S型Sb2WO6/g-C3N4复合光催化剂及其增强的可见光诱导的光催化氧化NO性能

doi:10.1016/S1872-2067(20)63631-2

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 69-77.DOI: 10.1016/S1872-2067(20)63631-2

S型Sb₂WO₆/g-C₃N₄复合光催化剂及其增强的可见光诱导的光催化氧化NO性能

任雨雨, 李源, 吴晓勇, 王金龙, 张高科^*

武汉理工大学矿物资源加工与环境湖北省重点实验室, 硅酸盐建筑材料国家重点实验室, 湖北武汉430070

收稿日期:2020-03-16 接受日期:2020-04-30 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 张高科
作者简介:第一联系人：† 共同第一作者.
基金资助:
国家自然科学基金(51472194);湖北省自然科学基金(2016CFA078)

S-scheme Sb₂WO₆/g-C₃N₄ photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance

Yuyu Ren, Yuan Li, Xiaoyong Wu, Jinlong Wang, Gaoke Zhang^*

Hubei Key Laboratory of Mineral Resources Processing and Environment, State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China

Received:2020-03-16 Accepted:2020-04-30 Online:2021-01-18 Published:2021-01-18
Contact: Gaoke Zhang
About author:^*Tel: +86-27-87651816; Fax: +86-27-87887445; E-mail: gkzhang@whut.edu.cn
First author contact:† Contributed to this work equally.
Supported by:
National Natural Science Foundation of China(51472194);Natural Science Foundation of Hubei Province(2016CFA078)

摘要/Abstract

摘要：

近年来, 随着工业化和城镇化的飞速发展, 作为一种典型的空气污染物, NO_x已经造成严重的环境问题, 甚至威胁到人类的身体健康. 为了解决这个问题, 科研工作者研发了许多NO_x去除技术, 其中光催化技术被认为是一种能有效地去除空气中NO_x的技术. 作为一种廉价、无毒、热稳定性强、能带结构合适的光催化材料, 石墨相氮化碳(g-C₃N₄)能够有效的利用可见光, 将NO光催化氧化为NO₃^-. 但是由于自身的光生载流子复合率较高, 光谱响应范围较窄等缺点, g-C₃N₄不能有效的光催化去除空气中持续流动的低浓度NO, 限制了其在光催化领域中的实际应用. 因此, 有必要合成出高催化活性、高光响应范围的S型复合光催化剂来克服以上光催化材料的不足. 为此, 我们利用超声辅助法制备了一系列的S型Sb₂WO₆/g-C₃N₄复合光催化剂, 呈现出优异的光催化活性: 与其纯组分相比, 所制备的15-Sb₂WO₆/g-C₃N₄复合光催化剂在可见光下照射30 min, 可去除68%以上的持续流动的NO(初始浓度400 ppb), 且五次循环实验后, Sb₂WO₆/g-C₃N₄复合光催化剂仍然具备良好的光催化活性和稳定性. 透射电子显微镜结果清楚地表明, Sb₂WO₆颗粒已成功地均匀地负载到g-C₃N₄纳米片表面. 紫外可见漫反射光谱的结果表明, Sb₂WO₆和g-C₃N₄的复合可以有效地提高对可见光的吸收能力. 与纯g-C₃N₄样品相比, 复合样的吸收带边具有明显的红移. 光致发光光谱结果表明, 在Sb₂WO₆/g-C₃N₄复合半导体中, 光生载流子的复合受到抑制. 光电流与电阻抗分析可知, 与纯Sb₂WO₆和g-C₃N₄相比较, 在15-Sb₂WO₆/g-C₃N₄复合光催化剂中的光生载流子的迁移速率和分离效率较高. 通过对样品的能带结构分析并已有参考文献, 我们认为Sb₂WO₆和g-C₃N₄的接触边界形成了S型异质结, 使光生载流子的转移速率更快, 改善了光生电子-空穴对分离, 而且增强可见光的利用效率, 从而提高了光催化性能. 自由基捕获实验结果证实, •O₂^-主导了Sb₂WO₆/g-C₃N₄复合光催化剂去除NO反应, h⁺也在一定程度上参与了光催化氧化NO的反应. 通过原位红外光谱技术研究了Sb₂WO₆/g-C₃N₄光催化NO氧化的反应机理, 研究发现, Sb₂WO₆/g-C₃N₄复合光催化剂光催化去除是氧诱导的反应. 具体反应机理是在可见光的驱动下, 光催化剂表面的光生电子会与被吸附的O₂反应生成•O₂^-, 并与光生h⁺一起, 共同将低浓度的NO光催化氧化为亚硝酸盐或硝酸盐. 该研究有助于深入研究光催化氧化NO机理, 并为设计高效光催化剂用于光催化氧化ppb级NO提供了一种极具前景的策略.

关键词: 钨酸锑, 石墨相C₃N₄, S型光催化剂, 光催化去除氮氧化物, 原位红外测试

Abstract:

Normal photocatalysts cannot effectively remove low-concentration NO because of the high recombination rate of the photogenerated carriers. To overcome this problem, S-scheme composites have been developed to fabricate photocatalysts. Herein, a novel S-scheme Sb₂WO₆/g-C₃N₄ nanocomposite was fabricated by an ultrasound-assisted method, which exhibited excellent performance for photocatalytic ppb-level NO removal. Compared with the pure constituents of the nanocomposite, the as-prepared 15%-Sb₂WO₆/g-C₃N₄ photocatalyst could remove more than 68% continuous-flowing NO (initial concentration: 400 ppb) under visible-light irradiation in 30 min. The findings of the trapping experiments confirmed that •O₂^- and h⁺ were the important active species in the NO oxidation reaction. Meanwhile, the transient photocurrent response and PL spectroscopy analyses proved that the unique S-scheme structure of the samples could enhance the charge separation efficiency. In situ DRIFTS revealed that the photocatalytic reaction pathway of NO removal over the Sb₂WO₆/g-C₃N₄ nanocomposite occurred via an oxygen-induced route. The present work proposes a new concept for fabricating efficient photocatalysts for photocatalytic ppb-level NO oxidation and provides deeper insights into the mechanism of photocatalytic NO oxidation.

Key words: Sb₂WO₆, g-C₃N₄, S-scheme photocatalyst, Photocatalytic NO oxidation, In situ DRIFTS

任雨雨, 李源, 吴晓勇, 王金龙, 张高科. S型Sb₂WO₆/g-C₃N₄复合光催化剂及其增强的可见光诱导的光催化氧化NO性能[J]. 催化学报, 2021, 42(1): 69-77.

Yuyu Ren, Yuan Li, Xiaoyong Wu, Jinlong Wang, Gaoke Zhang. S-scheme Sb₂WO₆/g-C₃N₄ photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance[J]. Chinese Journal of Catalysis, 2021, 42(1): 69-77.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63631-2

https://www.cjcatal.com/CN/Y2021/V42/I1/69

图/表 8

Fig. 1. XRD patterns (a), Raman spectra (b) and FT-IR spectra (c) of the Sb2WO6, g-C3N4, and 15-Sb2WO6/g-C3N4 samples.

Fig. 2. TEM (a), HRTEM (b), and HAADF-STEM (c) images and the corresponding EDS elemental mapping images (d-k) of the 15-Sb2WO6/g-C3N4 nanocomposite.

Fig. 3. XPS spectra of Sb2WO6, gC3N4, and 15-Sb2WO6/g-C3N4. (a) Survey spectra; (b) C 1s; (c) N 1s; (d) O 1s; (e) Sb 3d; (f) W 4f spectra.

Fig. 4. UV-vis diffuse reflection spectra of the as-prepared samples (a) and enlarged image (b) of the zone marked in (a); (Ahν)1/2 versus hν plots (c) and Mott-Schottky plots (d) of pure Sb2WO6 and g-C3N4.

Fig. 5. (a) Photocatalytic NO oxidation of the as-prepared samples; (b) Five consecutive runs of NO removal over the 15-Sb2WO6/g-C3N4 nanocomposite; XRD patterns (c) and FT-IR spectra (d) of 15-Sb2WO6/g-C3N4 nanocomposite before and after photocatalytic reaction.

Fig. 6. (a) PL spectra of g-C3N4 and Sb2WO6/g-C3N4 nanocomposites; Photocurrent responses (b) and EIS spectra (c) of Sb2WO6, g-C3N4, and 15-Sb2WO6/g-C3N4 samples; (d) Results of radical species trapping experiments of the 15-Sb2WO6/g-C3N4 sample and the removal of NO with different scavengers.

Fig. 7. In situ DRIFT spectra of the photocatalytic reaction of NO over 15-Sb2WO6/g-C3N4 nanocomposite under visible-light irradiation.

Fig. 8. S-scheme photocatalytic mechanism for Sb2WO6/g-C3N4 nanocomposite under visible-light irradiation.

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S型Sb₂WO₆/g-C₃N₄复合光催化剂及其增强的可见光诱导的光催化氧化NO性能

S-scheme Sb₂WO₆/g-C₃N₄ photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance

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