2D/2D BiOBr/g-C3N4 S型异质结光催化性能

doi:10.1016/S1872-2067(20)63765-2

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1519-1529.DOI: 10.1016/S1872-2067(20)63765-2

2D/2D BiOBr/g-C₃N₄ S型异质结光催化性能

张彬^a, 胡晓云^b, 刘恩周^a^,^#(), 樊君^a^,^*()

^a西北大学化工学院, 西安市特种能源材料重点实验室, 陕西西安710069
^b西北大学物理学院, 陕西西安710127

收稿日期:2020-11-23 接受日期:2021-01-18 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 刘恩周,樊君
基金资助:
国家自然科学基金(21676213);国家自然科学基金(11974276);国家自然科学基金(22078261);陕西省自然科学基础研究计划(2020JM-422);中国博士后科学基金(2016M600809)

Novel S-scheme 2D/2D BiOBr/g-C₃N₄ heterojunctions with enhanced photocatalytic activity

Bin Zhang^a, Xiaoyun Hu^b, Enzhou Liu^a^,^#(), Jun Fan^a^,^*()

^aXi’an Key Laboratory of Special Energy Materials, School of Chemical Engineering, Northwest University, Xi’an 710069, Shaanxi, China
^bSchool of Physics, Northwest University, Xi’an 710127, Shaanxi, China

Received:2020-11-23 Accepted:2021-01-18 Online:2021-09-18 Published:2021-05-16
Contact: Enzhou Liu,Jun Fan
About author:^# Tel: +86-13759963944; E-mail: liuenzhou@nwu.edu.cn
^* Tel: +86-13110493201; E-mail: fanjun@nwu.edu.cn;
Supported by:
National Natural Science Foundation of China(21676213);National Natural Science Foundation of China(11974276);National Natural Science Foundation of China(22078261);Natural Science Basic Research Program of Shaanxi(2020JM-422);China Postdoctoral Science Foundation(2016M600809)

摘要/Abstract

摘要：

近年来, 能源短缺和环境污染严重威胁人类的可持续发展. 光催化技术具有绿色环保、成本低等优势, 被认为是解决上述问题的最佳途径之一, 其实用化的核心是开发高效可见光催化材料. 石墨相氮化碳(g-C₃N₄)因其物理化学性质稳定、无毒、廉价及能带适宜等特点, 广泛应用于光催化领域. 然而, 光生载流子易复合、比表面积小等问题不利于其实际应用, 构建g-C₃N₄基2D/2D异质结不仅能促进载流子有效分离, 而且能为反应提供更多表面空间环境, 是提高g-C₃N₄催化活性的有效途径. 目前, I型和II型异质结虽能促进电荷分离, 但降低了电荷参与表面反应的电势; 而S型异质结电荷转移机制遵循热力学和动力学规律, 能很好保留高氧化还原能力的电子和空穴, 因而备受关注. 当前, 开发S型g-C₃N₄基2D/2D异质结有助于发展高效光催化体系.
本文首先以三聚氰胺为前驱体, 通过二次高温煅烧得到2D g-C₃N₄纳米片; 随后, 以Bi(NO₃)₃·5H₂O和KBr为反应物, 乙二胺和水为溶剂, 借助室温原位自组装法获得一系列不同质量比的BiOBr/g-C₃N₄异质结. 研究表明, BiOBr均匀分布于g-C₃N₄表面形成具有良好接触界面的2D/2D异质结, 而且BiOBr/g-C₃N₄比表面积可提高至g-C₃N₄的2.4倍. 当BiOBr与g-C₃N₄质量比为1.5:1时, 可见光照射30 min, 30 mg复合样品可将浓度为10 mg·L^-1的RhB (100 mL)几乎全部降解, 降解过程符合一级反应动力学, 降解速率是g-C₃N₄的48.2倍. 此外, 该体系具有一定的光催化析氢活性及良好的循环稳定性. X射线光电子能谱、紫外光电子能谱、莫特肖特基、电化学阻抗谱分析及活性物种捕获等实验结果表明, 由于还原性半导体g-C₃N₄与氧化型半导体BiOBr费米能级不同, 二者接触时, 电子从费米能级高的g-C₃N₄转移至费米能级低的BiOBr, 在复合材料界面产生强的内建电场, 借助带边弯曲和库仑力共同作用, 形成了具有S型电荷转移途径的2D/2D BiOBr/g-C₃N₄异质结. 在光照条件下, g-C₃N₄价带空穴能与BiOBr导带电子快速复合(一般认为是无用的电荷), 从而使具有高反应活性的g-C₃N₄导带电子与BiOBr价带空穴参与表面反应, 有效提高了体系的催化活性. 综合本文及其他相关研究可知, 在由氧化型和还原型半导体组成的异质结中, S型电荷转移机制具有一定普适性, 可指导开发高效光催化体系以解决能源和环境问题.

关键词: BiOBr/g-C₃N₄, 2D/2D, 光催化降解罗丹明B, 光产氢, S型异质结

Abstract:

The design and construction of heterojunction photocatalysts, which possess a staggered energy band structure and appropriate interfacial contact, is an effective way to achieve outstanding photocatalytic performance. In this study, 2D/2D BiOBr/g-C₃N₄ heterojunctions were successfully obtained by a convenient in situ self-assembly route. Under simulated sunlight irradiation, 99% of RhB (10 mg·L^-1, 100 mL) was efficiently degraded by 1.5-BiOBr/g-C₃N₄ within 30 min, which is better than the performance of both BiOBr and g-C₃N₄, and it has superior stability. In addition, the composite also exhibits enhanced photocatalytic activity for H₂ production. The enhanced activity can be attributed to the intimate interface contact, the larger surface area, and the highly efficient separation of photoinduced electron-hole pairs. Based on the experimental results, a novel S-scheme model was proposed to illuminate the transfer process of charge carriers. This study presents a simple way to develop novel step-scheme photocatalysts for environmental and related applications.

Key words: BiOBr/g-C₃N₄, 2D/2D, Photocatalytic RhB degradation, H₂ evolution, S-scheme heterojunction

张彬, 胡晓云, 刘恩周, 樊君. 2D/2D BiOBr/g-C₃N₄ S型异质结光催化性能[J]. 催化学报, 2021, 42(9): 1519-1529.

Bin Zhang, Xiaoyun Hu, Enzhou Liu, Jun Fan. Novel S-scheme 2D/2D BiOBr/g-C₃N₄ heterojunctions with enhanced photocatalytic activity[J]. Chinese Journal of Catalysis, 2021, 42(9): 1519-1529.

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图/表 16

Fig. 1. XRD patterns of X-BiOBr/g-C3N4.

Fig. 2. SEM images of g-C3N4 (a,b), BiOBr (c,d), and 1.5-BiOBr/g-C3N4 (e, f).

Fig. 3. TEM (a) and HRTEM (b) images of 1.5-BiOBr/g-C3N4.

Fig. 4. (a) Survey XPS spectrum of 1.5-BiOBr/g-C3N4; high-resolution XPS spectra of C 1s (b), N 1s (c), Bi 4f (d), O 1s (e), and Br 3d (f).

Fig. 5. (a) UV-vis absorption spectra of all samples; (b) Tacu plots of BiOBr and g-C3N4.

Fig. 6. Nitrogen adsorption-desorption isotherms.

Fig. 7. Photocatalytic degradation curves (a) and rate constant (k) (b) of all samples.

Fig. 8. Photocatalytic H2 evolution performance (a) and H2 evolution rates (b) of all samples.

Fig. 9. Cycling tests of RhB photodegradation (a) and H2 evolution (b) on the 1.5-BiOBr/g-C3N4 composite; (c) XRD patterns of the sample before and after reaction.

Fig. 10. Photoluminescence spectra (a), transient photocurrent responses (b), and electrochemical impedance spectroscopy (c) results of g-C3N4, BiOBr, and 1.5-BiOBr/g-C3N4.

Fig. 11. VB-XPS (a) and Mott-Schottky (b) plots of as-prepared BiOBr and g-C3N4.

Fig. 12. RhB photodegradation tests of 1.5-BiOBr/g-C3N4 with various scavengers.

Fig. 13. (a) UV absorption spectra of NBT; (b) Fluorescence spectra of TAOH.

Fig. 14. Type-II charge separation route in BiOBr/g-C3N4 system.

Fig. 15. (a) Band-gap structure of BiOBr and g-C3N4; (b) Internal electric field and band edge bending at the interface of BiOBr/g-C3N4 after contact; (c) S-scheme mechanism of BiOBr/g-C3N4 under light irradiation.

Fig. 16. Scheme 1. Preparation processes of the photocatalysts.

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2D/2D BiOBr/g-C₃N₄ S型异质结光催化性能

Novel S-scheme 2D/2D BiOBr/g-C₃N₄ heterojunctions with enhanced photocatalytic activity

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