2D/2D Coupled ZnIn2S4/TiO2 Heterojunction and Its Enhanced Photocatalytic Reduction of CO2

doi:10.15541/jim20250097

Abstract

Abstract:

As a typical photocatalytic material, titanium dioxide (TiO₂) has been widely applied in environmental remediation and energy conversion due to its excellent chemical stability, non-toxicity and low cost. However, its wide bandgap structure restricts light absorption to ultraviolet wavelengths, and severe recombination of photogenerated electron-hole pairs in bulk materials limits quantum efficiency. Here, a hydrothermal method was used to construct a novel 2D/2D coupled ZnIn₂S₄ (ZIS)@TiO₂ composite material. This heterojunction consists of ultrathin TiO₂ nanocages composited with ZIS nanosheets, exhibiting a unique hollow core-shell morphology. ZIS-T20 catalyst with composite 20 mg TiO₂ nanocages demonstrates significantly enhanced light absorption across a broad wavelength range of 400-720 nm. Under influence of the built-in electric field, photo-generated electrons cannot migrate from conduction band (CB) of ZIS to that of TiO₂, whereas the transfer of holes from valence band (VB) of ZIS to that of TiO₂ proceeds unimpededly. This spatial separation effect preserves electrons with high reduction potential in ZIS, overcoming inherent drawback of reduced redox capability in conventional type-I heterojunctions. In photocatalytic CO₂ reduction (PCR) reaction, ZIS@TiO₂ exhibits improved performance, achieving CO and CH₄ production rates of 58.87 and 12.03 μmol·g^-1·h^-1, respectively, with CO selectivity as high as 83.03%. Compared to individual components, the CO yield is 6.15 and 1.96 times higher than that of pristine ZIS and TiO₂, respectively. This work not only provides a new strategy for designing efficient 2D/2D heterojunction photocatalysts, but also offers valuable insights into understanding interfacial charge transfer mechanisms.

Key words: 2D/2D coupling, TiO₂ nanosheet, photocatalytic CO₂ reduction, heterojunction, ZnIn₂S₄

CLC Number:

TQ426

ZHU Jianhua, YANG Xin, RU Lingjie. 2D/2D Coupled ZnIn₂S₄/TiO₂Heterojunction and Its Enhanced Photocatalytic Reduction of CO₂[J]. Journal of Inorganic Materials, 2026, 41(2): 177-185.

Figures/Tables 9

Fig. 1 Morphologies and microstructures of materials (a) SEM and (b) TEM images of 125-Tyr; (c) SEM and (d) TEM images of ZIS; (e) SEM, (f) TEM and (g) HRTEM images of ZIS-T20; (h) Line scan of ZIS-T20; (i-m) Distributions of elements for ZIS-T20. Colorful figures are available on website

Fig. 2 (a) XRD patterns and (b) FT-IR spectra of materials Inset in (b) indicates the local magnification of ZIS. Colorful figures are available on website

Fig. 3 Physical and chemical properties of materials (a) N2 adsorption-desorption curves with inset showing the corresponding pore size distributions; (b) CO2 adsorption curves; (c) CO2-TPD profiles; (d) UV-Vis diffuse reflectance spectra with inset showing (αhv)2 versus hv plots; (e, f) Mott-Schottky spectra of (e) ZIS and (f) 125-Tyr. Colorful figures are available on website

Fig. 4 Quasi-in situ XPS spectra (a) Total spectra; (b) Zn2p, (c) In3d, (d) S2p, (e) Ti2p, and (f) O1s XPS spectra of ZIS-T20 before and under light irradiation

Fig. 5 Photoelectric performance tests of materials (a) Steady-state PL spectra; (b) TRPL spectra; (c) Transient photocurrents; (d) EIS plots. Colorful figures are available on website

Fig. 6 Photocatalytic performance tests of materials (a) Photocatalytic CO2 reduction rates of different samples; (b) Photocatalytic products of ZIS-T20 for 8 h; (c) Photocatalytic cycle tests of ZIS-T20; (d) Isotope trace of photocatalytic products

Table 1 Reported catalysts and their photocatalytic effects

Material	Photoreactor condition	Product	Production rate/ (μmol·g⁻¹·h⁻¹)	Ref.
Porous TiO₂ (B)	300 W Xe-lamp	CH₄CH₃OH	0.23 0.08	[40]
TiO₂ anatase	90 mW/cm² solar simulator	CO	0.55	[41]
Pure ZnIn₂S₄	300 W Xe-lamp	CO CH₄	1.56 0.026	[42]
3D-ZnIn₂S₄/TiO₂	300 W Xe-lamp	CH₄	1.135	[43]
2D/2D ZIS-T20	300 W Xe-lamp	CO CH₄	58.87 12.03	This work

Fig. 7 In situ DRIFTS spectra of ZIS-T20 during PCR reaction

Fig. 8 Schematic diagram of ZIS-T20 for PCR

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2D/2D Coupled ZnIn₂S₄/TiO₂Heterojunction and Its Enhanced Photocatalytic Reduction of CO₂

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