硅酸盐学报

等离子体协同S型Bi@Bi₂S₃/CeO₂复合纤维可控合成及CO₂光还原

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曹铁平 ¹ , 李跃军 ¹^,² , 孙大伟 ²

硅酸盐学报 | 研究论文 2026,54(1): 184-194

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硅酸盐学报 |研究论文 2026 , 54 (1) : 184 -194

等离子体协同S型Bi@Bi₂S₃/CeO₂复合纤维可控合成及CO₂光还原

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曹铁平¹, 李跃军¹^,², 孙大伟²

作者信息

^1．海南科技职业大学化学与材料工程学院，海口 571126

^2．白城师范学院化学学院，吉林白城 137000

通讯作者:

李跃军（1964—），男，教授。

作者简介:

曹铁平（1964—），女，教授。

Photoreduction of CO₂ with S-Scheme Bi@Bi₂S₃/CeO₂ Composite Fibers Assisted by Plasma

Tieping CAO¹, Yuejun LI¹^,², Dawei SUN²

Affiliations

^1.College of Chemistry and Materials Engineering, Hainan Vocational University of Science and Technology, Haikou 570100, China

^2.College of Chemistry, Baicheng Normal University, Baicheng 137000, Jilin, China

Corresponding Author:

LI Yuejun (1964-), male, Professor. E-mail: bc640628@163.com

CAO Tieping (1964-), female, Professor. E-mail: bcctp2008@163.com

出版时间: 2026-01-20 doi: 10.14062/j.issn.0454-5648.20250226

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摘要

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针对传统光催化剂载流子复合严重、CO₂吸附活化不足的难题，通过静电纺丝-水热两步法合成了Bi@Bi₂S₃/CeO₂复合纤维。扫描电子显微镜与透射电子显微镜揭示，Bi₂S₃以不同形貌构筑于CeO₂纤维表面，原位生成的Bi纳米颗粒均匀锚定在Bi₂S₃表面，形成独特的三维立体结构。X射线光电子能谱与电子顺磁共振谱证实，Bi₂S₃与CeO₂通过S型异质结实现载流子定向分离，高活性电子保留在Bi₂S₃导带用于CO₂还原，强氧化空穴留存于CeO₂价带驱动水氧化；Bi纳米颗粒的表面等离子体共振（SPR）效应使可见光吸收能力增强，同时可为体系分流更多高活性电子。在模拟太阳光照下，Bi@Bi₂S₃/CeO₂复合纤维生成CO速率达14.58 μmol·g^-1·h^-1（选择性72%），是纯CeO₂纳米纤维的10倍，同时有部分CH₄生成（5.68 μmol·g^-1·h^-1）。5次循环后活性仍保持90%以上。通过分级结构设计，协同S型异质结与SPR效应，为解决CeO₂基催化剂的性能瓶颈，实现CO₂光还原提供了“结构-界面-组分”三重调控的新模式。

关键词

表面等离子体共振 / S型异质结 / Bi@Bi₂S₃/CeO₂复合纤维 / 可控合成

Abstract

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Introduction

The photocatalytic CO₂ reduction technology has become a research hotspot in the field of carbon neutrality because it can simultaneously achieve "carbon fixation + solar energy conversion". CeO₂ has been widely applied in the field of photocatalysis due to the advantages of CO₂ adsorption by oxygen vacancies (Ce³⁺-O^-) and the carrier buffering capacity of the Ce³⁺/Ce⁴⁺redox couple. Bi₂S₃, due to its narrow bandgap (1.3–1.7 eV), unique layered structure, and broad light absorption range, has become an ideal candidate for broadening the spectral response. When constructing a heterojunction between Bi₂S₃ and CeO₂, the oxygen vacancies of CeO₂ can serve as CO₂ adsorption anchors, and the built-in electric field at the interface between the two can promote the directional migration of electrons and holes. In-situ introduction of metallic Bi nanoparticles can enhance the visible light absorption through the Surface Plasmon Resonance (SPR) effect and further inhibit the recombination of photogenerated carriers as electron traps. Meanwhile, one-dimensional nanofibers, because of their high aspect ratio, continuous pore structure, and mechanical stability, not only provide a three-dimensional template for the in-situ growth of Bi@Bi₂S₃, but also form microchannels through the interweaving of fibers, promoting the diffusion of CO₂ and the desorption of products, making them an ideal choice for photocatalytic carriers.

Experiment In this study, CeO₂ fibers prepared by the electrospinning technique were used as the substrate, ascorbic acid was used as the reducing agent, and deionized water, ethylene glycol, ethanol, and ethylenediamine were used as solvents respectively. Combined with the hydrothermal synthesis method, Bi@Bi₂S₃ composite CeO₂ nanofibers in the shapes of nanosheets, nanospheres, nanorods, and nanocubes were prepared. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) revealed that Bi₂S₃ was constructed on the surface of CeO₂ fibers in different morphologies, and the in-situ generated Bi nanoparticles were uniformly anchored at the interface of Bi₂S₃, forming a unique three-dimensional structure. X-ray Photoelectron Spectroscopy (XPS) and Electron Paramagnetic Resonance (EPR) confirmed that Bi₂S₃ and CeO₂ achieved directional separation of carriers through a type-S heterojunction. Highly active electrons were retained in the conduction band of Bi₂S₃ for CO₂ reduction, and strongly oxidizing holes were retained in the valence band of CeO₂ to drive water oxidation. The SPR effect of Bi nanoparticles enhanced the visible light absorption ability, and at the same time, they served as electron bridges to shorten the charge migration path.

Results and discussion

The photocatalytic CO₂ reduction reaction was carried out using a self-made airtight reaction device, with a 300 W Xe lamp (AM 1.5G filter, 100 mW·cm^-2) as the light source to simulate sunlight. After 3 hours of light irradiation, the Bi@Bi₂S₃/CeO₂ ternary composite fiber system showed excellent photocatalytic CO₂ activity. Among them, the nanosheet structure, with its high specific surface area and large pore volume, could form more active sites, resulting in the best photocatalytic CO₂ reduction effect. The yields of CO and CH₄ reached 14.58 μmol·g^-1·h^-1and 5.68 μmol·g^-1·h^-1respectively. Different structural characteristics such as the high light absorption efficiency of the cavity in the pompon structure, the strong local electric field at the edges of the cube structure, and the rapid separation of products in the rod-like structure all effectively improved the CO₂ reduction efficiency. The generation rates of CO were 12.26, 11.71, and 10.55 μmol·g^-1·h^-1 respectively, and the generation rates of CH₄ also reached 4.34, 4.12, and 3.38 μmol·g^-1·h^-1respectively. Meanwhile, the Bi@Bi₂S₃/CeO₂ ternary composite fibers showed good photocatalytic stability. Under the above reaction conditions, after 5 consecutive cycles (accumulated 15 hours), the yields of CO and CH₄ still remained above 90% of the initial values.

Conclusion

In this study, a Bi@Bi₂S₃/CeO₂ composite photocatalyst was successfully prepared using CeO₂ nanofibers as the substrate and combining the hydrothermal method. Material characterization showed that Bi₂S₃ and CeO₂ constructed a S-scheme heterojunction through interfacial interaction, achieving efficient separation of photogenerated carriers. Highly active electrons were retained in the conduction band of Bi₂S₃ for CO₂ reduction, and holes were retained in the valence band of CeO₂ to drive water oxidation. The Bi nanoparticles deposited on the surface enhanced the visible light absorption through the SPR effect, and served as electron bridges to accelerate charge migration and prolong the lifetime of photogenerated carriers. Bi@Bi₂S₃/CeO₂ showed excellent photocatalytic CO₂ reduction performance. This study provides a new idea for the design of efficient CeO₂-based photocatalysts: retaining highly active carriers through a S-scheme heterojunction and optimizing light absorption and charge transfer by combining the SPR effect of non-noble metal nanoparticles. This strategy has important reference value for the development of low-cost and highly stable CO₂ reduction catalysts and is expected to promote the practical application of photocatalytic technology in the field of carbon cycle.

Key words

plasmon synergy / S-scheme heterojunction / Bi@Bi₂S₃/CeO₂ composite fibers / controlled synthesis

引用本文

曹铁平, 李跃军, 孙大伟. 等离子体协同S型Bi@Bi₂S₃/CeO₂复合纤维可控合成及CO₂光还原. 硅酸盐学报, 2026 , 54 (1) : 184 -194 . DOI: 10.14062/j.issn.0454-5648.20250226

Tieping CAO, Yuejun LI, Dawei SUN. Photoreduction of CO₂ with S-Scheme Bi@Bi₂S₃/CeO₂ Composite Fibers Assisted by Plasma[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (1) : 184 -194 . DOI: 10.14062/j.issn.0454-5648.20250226

基金

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国家自然科学基金(21573003)

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2026年第54卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250226

接收时间：2025-03-23
首发时间：2026-10-27
出版时间：2026-01-20

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收稿日期：2025-03-23
修回日期：2025-05-01

基金

国家自然科学基金(21573003)

作者信息

^1．海南科技职业大学化学与材料工程学院，海口 571126

^2．白城师范学院化学学院，吉林白城 137000

通讯作者:

李跃军（1964—），男，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250226

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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