Au纳米粒子表面等离子共振效应(SPR)增强Au/Bi2WO6异质纳米结构的光催化活性

doi:10.15541/jim20170376

无机材料学报 ›› 2018, Vol. 33 ›› Issue (6): 659-666.DOI: 10.15541/jim20170376 CSTR: 32189.14.10.15541/jim20170376

所属专题：光催化材料与技术

Au纳米粒子表面等离子共振效应(SPR)增强Au/Bi₂WO₆异质纳米结构的光催化活性

王丹军, 王婵, 赵强, 郭莉, 杨晓, 吴娇, 付峰

延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 延安 716000;

收稿日期:2017-08-07 修回日期:2017-10-29 出版日期:2018-06-20 网络出版日期:2018-05-24
基金资助:
国家自然科学基金(21666039, 21663030);陕西省科技厅项目(2013SZS20-P01, 2015SF291);陕西省教育厅基金(15JS119);陕西省大学生创新创业训练计划项目(1517, 1563);地方高校国家级大学生创新创业训练计划项目 (12280);延安大学研究生创新项目(YCX201733)

Au Nanoparticles (NPs) Surface Plasmon Resonance Enhanced Photocatalytic Activities of Au/Bi₂WO₆ Heterogeneous Nanostructures

WANG Dan-Jun, WANG Chan, ZHAO Qiang, GUO Li, YANG Xiao, WU Jiao, FU Feng

College of Chemistry & Chemical Engineering, Yan’an University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan’an 716000, China;

Received:2017-08-07 Revised:2017-10-29 Published:2018-06-20 Online:2018-05-24
Supported by:
National Natural Science Foundation of China(21666039, 21663030);Science and Technology Department of Shaanxi Province(2013SZS20-P01, 2015SF291);Natural Science Program of Education Department of Shaanxi Province (15JS119);College Students’ Innovation and Entrepreneurship Training Programs of Shaanxi Province (1517, 1563);National Local College Students’ Innovation and Entrepreneurship Training Program(12280);Graduate Innovation Training Program of Yan’an University(YCX201733)

摘要/Abstract

摘要：

采用水热-光还原法在三维Bi₂WO₆的二级结构纳米片表面原位沉积Au纳米粒子(Au NPs), 成功获得了具有可见光响应活性的Au/Bi₂WO₆异质光催化剂, 并借助XRD、FE-SEM、HR-TEM、XPS和 UV-Vis-DRS谱等手段对其物相组成、形貌和光吸收特性进行表征, 以罗丹明B(RhB)和苯酚为模型污染物对其光催化性能进行研究。实验结果表明, 与纯Bi₂WO₆相比, 所得Au/Bi₂WO₆异质纳米结构对染料降解具有较高的活性, 当Au负载量为1.5at%时, Au/Bi₂WO₆复合催化剂的催化活性最好, 其光催化降解RhB和苯酚的表观速率常数分别是纯Bi₂WO₆的1.5倍和2.2倍。自由基捕获实验表明, 光生空穴(h⁺)和∙O₂^-是RhB在Au/Bi₂WO₆催化材料上光催化降解的主要活性物种。机理分析表明, Au/Bi₂WO₆活性增强归因于光生电子从Bi₂WO₆的导带向AuNPs表面迁移, 降低光生电子-空穴对的复合率, 同时, Au NPs 的等离子共振效应(SPR)拓展了催化剂在可见光区的响应范围, 从而显著提高了Au/Bi₂WO₆异质光催化的剂活性。Au NPs修饰Bi₂WO₆异质催化剂光太阳能驱动在污水处理方面具有潜在应用。

关键词: Au/Bi₂WO₆异质纳米结构, 光催化剂, 光还原法, 电子转移, 等离子共振效应(SPR)

Abstract:

Novel visible-light-responsive Au/Bi₂WO₆ heterogeneous nanostructures were successfully prepared through in situ growth gold nanoparticles (Au NPs) on the second-structural nanosheets of three-dimensional (3D) Bi₂WO₆ via a facile photoreduction process. XRD, FE-SEM, HR-TEM, FT-IR, XPS, and UV-Vis-DRS spectra were employed to investigate the phase composition, morgphology and light-absorption properties of as-preapared samples. Rhodamine B(RhB) and phenol were selected as model pollutants to evaluate photocatalytic activities of samples. The experimental results reveal that the as-prepared Au/Bi₂WO₆ heterogeneous nanostructures exhibit much higher photocatalytic activities than pure Bi₂WO₆ for dye degradation. It is also revealed that 1.5at%Au/Bi₂WO₆ sample exhibit the best photocatalytic activities in the degradation process of RhB and phenol, the apparent rate constant is about 1.5 and 2.2 times as high as that of pure Bi₂WO₆ under visible light irradiation, respectively. Moreover, the trapping experiments results show that photogenerated hole (h⁺) and ·O₂^- serve as the main active species for the photodegradation of RhB over Au/Bi₂WO₆ heterogeneous nanostructures. The enhanced photocatalytic efficiencies of Au/Bi₂WO₆ heterogeneous nanostructures are attributed to the charge transfer from Bi₂WO₆ to the deposited Au NPs as well as their surface plasmon resonance (SPR) absorption, which enhance the migration efficiency of the electron-holes and retard the recombination of electrons-hole pairs. Au NPs decorated Bi₂WO₆ heterogeneous nanostructures have considerable potential applications in solar-driven wastewater treatment.

Key words: Au/Bi₂WO₆ heterogeneous nanostructures, photocatalyst, photo-reduction process, electron transfer, surface plasmon resonance (SPR)

中图分类号:

O643

王丹军, 王婵, 赵强, 郭莉, 杨晓, 吴娇, 付峰. Au纳米粒子表面等离子共振效应(SPR)增强Au/Bi₂WO₆异质纳米结构的光催化活性[J]. 无机材料学报, 2018, 33(6): 659-666.

WANG Dan-Jun, WANG Chan, ZHAO Qiang, GUO Li, YANG Xiao, WU Jiao, FU Feng. Au Nanoparticles (NPs) Surface Plasmon Resonance Enhanced Photocatalytic Activities of Au/Bi₂WO₆ Heterogeneous Nanostructures[J]. Journal of Inorganic Materials, 2018, 33(6): 659-666.

图/表 9

图1 纯Bi2WO6和Au/Bi2WO6焙烧前(a)后(b)的XRD图谱

Fig.1 XRD patterns of pure Bi2WO6 and Au/ Bi2WO6(a) Before calcinations; (b) After calcinations

图2 1.5at% Au/Bi2WO6的XPS图谱

Fig. 2 XPS spectra of 1.5at% Au/Bi2WO6 sample(a) Survey; (b) W4f; (c) Bi4f; (d) Au4f; (e) O1s

图3 光催化剂的FE-SEM电镜照片

Fig. 3 High magnification SEM images of as-prepared samples(a)-(c) Pure Bi2WO6; (d)-(f) 1.5at% Au/Bi2WO6

图4 (a)~(c) 纯Bi2WO6和(d)~(f) 1.5at% Au/Bi2WO6异质纳米结构的TEM/HR-TEM电镜照片

Fig. 4 TEM/HR-TEM images of (a)-(c) pure Bi2WO6 and (d)-(f) 1.5% Au/Bi2WO6 heterogeneous nanostructures

图5 Au/Bi2WO6的UV-Vis-DRS图谱

Fig. 5 UV-Vis absorbance spectra of Au/Bi2WO6 heterogeneous nanostructures the Au/Bi2WO6 sample

图6 (a)不同Au/Bi2WO6催化剂降解RhB的活性和(b) Au/Bi2WO6催化剂降解RhB的表观速率常数比较

Fig. 6 (a) Photocatalytic degradation acitvities and (b) apparent rate constant (kapp) for the degradation of different Au/Bi2WO6 photocatalysts on RhB

图7 (a)不同Au/Bi2WO6催化剂降解苯酚的活性和(b) Au/Bi2WO6催化剂降解苯酚的表观速率常数比较

Fig. 7 (a) Photocatalytic acitvities of Bi2WO6 and 1.5at% Au/Bi2WO6 photocatalysts and (b) apparent rate constant (kapp) for the degradation over Bi2WO6 and 1.5at%Au/Bi2WO6 against phenol

图8 可见光照射下1.5at% Au/Bi2WO6光催化降解RhB的活性物种捕获实验

Fig. 8 Trapping experiments of active species in the system of photodegradation of RhB by 1.5% Au/Bi2WO6 under visible light irradiation

图9 可见光照射下Au/Bi2WO6的能带结构和光可见光照射下光催化降解RhB的机理图

Fig. 9 Schematic illustration of the detailed energy alignment in the Au/Bi2WO6 hegerogeneous nanostructure and the proposed mechanism of photocatalytic degradation of RhB by Au/Bi2WO6 under visible light irradiation

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Au纳米粒子表面等离子共振效应(SPR)增强Au/Bi₂WO₆异质纳米结构的光催化活性

Au Nanoparticles (NPs) Surface Plasmon Resonance Enhanced Photocatalytic Activities of Au/Bi₂WO₆ Heterogeneous Nanostructures

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