原位制备具有增强光催化活性的S型Bi2Se3/g-C3N4光催化剂

doi:10.1016/S1872-2067(21)63911-6

摘要/Abstract

摘要：

光催化氧化是一种应用前景良好的环境治理技术. 与絮凝、物理吸附和化学氧化等常见的方法相比, 光催化氧化具有环境友好、氧化完全、方便和廉价等优势. 特别是可见光光催化氧化, 可利用太阳能中占比最高的可见光, 在应用中更具优势. 因而, 探索可见光响应性能优异的光催化剂一直是光催化氧化领域的一个重要研究内容.
硒化铋(Bi₂Se₃)是一种带隙(带隙宽度在0.3~1.3 eV)非常窄的半导体, 能吸收全部波长范围的可见光和近红外光. 此外, Bi₂Se₃还具有独特的金属表面态, 其表面具有良好的导电性. 这些特性使其在可见光光催化氧化领域具有很大的应用潜力. 然而, 由于Bi₂Se₃价带位置高, 氧化能力很弱, 其价带上的空穴在光催化反应中难以被消耗, 导致空穴大量累积, 并迅速与光生电子复合, 大幅降低了Bi₂Se₃的光催化性能. 因此, 一直以来, Bi₂Se₃很少被用于光催化反应. 如何充分利用Bi₂Se₃的光响应优势, 制备出性能优异的光催化剂, 仍是具有挑战性和吸引力的研究方向.
本文采用预先制备的Bi₂O₃/g-C₃N₄复合物作为前驱体, 通过原位转化的方法, 将前驱体置于热的Se蒸汽中, 使前驱体上的Bi₂O₃与Se蒸汽反应, 完全转化为Bi₂Se₃纳米颗粒, 从而制得Bi₂Se₃/g-C₃N₄复合光催化剂(Bi₂Se₃含量约为4 wt%). 透射电镜结果表明, 所形成的Bi₂Se₃纳米颗粒较均匀地分布在g-C₃N₄表面. 表面功函数分析发现, Bi₂Se₃与g-C₃N₄结合后, 它们的费米能级分别由原来的‒0.55和‒0.18 eV变为平衡时的‒0.22 eV, 可形成指向g-C₃N₄的内建电场, 有利于形成梯型(S型)异质结. 在此基础上, 能级位移、荧光分析、结构计算和反应自由基测试等结果表明, Bi₂Se₃和g-C₃N₄之间形成了S型异质结. 在可见光光催化降解苯酚的实验中, 所制备的Bi₂Se₃/g-C₃N₄复合物的光催化活性明显优于单一的Bi₂Se₃和g-C₃N₄. 结合比表面、孔结构、光吸收和荧光等对比分析, 认为Bi₂Se₃/g-C₃N₄的这种S型异质结构在其光催化活性增强中起到了关键作用. 在光照条件下, 其g-C₃N₄导带中光生电子向Bi₂Se₃的价带迁移, 并与光生空穴复合, 从而使Bi₂Se₃导带上可保留更多的高活性光生电子参与光催化反应, 由此Bi₂Se₃/g-C₃N₄的光催化活性增强. 循环性能测试和光还原实验结果表明, 所制备的Bi₂Se₃/g-C₃N₄复合光催化剂具有良好的稳定性. 本文工作为高可见光吸收的光催化剂制备和性能增强提供了新途径和新视野.

关键词: S型异质结, 硒化铋, 石墨态氮化碳, 原位制备, 光催化

Abstract:

Bismuth selenide (Bi₂Se₃) is an attractive visible-light-responsive semiconductor that can absorb a full range of visible and near-infrared light. However, its poor redox capacity and rapid carrier recombination limit its application in photocatalytic oxidation. In this study, we adopted Bi₂Se₃ as the couple part of graphitic carbon nitride (g-C₃N₄) to construct a Bi₂Se₃/g-C₃N₄ composite photocatalyst. Through in situ fabrication, the self-developed Bi₂O₃/g-C₃N₄ precursor was transformed into a Bi₂Se₃/g-C₃N₄ heterojunction. The as-prepared Bi₂Se₃/g-C₃N₄ composite exhibited much higher visible-light-driven photocatalytic activity than pristine Bi₂Se₃ and g-C₃N₄ in the removal of phenol. The enhanced photocatalytic activity was ascribed to the S-scheme configuration of Bi₂Se₃/g-C₃N₄; this was confirmed by the energy-level shift, photoluminescence analysis, computational structure study, and reactive-radical testing. In the S-scheme heterojunction, photo-excited electrons in the conduction band of g-C₃N₄ migrate to the valence band of Bi₂Se₃ and combine with the excited holes therein. By consuming less reactive carriers, the S-scheme heterojunction can not only effectively promote charge separation, but also preserve more reactive photo-generated carriers. This property enhances the photocatalytic activity.

Key words: S-scheme heterojunction, Bismuth selenide, Graphitic carbon nitride, In situ fabrication, Photocatalysis

赫荣安, 欧斯娇, 刘烨萱, 刘宇, 许第发. 原位制备具有增强光催化活性的S型Bi₂Se₃/g-C₃N₄光催化剂[J]. 催化学报, 2022, 43(2): 370-378.

Rongan He, Sijiao Ou, Yexuan Liu, Yu Liu, Difa Xu. In situ fabrication of Bi₂Se₃/g-C₃N₄ S-scheme photocatalyst with improved photocatalytic activity[J]. Chinese Journal of Catalysis, 2022, 43(2): 370-378.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63911-6

https://www.cjcatal.com/CN/Y2022/V43/I2/370

图/表 12

Fig. 1. XRD patterns of Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4 composite.

Fig. 2. TEM (a) and HRTEM (b,c) morphologies of Bi2Se3/g-C3N4 composite.

Fig. 3. N2 adsorption-desorption isotherms (a) and pore-size distributions (b) of Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4.

Fig. 4. DRS spectra of Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4 composite.

Fig. 5. PL spectra (a) and EIS spectra (b) of Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4 under excitation light of 360 nm.

Fig. 6. XPS-survey spectra (a) and high-resolution XPS spectra (b-d) of samples.

Fig. 7. Band structure of Bi2Se3.

Fig. 8. CPDs (a) and the corresponding Fermi levels (b) of Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4.

Fig. 9. VB-XPS spectra of pure Bi2Se3 and g-C3N4.

Fig. 10. (a) Photocatalytic degradation of phenol over Bi2Se3, g-C3N4, and Bi2Se3/g-C3N4; (b) Temporal UV spectra of phenol over Bi2Se3/g-C3N4; (c) The kinetic curves of samples; (d) Stability test result of Bi2Se3/g-C3N4 with irradiation time of 2 h.

Fig. 11. DMPO-•O2- (a) and DMPO-•OH (b) test results of samples under a Xe lamp.

Fig. 12. Photocatalytic mechanism of Bi2Se3/g-C3N4.

参考文献

[1]	M. M. Khin, A. S. Nair, V. J. Babu, R. Murugan, S. Ramakrishna, Energy Environ. Sci., 2012,5, 8075-8819.
[2]	E. Brillas, C. A. Martínez-Huitle, Appl. Catal. B, 2015, 166-167, 603-643.
[3]	P. A. K. Reddy, P. V. L. Reddy, E. Kwon, K. Kim, T. Akter, S. Kalagara, Environ. Int., 2016,91, 94-103.
[4]	J. Wang, S. Wang, J. Environ. Manage., 2016,182, 620-640.
[5]	R. Wang, M. Shi, F. Xu, Y. Qiu, P. Zhang, K. Shen, Q. Zhao, J. Yu, Y. Zhang, Nat. Commun., 2020,11, 4465.
[6]	Y. Yang, H. Tan, B. Cheng, J. Fan, J. Yu, W. Ho, Small Methods, 2021,5, 2001042.
[7]	F. He, A. Meng, B. Cheng, W. Ho, J. Yu, Chin. J. Catal., 2020,41, 9-20.
[8]	R. He, R. Chen, J. Luo, S. Zhang, D. Xu, Acta Phys.-Chim. Sin., 2021,37, 2011022.
[9]	X. Liu, S. Gu, Y. Zhao, G. Zhou, W. Li, J. Mater. Sci. Technol., 2020,56, 45-68.
[10]	R. He, D. Xu, B. Cheng, J. Yu, W. Ho, Nanoscale Horiz., 2018,3, 464-504.
[11]	G. Gorle, A. Bathinapatla, Y. Chen, Y. Ling, RSC Adv., 2018,8, 19827-19834.
[12]	S. K. Mishra, S. Satpathy, O. Jepsen, J. Phys.: Condens. Matter, 1997,9, 461-470.
[13]	H. Zhang, C. Liu, X. Qi, X. Dai, Z. Fang, S. Zhang, Nat. Phys., 2009,5, 438-442.
[14]	C. Han, J. Yang, C. Yan, Y. Li, F. Liu, L. Jiang, J. Ye, Y. Liu, Cryst Eng Comm, 2014,16, 2823-2834.
[15]	L. Ma, C. Yang, X. Tian, Y. Nie, Z. Zhou, Y. Li, J. Cleaner Prod., 2018,171, 538-547.
[16]	J. He, T. M. Tritt, Science, 2017,357, 1369.
[17]	D. Kong, W. Dang, J. J. Cha, H. Li, S. Meister, H. Peng, Z. Liu, Y. Cui, Nano Lett., 2010,10, 2245-2250.
[18]	D. Li, J. Lao, C. Jiang, C. Luo, R. Qi, H. Lin, R. Huang, G. I. N. Waterhouse, H. Peng, Int. J. Hydrogen Energy, 2019,44, 30876-30884.
[19]	J. G. Analytis, R. D. Mcdonald, S. C. Riggs, J. Chu, G. S. Boebinger, I. R. Fisher, Nat. Phys., 2010,6, 960-964.
[20]	D. Kim, S. Cho, N. P. Butch, P. Syers, K. Kirshenbaum, S. Adam, J. Paglione, M. S. Fuhrer, Nat. Phys., 2012,8, 459-463.
[21]	D. R. Kumar, T. T. Nguyen, C. Lamiel, J. Shim, Mater. Lett., 2016,165, 257-262.
[22]	M. J. Chatterjee, S. T. Ahamed, M. Mitra, C. Kulsi, A. Mondal, D. Banerjee, Appl. Surf. Sci., 2019,470, 472-483.
[23]	C. Kulsi, A. Ghosh, A. Mondal, K. Kargupta, S. Ganguly, D. Banerjee, Appl. Surf. Sci., 2017,392, 540-548.
[24]	Y. Huang, K. Wang, T. Guo, J. Li, X. Wu, G. Zhang, Appl. Catal. B, 2020,277, 119232.
[25]	S. Tian, J. Meng, J. Huang, Q. Li, Chin. J. Chem. Phys., 2020,33, 427-433.
[26]	Z. Wang, Y. Chen, L. Zhang, B. Cheng, J. Yu, J. Fan, J. Mater. Sci. Technol., 2020,56, 143-150.
[27]	R. He, H. Liu, H. Liu, D. Xu, L. Zhang, J. Mater. Sci. Technol., 2020,52, 145-151.
[28]	C. Cheng, B. He, J. Fan, B. Cheng, S. Cao, J. Yu, Adv. Mater., 2021,33, 2100317.
[29]	Z. Mei, G. Wang, S. Yan, J. Wang, Acta Phys.-Chim. Sin., 2020,37, 2009097.
[30]	Z. Li, Z. Wu, R. He, L. Wan, S. Zhang, J. Mater. Sci. Technol., 2020,56, 151-161.
[31]	L. Liu, T. Hu, K. Dai, J. Zhang, C. Liang, Chin. J. Catal., 2021,42, 46-55.
[32]	Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, Chem, 2020,6, 1543-1559.
[33]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Yu, Nat. Commun., 2020,11, 4613.
[34]	W. Wang, W. Zhao, H. Zhang, X. Dou, H. Shi, Chin. J. Catal., 2021,42, 97-106.
[35]	J. Wang, G. Wang, B. Cheng, J. Yu, J. Fan, Chin. J. Catal., 2021,42, 56-68.
[36]	Q. Xie, W. He, S. Liu, C. Li, J. Zhang, P. K. Wong, Chin. J. Catal., 2020,41, 140-153.
[37]	H. Deng, X. Fei, Y. Yang, J. Fan, J. Yu, B. Cheng, L. Zhang, Chem. Eng. J., 2021,409, 127377.
[38]	X. Fei, H. Tan, B. Cheng, B. Zhu, L. Zhang, Acta Phys.-Chim. Sin., 2020,37, 2010027.
[39]	C. Bie, B. Cheng, J. Fan, W. Ho, J. Yu, Energy Chem, 2021,3, 100051.
[40]	L. Yang, X. Liu, Z. Liu, C. Wang, G. Liu, Q. Li, X. Feng, Ceram. Int., 2018,44, 20613-20619.
[41]	C. Bie, H. Yu, B. Cheng, W. Ho, J. Fan, J. Yu, Adv. Mater., 2021,33, 2003521.
[42]	S. Wageh, A. A. Al-Ghamdi, L. Liu, Acta Phys.-Chim. Sin., 2020,37, 2010024.
[43]	Y. Li, M. Zhang, L. Zhou, S. Yang, Z. Wu, Y. Ma, Acta Phys.-Chim. Sin., 2020,37, 2009030.
[44]	Y. Li, M. Zhou, B. Cheng, Y. Shao, J. Mater. Sci. Technol., 2020,56, 1-17.
[45]	Y. Li, X. Li, H. Zhang, J. Fan, Q. Xiang, J. Mater. Sci. Technol., 2020,56, 69-88.
[46]	W. Ong, L. Tan, H.N. Yun, S. Yong, S. Chai, Chem. Rev., 2016,116, 7159-7329.
[47]	P. Xia, S. Cao, B. Zhu, M. Liu, M. Shi, J. Yu, Y. Zhang, Angew. Chem. Int. Ed., 2020,59, 5218-5225.
[48]	S. Patnaik, D. P. Sahoo, K. Parida, Carbon, 2021,172, 682-711.
[49]	D. Qin, Y. Xia, Q. Li, C. Yang, Y. Qin, K. Lv, J. Mater. Sci. Technol., 2020,56, 206-215.
[50]	Y. Ren, Y. Li, X. Wu, J. Wang, G. Zhang, Chin. J. Catal., 2021,42, 69-77.
[51]	F. He, B. Zhu, B. Cheng, J. Yu, W. Ho, W. Macyk, Appl. Catal. B, 2020,272, 119006.
[52]	R. He, J. Zhou, H. Fu, S. Zhang, C. Jiang, Appl. Surf. Sci., 2018,430, 273-282.
[53]	R. He, K. Cheng, Z. Wei, S. Zhang, D. Xu, Appl. Surf. Sci., 2019,465, 964-972.
[54]	Y. Xia, B. Cheng, J. Fan, J. Yu, G. Liu, Small, 2019,15, 1902459.
[55]	J. A. Sobota, S. Yang, J. G. Analytis, Y. L. Chen, I. R. Fisher, P. S. Kirchmann, Z. Shen, Phys. Rev. Lett., 2012,108, 117403.

原位制备具有增强光催化活性的S型Bi₂Se₃/g-C₃N₄光催化剂

In situ fabrication of Bi₂Se₃/g-C₃N₄ S-scheme photocatalyst with improved photocatalytic activity

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 12

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[5]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[6]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[7]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[8]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[9]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[10]	李世杰, 王春春, 董珂欣, 张鹏, 陈晓波, 李鑫. 新型MIL-101(Fe)/BiOBr S型异质催化剂用于高效光催化降解抗生素和还原六价铬: 光催化性能分析和光催化机理研究[J]. 催化学报, 2023, 51(8): 101-112.
[11]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[12]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[13]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[14]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[15]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.