中空管状In2O3修饰氮化碳395 nm光催化木质素C-C键高产率裂解

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

催化学报 ›› 2026, Vol. 83: 209-218.DOI: 10.1016/S1872-2067(25)64924-2

中空管状In₂O₃修饰氮化碳395 nm光催化木质素C-C键高产率裂解

李伊馨, 邱健豪^*(), 夏广路, 刘琪英, 方碧瑶, 刘梦, 陈晨, 姚建峰^*()

南京林业大学化学工程学院, 森林食物资源挖掘与利用全国重点实验室, 江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2025-08-18 接受日期:2025-10-17 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: jhq@njfu.edu.cn (邱健豪), jfyao@njfu.edu.cn (姚建峰).
基金资助:
国家重点研发项目(2024YFB4206003)

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

Yixin Li, Jianhao Qiu^*(), Guanglu Xia, Qiying Liu, Biyao Fang, Meng Liu, Chen Chen, Jianfeng Yao^*()

National Key Laboratory for the Development and Utilization of Forest Food Resources, Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2025-08-18 Accepted:2025-10-17 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: jhq@njfu.edu.cn (J. Qiu), jfyao@njfu.edu.cn (J. Yao).
Supported by:
National Key Research and Development Program of China(2024YFB4206003)

摘要/Abstract

摘要：

在全球可持续发展战略背景下, 生物质资源高效转化成为研究焦点. 木质素作为富含芳香结构的可再生原料, 是高值化学品的重要来源, 但其C_α-C_β键解离能高, 选择性断裂难度大. 相较于热催化木质素转化, 光催化技术具有绿色、可持续且选择性较高的优势, 具有较大的潜力. 石墨相氮化碳(g-C₃N₄)作为一种较为绿色的光催化剂, 能够通过π-π堆积作用活化木质素底物. 但存在比表面积较小、光生载流子复合较快等问题, 通过异质结构建能够有效解决上述问题. MOF衍生的金属氧化物能够在一定程度上维持MOF的形貌, 并具备较高的稳定性、较窄的带隙能、较大的比表面积和介孔结构, 有效增强传质并促进活性物种的生成.
本研究旨在开发Z型g-C₃N₄/中空管状In₂O₃异质结用于光催化选择性断裂木质素C-C键. 其中, 具有中空管状结构的In₂O₃是由MIL-68(In)煅烧制备. 首先制备呈规则棱柱状结构的MIL-68(In)与g-C₃N₄, 经均匀混合后通过煅烧制得复合材料. MOF衍生的In₂O₃比表面积为48 m²·g^-1, 显著高于常规方法制备的In₂O₃ (比表面积: 3 m²·g^-1), 复合材料的比表面积进一步提升至76 m²·g^-1, 且性能明显优于In₂O₃与g-C₃N₄. 以含C_α-C_β键的2-苯氧基-1-苯乙醇(PP-ol)为木质素模型底物, 在395 nm光照下测试催化性能, 结果显示复合材料的PP-ol转化率达92.1%, 苯甲醛收率为82.4%, 显著高于单一组分及物理混合样品. 不同波长实验结果表明, 反应效率与光吸收曲线高度吻合; 不同气氛实验证明, 空气气氛下反应高效, 纯O₂可进一步提升性能, 氮气中则几乎无反应, 证明O₂是该反应高效进行的关键因素; 连续4次循环后, 催化剂活性与结构保持稳定. 此外, 该材料对其他3种木质素β-O-4模型物的转化率均超80%, 对有机溶剂法提取的桦木木质素的解聚效果显著, 产物以芳香醛、酯类为主. 光电化学测试证实了Z型异质结的形成有效促进了光生载流子的分离与迁移; 活性物种捕获与电子顺磁共振实验证实, ¹O₂是C_α-C_β键断裂的关键物种, 主要将PP-ol转化成苯甲醛, 光生空穴可将PP-ol转化为苯甲酸. 中空管状In₂O₃的高比表面积及孔隙率有效提升了O₂吸附, 促进了¹O₂的生成. 光照下, In₂O₃与g-C₃N₄受激发产生电子-空穴对, 由于形成了Z型异质结, g-C₃N₄导带电子将O₂还原为•O₂^-, 后者经空穴氧化生成¹O₂; In₂O₃价带空穴从C_β-H提取氢生成C_β自由基并与¹O₂及氢质子结合形成过氧化物中间体, 经六元环过渡态后发生C_α-C_β键断裂, 最终生成苯甲醛和甲酸苯酯.
综上, Z型g-C₃N₄/In₂O₃异质结通过中空结构增强O₂吸附、光利用及木质素底物传质, 异质结促进载流子分离, 实现了在温和条件下高效断裂木质素C_α-C_β键. 这项工作可促进金属有机框架材料在生物质转化中的应用, 并为光催化木质素的选择性解聚提供启示.

关键词: 木质素, C-C键断裂, 光催化, 金属有机框架, g-C₃N₄, In₂O₃

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

李伊馨, 邱健豪, 夏广路, 刘琪英, 方碧瑶, 刘梦, 陈晨, 姚建峰. 中空管状In₂O₃修饰氮化碳395 nm光催化木质素C-C键高产率裂解[J]. 催化学报, 2026, 83: 209-218.

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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图/表 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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中空管状In₂O₃修饰氮化碳395 nm光催化木质素C-C键高产率裂解

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

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