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. 2024 May 26;29(11):2514.
doi: 10.3390/molecules29112514.

A Convenient In Situ Preparation of Cu2ZnSnS4-Anatase Hybrid Nanocomposite for Photocatalysis/Photoelectrochemical Water-Splitting Hydrogen Production

Ke-Xian Li  1   2   3 , Cai-Hong Li  1   3   4 , Hao-Yan Shi  1   3 , Rui Chen  1   3 , Ao-Sheng She  1   3 , Yang Yang  1   2   3 , Xia Jiang  1   3 , Yan-Xin Chen  1   2   3 , Can-Zhong Lu  1   2   3
Affiliations

A Convenient In Situ Preparation of Cu2ZnSnS4-Anatase Hybrid Nanocomposite for Photocatalysis/Photoelectrochemical Water-Splitting Hydrogen Production

Ke-Xian Li et al. Molecules. .

Abstract

This study details the rational design and synthesis of Cu2ZnSnS4 (CZTS)-doped anatase (A) heterostructures, utilizing earth-abundant elements to enhance the efficiency of solar-driven water splitting. A one-step hydrothermal method was employed to fabricate a series of CZTS-A heterojunctions. As the concentration of titanium dioxide (TiO2) varied, the morphology of CZTS shifted from floral patterns to sheet-like structures. The resulting CZTS-A heterostructures underwent comprehensive characterization through photoelectrochemical response assessments, optical measurements, and electrochemical impedance spectroscopy analyses. Detailed photoelectrochemical (PEC) investigations demonstrated notable enhancements in photocurrent density and incident photon-to-electron conversion efficiency (IPCE). Compared to pure anatase electrodes, the optimized CZTS-A heterostructures exhibited a seven-fold increase in photocurrent density and reached a hydrogen production efficiency of 1.1%. Additionally, the maximum H2 production rate from these heterostructures was 11-times greater than that of pure anatase and 250-times higher than the original CZTS after 2 h of irradiation. These results underscore the enhanced PEC performance of CZTS-A heterostructures, highlighting their potential as highly efficient materials for solar water splitting. Integrating Cu2ZnSnS4 nanoparticles (NPs) within TiO2 (anatase) heterostructures implied new avenues for developing earth-abundant and cost-effective photocatalytic systems for renewable energy applications.

Keywords: Cu2ZnSnS4–anatase nanocomposite; copper-based sulfides; heterojunction; photocatalytic H2 generation.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
XRD patterns of the Cu2SnZnS4 (CZTS), the anatase TiO2, and the CZTS–AX (X = 1, 3, 5, 7, 9).
Figure 2
Figure 2
SEM and EDS-mapping images (Cu, Zn, S, Sn, O, and Ti) of (a–d) anatase; (e–k) CZTS; (l–u) CZTS–A5.
Figure 3
Figure 3
The TEM/HRTEM images and the corresponding SAED patterns of (a,b) CZTS and (c,d) CZTS–A5.
Figure 4
Figure 4
XPS spectra of the CZTS NPs and the CZTS–A5 nanocomposites, which involve (a) Cu 3d, (b) Zn 2p, (c) Sn 3d, (d) S 2p, (e) Ti 2p, and (f) O 1s.
Figure 5
Figure 5
CZTS, TiO2 (anatase), and CZTS–AX (X = 1, 3, 5, 7, 9) nanocomposites of FTIR spectra (a), CZTS, TiO2 (anatase), and CZTS–A5 nanocomposites of (b) UV–Vis analysis, (c,d) EPR spectra of CZTS NPs, TiO2 (anatase) NPs, and hybrid CZTS–A5 nanocomposites recorded at room temperature. (e,f) N2 adsorption–desorption isotherms of CZTS NPs, hybrid CZTS–A5 nanocomposites, and TiO2 (anatase).
Figure 6
Figure 6
(a,b) CZTS NPs, hybrid CZTS–A5 nanocomposites, and TiO2 (anatase) photocatalyzes the water–splitting H2 generation for 10 h using ethanol as a sacrificial agent under full spectrum light (the slopes associated with the hydrogen reaction rate simulations are 0.613, 0.414, 0.374, 0.274, and 0.177 mmol/g/h, respectively); (c) The photocatalytic activity of CZTS, CZTS–A5, and TiO2 (anatase) with the existence of ethanol as a sacrificial agent for 10 h; (d) Cyclic test of H2 generation in CZTS–A5 samples under full spectrum light irradiation; (e) Chopped linear sweep voltammetry (LSV) curve; and (f) chrono amperometry data plot of CZTS, CZTS–A5, and TiO2 (anatase) samples observed under the bias voltage of 1.5V (vs. RHE, the electrolyte is 0.5 M Na2SO4, pH = 6).
Figure 7
Figure 7
Relationship between photocurrent density and monochromatic light in electrochemical noise (ECN) mode (a) and photocurrent density and monochromatic light to generate IPCE (%) spectra (b); spectra of the relationship between photocurrent density and IPCE (%) spectra evaluated at different wavelengths of monochromatic light by applying different bias voltages (c,d) (electrolyte is 0.5 M Na2SO4, pH = 6).
Figure 8
Figure 8
(a) Band gap plot determined by examining the relationship between (IPCE% × hv)1/2 and photon energy (hv); (b) EIS impedance plot; (c) Mott–Schottky plot.
Figure 9
Figure 9
Proposed band gap structure diagram of the Cu2SnZnS4–TiO2 (anatase) hybrid nanocomposites.
Figure 10
Figure 10
Schematic illustration for the fabrication strategy of the CZTS and the CZTS–Ax nanocomposite.
See this image and copyright information in PMC

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