CuS cathode at 0.2 C rate during cycling. (h) CV curves in the 1stcycle atthe scanning rate of 0.02 mV·s^?1 inthe potential rangeof 0.02?2.7 V. The cycling performance at: (i) 0.2 and 4 C and (j) 0.1, 0.2, 0.5, 1 and 2 C rates for CuS NWs bundles. Reproduced with permission from Ref. [8] (Copyright 2014, Elsevier).

Fig.17 Energy level diagrams of the materials referenced to the vacuum level. Adapted from Ref. [79].

Tab.4 Solar parameters showing the performance of QDSSCs using CuS nanostructures and their nanohybrids [69,202–216]

Fig.18 SEM images of CuS CEs deposited at (a₁)(a₂) 1 h, (b₁)(b₂) 2 h, and (c₁)(c₂) 3 h. (d₁) Nyquist plots of the symmetric cells of CuS-1 h, CuS-2 h, CuS-3 h, and Pt CEs containing polysulfide electrolyte. The inset shows Nyquist plot of Pt at a higher impedance range and the equivalent circuit diagram. (e₁) Tafel polarization curves of the symmetrical dummy cells of CuS and Pt CEs. (f₁) J?V plots for TiO₂/CdS/CdSe/ZnS QDSSCs based on CuS and Pt CEs. Reproduced with permission from Ref. [203] (Copyright 2017, Elsevier).

Fig.19 (a)(b) SEM images of 3D CuS NWs anodized for 15 min. (c) The thickness statistics histogram of the 3D copper sulfide NPs anodized for 15 min. (d) J?E curves of the 3D CuS nanoplates anodized for different anodization time. (e) The corresponding F?N plots. (f) Variations of E_to and β with the anodization time. (g) The CV curve. Reproduced with permission from Ref. [226] (Copyright 2018, Elsevier).

Fig.20 (a) Schematic illustration of the mechanism of photocatalytic degradation of dye by CuS nanostructures. Reproduced with permission from Ref. [237]. (b) Schematic illustration of the synthesis of CQDs/CuS NC, and the mechanism of photocatalytic degradation of MB by CQDs/CuS NC. Adapted from Ref. [238].

Tab.5 Photocatalytic degradation of different dyes using CuS nanostructures and its nanohybrids [22,42,58,81,88,233,238,241–249]

Fig.21 FESEM images of hierarchical CuS microspheres of (a)(b) 0.25:1, 12 h, (c) 0.50:1, 12 h, (d) 0.75:1, 12 h, (e) 0.5:1, 18 h, (f) 0.50:1, 12 h, and (g)(h) 0.50:1, 24 h. (i)(k)(m) Kinetics of the photocatalytic degradation and (j)(l)(n) 1st order linear transforms of ln(C/C₀) = kt for RhB (panels (i)(j)), MB (panels (k)(l)), and MO (panels (m)(n)) by H₂O₂, CuS microspheres with and without H₂O₂, and commercial TiO₂ NPs with H₂O₂. TEM images of CuS microspheres for molar ratio (CuO:TU) of 0.50:1 at (o) 6 h, (p) 12 h, (q) 18 h, and (r) 24 h. (s) HRTEM image and (t) selected area electron diffraction (SAED) pattern of the CuS-0.50:1-24 microspher. (u) Cycle runs of the hierarchical CuS microsphere (CuS-0.50:1-24 sample). (v) Schematic representation of the formation of CuS microsphere from the CuO template. Reproduced with permission from Ref. [252] (Copyright 2020, Elsevier).

Fig.22 (a) SEM images of CuS-7. (b) Schematic illustration of the photocatalytic degradation mechanism using the (rGO/CuS-7) photocatalyst for MG dye. (c) Variation of MG concentration in dark and direct sunlight irradiation at different periods with and without CuS and different rGO/CuS photocatalysts. (d) Variation of MG concentration with timein the presence of 0.3 and 0.5 g·L^?1 (rGO/CuS-7) doses. The inset represents the corresponding photodegradation efficiency (97.6% for 0.3 g·L^?1 and 99.2% for 0.5 g·L^?1) after 90 min irradiation. (e) The reaction kinetics of the photodegradation of MG using CuS and different rGO/CuS photocatalysts. (f) The decrease of the absorption peak (at λ = 618 nm) with time, showing elimination of MG with (rGO/CuS-7) photocatalyst at pH 5.0 under solar irradiation. (g) Variation of MG concentration with time under direct sunlight using 0.3 g·L^?1 of rGO/CuS-7 photocatalyst at pH 5 at different dye concentrations; the insets represent the photodegradation efficiency (97.6% for 10 ppm, 91.0% for 15 ppm and 83.4% for 20 ppm) after 90 min irradiation. (h) Reusability of CuS (rGO/CuS-7) photocatalyst for degradation of 10 ppm MG dye solution at pH 5 under direct sunlight for several runs. Reproduced with permission from Ref. [249] (Copyright 2020, Elsevier).

Fig.23 (a) Energy band diagram of TiO₂ and CuS and (b) schematic illustration of charge carrier transfer for H₂ generation on CuS/TiO₂ NCs. Adapted from Ref. [256].

Fig.24 Schematic presentation of the band energy level and charge carrier’s transfer: (a) CuS/CdS; (b) CuS/Cu₂S/CdS. Adapted from Ref. [246].

Fig.25 (a) Schematic representation of photodegradation mechanism of the CNT/CuS composite. (b) Photodegradation of RhB of 3% CNT/CuS was used four times. (c) Nyquist plots of CuS (12 h, 20 C) and CNT/CuS composites. (d) Transient photocurrent?time response curves of CuS (12 h, 20 C) and CNT/CuS composites. (e) Effects of IPA, BQ, and MeOH on the photodegradation percentage of RhB over 3% CNT/CuS [32].

Fig.26 SEM images of (a) TiO₂ nanobelts and (b) Au/CuS/CdS/TiO₂ nanobelts. (c) TEM image of Au/CuS/CdS/TiO₂ nanobelts and (d) HRTEM image of Au/CuS/CdS/TiO₂ nanobelts. (e) V_oc response curves. (f) Schematic illustration of the possible photocatalytic mechanism of quaternary composite. (g) Nyquist plots and (h) the photocatalytic stability of quaternary composite on the degradation of moxifloxacin. Reproduced with permission from Ref. [267] (Copyright 2020, Elsevier).

Fig.27 SEM imagesof (a₁) Cu dendrite, (b₁) CuS10 dendrite, (c₁) CuS30 dendrite, and (d₁) CuS50 dendrite. (e₁) Amperometric responses of CuS30 (a), CuS10 (b), CuS50 (c), Cu dendrite (d), and CuS film (e) with stepwise addition of glucose stock solution at 0.55 V. (f₁) The current response of various electrodes from A against the glucose concentration (mmol·L^?1). (g₁) Amperometric response of CuS30 dendrite sensor in successive addition of 1 mmol·L^?1 glucose and 0.1 mmol·L^?1 different interferent species (Fr, Su, AA, DA, UA) in 0.5 mol·L^?1 NaOH at 0.55 V. (h₁) Long-term stability of the CuS30 dendrite electrode measured in 30 d. Reproduced with permission from Ref. [271] (Copyright 2017, Elsevier).

Fig.28 CV curves of (a) CuS-W, (b) CuS-E, and (c) CuS-W/E modified electrode in the absence (Curve a) and presence (Curve b) of 1 mmol·L^?1 glucose in 0.1 mol·L^?1 NaOH solution at 50 mV·s^?1. (d) The bar diagram of peak current against modified electrodes. (e) CV response of CuS-modified GC electrode at 50?500 mV·s^?1 with 1 mmol·L^?1 glucose in 0.1 mol·L^?1 NaOH solution (the inset shows the corresponding calibration plot). (f) Linear sweep voltammetry (LSV) result obtained for glucose in the range of 0?500 μmol·L^?1 (the inset shows the corresponding calibration plot). Amperometric response for the CuS-modified GC electrode (g) at different applied potential with successive addition of 10 μmol·L^?1 glucose in 0.1 mol·L^?1 NaOH and (h) with the addition of different concentrations of glucose in 0.1 mol·L^?1 NaOH solution (the inset shows the corresponding calibration curve of glucose concentration versus peak current response at an applied potential of 0.5 V). Amperometric response of the CuS-modified GC electrode with successive addition of 10 μmol·L^?1 glucose in 0.1 mol·L^?1 NaOH solution: (i) ambient condition; (j) 0.1 mol·L^?1 NaOH solution containing 0.1 mol·L^?1 NaCl; (k) N₂ saturated 0.1 mol·L^?1 NaOH solution. (l) Bar diagram representing normalized current response obtained in amperometric measurement for the addition of glucose (50 μmol·L^?1) and interference compounds (20 μmol·L^?1) at CuS-modified GC electrode in 0.1 mol·L^?1 NaOH at an applied potential of 0.5 V. (m) Schematic representation of the change of morphology caused by different solvents. (n) Schematic illustration of glucose detection using CuS-modified electrode. Reproduced with permission from Ref. [39] (Copyright 2017, Elsevier).

Fig.29 (a)(b)(c) The schematic representation of electromagnetic wave absorption mechanism. The resistance loss (R_L) curves at varied layer thickness at ν = 2?18 GHz: (d) Ti₃C₂T_x MXene; (e) CuS; (f) CuS:Ti₃C₂T_x = 1:1; (g) CuS:Ti₃C₂T_x = 2:1. Reproduced with permission from Ref. [276] (Copyright 2020, Elsevier).

Fig.30 Photothermal curves (808 nm laser) depending on (a) the concentration of CuS/BSA?HMONs aqueous solutions at 1 W·cm^?2, (b) the laser power at 100 μg·mL^?1 of the aqueous solution of composite, and (c) the temperature variation with time at 200 μg·mL^?1 during four cycles of laser on/off at 1.0 W·cm^?2. (d) In vitro DOX release profiles from CuS/BSA?HMONs?DOX at different pH in the absence or presence of 10 mmol·L^?1 GSH. (e) In vitro DOX release profiles from CuS/BSA?HMONs?DOX at different pHs in presence of 10 mmol·L^?1 GSH with NIR laser irradiation (808 nm, 1 W·cm^?2). (f) In vitro photoacoustic (PA) images and its variation with Cu concentrations. Schematic illustration of (g) the formation of CuS/BSA-HMONs-DOX NPs and (h) the mechanism of CuS/BSA?HMONs?DOX as a nano theranostic splatform for in vivo PA imaging-guided tumor synergistic chemotherapy-PTT. Reproduced with permission from Ref. [316] (Copyright 2020, Elsevier).

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