木质纤维素基生物质炭改性半导体及其光催化应用

doi:10.16085/j.issn.1000-6613.2024-0295

摘要/Abstract

摘要：

因木质纤维素基生物质炭具有表面官能团丰富、结构易于调控及化学性质稳定等优点，其被广泛应用于催化、吸附及电化学等领域。其中，在光催化材料的构筑中，生物质炭能够改善半导体吸光差、光生载流子分离效率低、活性位点较少、比表面积较小等问题，进而优化其光催化性能。本文重点讨论了纤维素和木质素基生物质炭用于不同半导体（TiO₂、g-C₃N₄及ZnO等）的改性，改性方式包括复合改性和掺杂改性，复合改性又分为碳点复合和以炭为载体两种形式。同时，详细介绍了改性后的催化剂在各种光催化应用[光催化有机污染物降解、Cr(Ⅵ)还原、产氢及产H₂O₂等]中的性能表现。最后，从催化材料设计和光催化应用角度分别讨论了木质纤维素基生物质炭改性半导体用于光催化的研究现状及存在的问题，并提出了相应的解决方案。另外，还展望了该领域的未来发展前景。本文能够为生物质衍生炭的应用及光催化材料的设计提供较为深入的见解和指引。

关键词: 纤维素, 木质素, 生物质炭, 半导体, 光催化

Abstract:

Lignocellulose-derived biochar has been widely used in the fields of catalysis, adsorption and electrochemistry due to its merits including abundant surface functional groups, tunable structures and stable chemical properties. Among them, in the construction of photocatalysts, biochar can improve the weak light absorption, low separation efficiency of photo-generated charge carriers, insufficient active sites and low specific surface area of semiconductors so as to optimize their photocatalytic performances. This review mainly focused on different semiconductors (TiO₂, g-C₃N₄ and ZnO, etc.) decorated by cellulose and lignin-derived biochar. The modification strategies included carbon combination and carbon doping, and the strategy of carbon combination could be further distinguished into carbon dot combination and carbon as scaffolds. Meanwhile, performances of modified catalysts in diverse photocatalytic applications (photocatalytic degradation of organic pollutants, reduction of Cr(Ⅵ), H₂ evolution and H₂O₂ production, et al.) were introduced in detail. Finally, the research status and existing problems of lignocellulose-derived biochar-modified semiconductors for photocatalysis were discussed respectively from the perspective of catalyst design and photocatalytic application, and the corresponding solutions were proposed. In addition, the future development prospects in this field were also presented. This review could provide insight and guidance on the application of biomass-derived carbon and the design of photocatalysts.

Key words: cellulose, lignin, biochar, semiconductor, photocatalysis

中图分类号:

TB34

方碧瑶, 邱健豪, 李伊馨, 姚建峰. 木质纤维素基生物质炭改性半导体及其光催化应用[J]. 化工进展, 2025, 44(2): 957-970.

FANG Biyao, QIU Jianhao, LI Yixin, YAO Jianfeng. Lignocellulose-derived biochar-modified semiconductors and their photocatalytic applications[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 957-970.

图/表 12

参考文献 71

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半导体	形态	制备方法	应用	降解/生成率	光源	参考文献
TiO₂	片状	焙烧	四环素降解	100%	可见光	[11]
TiO₂	块状	焙烧	Cr(Ⅵ)还原	100%	可见光	[20]
TiO₂	珠状	焙烧	头孢曲松钠降解	91.92%	可见光	[22]
TiO₂	原子	焙烧	二嗪磷降解	98.34%	可见光	[23]
TiO₂	原子	水热	双酚A降解	79%	太阳光	[24]
TiO₂	点状	焙烧	亚甲基蓝降解	92%	可见光	[27]
TiO₂	点状	水热	罗丹明B降解、Cr(Ⅵ)还原	84%(膜)/100%(气凝胶)	可见光	[8]
TiO₂	原子	水热	亚甲基蓝降解	85%	可见光	[28]
TiO₂	块状	焙烧	甲基橙降解	100%	紫外光	[54]
g-C₃N₄	纤维状	焙烧	H₂O₂制备	1.1mmol·L^-1·h^-1	可见光	[29]
g-C₃N₄	纤维状	焙烧	H₂O₂制备	58.67μmol·L^-1·h^-1	可见光	[31]
g-C₃N₄	纳米管状	水热	双酚A降解	91%	可见光	[32]
g-C₃N₄	块状	水热	亚甲基蓝降解	72.04%	可见光	[33]
g-C₃N₄	原子	焙烧	H₂制备	1.41mmol·L^-1·h^-1	可见光	[34-35]
g-C₃N₄	纤维状	水热	亚甲基蓝降解	99.9%	可见光	[36]
ZnO	点状	水热	亚甲基蓝降解	100%	太阳光	[39]
ZnO	点状	水热	Cr(Ⅵ)还原	96.2%	紫外光	[40]
ZnO	棒状	焙烧	苯酚降解	99.8%	可见光	[43]
ZnO	原子	焙烧	甲基橙降解	79.78%	紫外光	[44]
ZnO	原子	水热	亚甲基蓝降解	100%	紫外光	[37]
ZnIn₂S₄	点状	水热	5-羟甲基糠醛氧化	2980μmol·g^-1	可见光	[45]
Fe₂O₃	点状	脱水氧化	靛蓝胭脂红降解	100%	可见光	[10]
α-FeOOH	点状	水热	Cr(Ⅵ)还原	100%	紫外光	[46]
SiO₂	块状	焙烧	四环素降解	90%	可见光	[47]
CoFe₂O₄	球状	水热	罗丹明B降解	100%	可见光	[48]
BiOBr	纤维状	焙烧	罗丹明B降解	100%	可见光	[49]
ZrO₂	原子	焙烧	Cr(Ⅵ)还原	99.8%	可见光	[50]
Ni/NiO	块状	焙烧	H₂制备	13.5mmol·g^-1·h^-1	可见光	[51]
SrTiO₃	纤维状	焙烧	四环素降解	99.7%	紫外光	[55]

半导体	形态	制备方法	应用	降解/生成率	光源	参考文献
TiO₂	片状	焙烧	四环素降解	100%	可见光	[11]
TiO₂	块状	焙烧	Cr(Ⅵ)还原	100%	可见光	[20]
TiO₂	珠状	焙烧	头孢曲松钠降解	91.92%	可见光	[22]
TiO₂	原子	焙烧	二嗪磷降解	98.34%	可见光	[23]
TiO₂	原子	水热	双酚A降解	79%	太阳光	[24]
TiO₂	点状	焙烧	亚甲基蓝降解	92%	可见光	[27]
TiO₂	点状	水热	罗丹明B降解、Cr(Ⅵ)还原	84%(膜)/100%(气凝胶)	可见光	[8]
TiO₂	原子	水热	亚甲基蓝降解	85%	可见光	[28]
TiO₂	块状	焙烧	甲基橙降解	100%	紫外光	[54]
g-C₃N₄	纤维状	焙烧	H₂O₂制备	1.1mmol·L^-1·h^-1	可见光	[29]
g-C₃N₄	纤维状	焙烧	H₂O₂制备	58.67μmol·L^-1·h^-1	可见光	[31]
g-C₃N₄	纳米管状	水热	双酚A降解	91%	可见光	[32]
g-C₃N₄	块状	水热	亚甲基蓝降解	72.04%	可见光	[33]
g-C₃N₄	原子	焙烧	H₂制备	1.41mmol·L^-1·h^-1	可见光	[34-35]
g-C₃N₄	纤维状	水热	亚甲基蓝降解	99.9%	可见光	[36]
ZnO	点状	水热	亚甲基蓝降解	100%	太阳光	[39]
ZnO	点状	水热	Cr(Ⅵ)还原	96.2%	紫外光	[40]
ZnO	棒状	焙烧	苯酚降解	99.8%	可见光	[43]
ZnO	原子	焙烧	甲基橙降解	79.78%	紫外光	[44]
ZnO	原子	水热	亚甲基蓝降解	100%	紫外光	[37]
ZnIn₂S₄	点状	水热	5-羟甲基糠醛氧化	2980μmol·g^-1	可见光	[45]
Fe₂O₃	点状	脱水氧化	靛蓝胭脂红降解	100%	可见光	[10]
α-FeOOH	点状	水热	Cr(Ⅵ)还原	100%	紫外光	[46]
SiO₂	块状	焙烧	四环素降解	90%	可见光	[47]
CoFe₂O₄	球状	水热	罗丹明B降解	100%	可见光	[48]
BiOBr	纤维状	焙烧	罗丹明B降解	100%	可见光	[49]
ZrO₂	原子	焙烧	Cr(Ⅵ)还原	99.8%	可见光	[50]
Ni/NiO	块状	焙烧	H₂制备	13.5mmol·g^-1·h^-1	可见光	[51]
SrTiO₃	纤维状	焙烧	四环素降解	99.7%	紫外光	[55]

半导体	形态	制备方法	应用	降解/生成率	光源	参考文献
TiO₂	块状	水热	亚甲基蓝降解	100%	可见光	[57]
TiO₂	球状	水热	布洛芬、双氯芬酸降解	100%/100%	太阳光	[58]
TiO₂	块状	—	对乙酰氨基酚降解	43.3%	太阳光	[68]
TiO₂	纤维状	焙烧	罗丹明B降解	100%	可见光	[59]
g-C₃N₄	点状	水热	Cr(Ⅵ)还原、左氟沙星降解	100%/94.8%	可见光	[60]
g-C₃N₄	点状	焙烧	亚甲基蓝、木质素降解	94.6%/93.1%	可见光	[61]
g-C₃N₄	块状	焙烧	四环素降解	87.05%	可见光	[62]
ZnO	块状	焙烧	甲基橙	100%	太阳光	[56]
ZnO	片状	焙烧	甲基橙降解	100%	太阳光	[63]
ZnO	块状	焙烧	亚甲基蓝降解	96.3%	可见光	[9]
ZnO	花状	焙烧	磺胺二甲嘧啶降解、H₂制备	95%/29.0μmol·h^-1	太阳光	[64]
BiOBr	块状	水热	四环素降解、Cr(Ⅵ)还原	78.1%/100%	可见光	[65]
BiOBr	原子	水热	罗丹明B降解	99.2%	可见光	[66]
Bi₂O₃	原子	焙烧	土霉素降解	40%	可见光	[67]

半导体	形态	制备方法	应用	降解/生成率	光源	参考文献
TiO₂	块状	水热	亚甲基蓝降解	100%	可见光	[57]
TiO₂	球状	水热	布洛芬、双氯芬酸降解	100%/100%	太阳光	[58]
TiO₂	块状	—	对乙酰氨基酚降解	43.3%	太阳光	[68]
TiO₂	纤维状	焙烧	罗丹明B降解	100%	可见光	[59]
g-C₃N₄	点状	水热	Cr(Ⅵ)还原、左氟沙星降解	100%/94.8%	可见光	[60]
g-C₃N₄	点状	焙烧	亚甲基蓝、木质素降解	94.6%/93.1%	可见光	[61]
g-C₃N₄	块状	焙烧	四环素降解	87.05%	可见光	[62]
ZnO	块状	焙烧	甲基橙	100%	太阳光	[56]
ZnO	片状	焙烧	甲基橙降解	100%	太阳光	[63]
ZnO	块状	焙烧	亚甲基蓝降解	96.3%	可见光	[9]
ZnO	花状	焙烧	磺胺二甲嘧啶降解、H₂制备	95%/29.0μmol·h^-1	太阳光	[64]
BiOBr	块状	水热	四环素降解、Cr(Ⅵ)还原	78.1%/100%	可见光	[65]
BiOBr	原子	水热	罗丹明B降解	99.2%	可见光	[66]
Bi₂O₃	原子	焙烧	土霉素降解	40%	可见光	[67]

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