Hollow tubular In2O3 modified carbon nitride for photocatalytic high-yield cleavage of lignin C-C bonds under 395 nm light

doi:10.1016/S1872-2067(25)64924-2

Abstract

Abstract:

The selective cleavage of C_α-C_β bonds is of great significance to lignin valorization, and photocatalysis offers an eco-friendly pathway to achieve this process. Here, graphitic carbon nitride (g-C₃N₄) modified with hollow tubular In₂O₃ was constructed via the calcination method for the photocatalytic cleavage of lignin C_α-C_β bonds. MIL-68(In) was used as the precursor of In₂O₃, imparting a unique hollow tubular structure and a relatively large specific surface area. The hollow tubular structure is helpful for light penetration and scattering, as well as rapid migration of the lignin substrate. The Z-scheme g-C₃N₄/In₂O₃ heterojunction exhibited 92.1% conversion (corresponding benzaldehyde yield: 82.4%) of the lignin model compound 2-phenoxy-1-phenylethanol (PP-ol), outperforming pure In₂O₃ and g-C₃N₄ by 40- and 2.3-fold, respectively, under 395 nm light illumination. By varying the illumination wavelength, the conversion and yields of the g-C₃N₄/In₂O₃ composites were found to follow wavelength-dependent reactivities. Additionally, photogenerated holes are capable of converting PP-ol into benzoic acid, whereas ¹O₂ mainly converts PP-ol into benzaldehyde. This work could encourage the application of metal-organic frameworks in biomass conversion and provide insight into photocatalytic lignin valorization.

Key words: Lignin, C-C bond cleavage, Photocatalysis, Metal-organic frameworks, g-C₃N₄, In₂O₃

Yixin Li, Jianhao Qiu, Guanglu Xia, Qiying Liu, Biyao Fang, Meng Liu, Chen Chen, Jianfeng Yao. Hollow tubular In₂O₃ modified carbon nitride for photocatalytic high-yield cleavage of lignin C-C bonds under 395 nm light[J]. Chinese Journal of Catalysis, 2026, 83: 209-218.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64924-2

https://www.cjcatal.com/EN/Y2026/V83/I4/209

Figures/Tables 6

Fig. 1. (a) Preparation diagram of g-C3N4/M-In2O3 composites. (b) XRD patterns of MIL-68(In), M-In2O3, g-C3N4 and g-C3N4/M-In2O3 composites. (c) FTIR spectra of MIL-68(In), M-In2O3, g-C3N4 and CNMI-30. (d) N2 adsorption-desorption isotherms of M-In2O3, O-In2O3, g-C3N4 and CNMI-30.

Fig. 2. SEM (a) and TEM (b) images of M-In2O3. (c) SEM and TEM images of g-C3N4. SEM (d) and TEM (e,f) images of CNMI-30. (g?k) EDS mapping images of CNMI-30. XPS spectra of M-In2O3, g-C3N4 and CNMI-30: N 1s (l), O 1s (m), and In 3d (n).

Fig. 3. (a) The formula for the photocatalytic Cα-Cβ bond cleavage of PP-ol. Photocatalytic PP-ol conversion over MIL-68(In), M-In2O3, g-C3N4, their composites (b) and CNMI-P (c). (d) Photocatalytic PP-ol conversion over CNMI-30 under different light wavelengths (inset is the UV-vis DRS of CNMI-30). Photocatalytic PP-ol conversion over CNMI-30 with various irradiation times (e) and reaction atmospheres (f).

Fig. 4. Photocurrent curves (a), EIS Nyquist plots (b), TRPD spectra (c) and UV-vis DRS (d) of M-In2O3, g-C3N4 and CNMI-30, corresponding (αhv)2 vs. hv curves (e) and VB XPS spectra (f) of M-In2O3 and g-C3N4.

Fig. 5. (a) Control experiments employing various scavengers for the photocatalytic depolymerization of PP-ol. (b) EPR spectra of TEMP-1O2 adducts over CNMI-30 under dark conditions and following 10-min of light exposure. (c) O2 adsorption isotherms of M-In2O3, g-C3N4, CNMI-30 and O-In2O3.

Fig. 6. Proposed mechanism for the photocatalytic cleavage of the Cα-Cβ bond in PP-ol via CNMI-30.

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Hollow tubular In₂O₃ modified carbon nitride for photocatalytic high-yield cleavage of lignin C-C bonds under 395 nm light

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