反溶剂沉淀法合成Fe3+掺杂ZnO纳米结构及其可见光催化性能

doi:10.11949/j.issn.0438-1157.20181233

化工学报 ›› 2019, Vol. 70 ›› Issue (3): 1198-1207.DOI: 10.11949/j.issn.0438-1157.20181233

• 材料化学工程与纳米技术 • 上一篇下一篇

反溶剂沉淀法合成Fe³⁺掺杂ZnO纳米结构及其可见光催化性能

段云彪¹(),徐存英^2,³(),王祥²,刘海²,黄梦婷²

1. 昆明理工大学材料科学与工程学院，云南昆明 650093
2. 昆明理工大学冶金与能源工程学院，云南昆明 650093
3. 复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093

收稿日期:2018-10-19 修回日期:2018-12-05 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 徐存英
作者简介:<named-content content-type="corresp-name">段云彪</named-content>（1963—），男，高级实验师，<email>1037550651@qq.com</email>|徐存英（1971—），女，博士，教授，<email>xucunying@foxmail.com</email>
基金资助:
国家自然科学基金项目(51764027)

Synthesis of Fe³⁺-doped ZnO nanostructures by antisolvent precipitation method and their visible photocatalytic activity

Yunbiao DUAN¹(),Cunying XU^2,³(),Xiang WANG²,Hai LIU²,Mengting HUANG²

1. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
2. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
3. State Key Laboratory of Complex Nonferrous Metal Resources Cleaning Utilization, Kunming 650093, Yunnan, China

Received:2018-10-19 Revised:2018-12-05 Online:2019-03-05 Published:2019-03-05
Contact: Cunying XU

摘要/Abstract

摘要：

以氯化胆碱-草酸低共熔溶剂(ChCl-OA DES)为溶剂，ZnO和Fe₂O₃为原料，通过简单的反溶剂沉淀法制备出不同掺杂浓度的Fe³⁺掺杂ZnO(Fe-ZnO)纳米结构。采用SEM、XRD、拉曼光谱、XPS等手段对所制Fe-ZnO结构与形貌进行了表征。结果表明，Fe-ZnO是由直径为20～30 nm纳米晶组装而成的微米棒。不同掺杂浓度的Fe-ZnO纳米晶均为六方铅锌矿结构，Fe³⁺很好地进入ZnO晶格。同时考察了所制Fe-ZnO的光吸收特性和光催化活性，发现Fe³⁺掺杂使其吸收峰红移至可见光范围，有效增强了可见光区域的催化活性。当Fe掺杂量为1.0%(atom)时，样品的光催化活性最好，比ZnO增大了约102倍。这说明Fe³⁺掺杂可改善ZnO对可见光光子的捕获能力。

关键词: 低共熔溶剂, 反溶剂沉淀法, 制备, 铁掺杂氧化锌, 纳米结构, 催化

Abstract:

Fe³⁺-doped ZnO (Fe-ZnO) nanostructures with different dopant concentrations were successfully synthesized by a simple antisolvent precipitation method from the choline chloride-oxalic acid deep eutectic solvent (ChCl-OA DES). The structure and morphology of the prepared Fe-ZnO were characterized by SEM, XRD, Raman spectroscopy and XPS. The as-prepared Fe³⁺-doped ZnO sample was micro-rods that were composed of nanoparticles with diameter of 20—30 nm. All of Fe³⁺-doped ZnO samples with various Fe³⁺-doping concentration were hexagonal wurtzite structure and the Fe³⁺ ions were well incorporated into the ZnO crystal lattice. In addition, the optical properties and photocatalytic activities of the samples were investigated based on ultraviolet-visible (UV-Vis) spectra analysis as well as the degradation of Rhodamine B in aqueous solution under visible light. Compared with ZnO catalysts, the threshold wavelength of Fe³⁺-doped ZnO nanostructure was shifted to the full visible light region (red shift) and their absorption in the visible region increased with increasing of Fe³⁺-doping concentration from 0 to 5.0%(atom). The content of iron ion was found to be significant to the photocatalytic efficiency of Fe-ZnO nanostructures. The results demonstrated that the most optimal Fe³⁺-doping concentration was 1.0% (atom), and its photocatalytic activity was increased by 102% compared with ZnO under visible light. The enhanced photoactivity of the Fe³⁺-doped ZnO nanostructure was mainly due to the improved visible photon harvesting achieved by Fe³⁺ doping.

Key words: deep eutectic solvent, antisolvent precipitation method, preparation, Fe-doped ZnO, nanostructure, catalysis

中图分类号:

TQ 426.8

段云彪, 徐存英, 王祥, 刘海, 黄梦婷. 反溶剂沉淀法合成Fe³⁺掺杂ZnO纳米结构及其可见光催化性能[J]. 化工学报, 2019, 70(3): 1198-1207.

Yunbiao DUAN, Cunying XU, Xiang WANG, Hai LIU, Mengting HUANG. Synthesis of Fe³⁺-doped ZnO nanostructures by antisolvent precipitation method and their visible photocatalytic activity[J]. CIESC Journal, 2019, 70(3): 1198-1207.

图/表 10

图1 不同Fe3+掺杂浓度ZnO的SEM图

Fig.1 SEM images of ZnO nanocrystals with different Fe3+-doping concentrations

图2 Fe3+掺杂浓度为1.0%样品的TEM 图及EDS谱图

Fig.2 TEM image and EDS spectraum of Fe-ZnO sample [1.0%(atom) Fe]

图3 不同Fe3+掺杂浓度ZnO的XRD谱图

Fig. 3 XRD patterns of Fe3+-doped ZnO nanocrystals with different Fe3+ concentrations

图4 不同Fe3+掺杂浓度ZnO的拉曼光谱

Fig.4 Raman spectra of Fe3+-doped ZnO nanocrystals with different Fe3+ concentrations

图5 纯ZnO和Fe-ZnO的精细X射线光电子能谱

Fig.5 Narrow scan XPS spectrum of ZnO and Fe-ZnO

图6 溶有金属氧化物的ChCl-OA DES加到纯水中所得沉淀物XRD谱图

Fig.6 XRD patterns of precipitate formed from ChCl-OA DES containing metal oxides by adding water

图7 不同Fe3+掺杂浓度ZnO的紫外-可见吸收光谱

Fig. 7 UV–Vis absorption spectra of Fe3+-doped ZnO nanocrystals with different Fe3+ concentrations

图8 所制样品在可见光照射下光催化降解Rhodamine B

Fig. 8 Photodegradability of RhB under visible light([RhB] = 10 mg/L, catalyst suspended = 3 g/L, pH = 9, T = 25℃)

表1 纯ZnO和不同Fe3+掺杂量Fe-ZnO光催化降解RhB的比较

Table 1 Comparison of photocatalytic degradation of RhBbetween pure ZnO and different Fe3+ doping amount of Fe-ZnO

Fe³⁺掺杂量/%(atom)	降解率/%	降解率提高/%
0.0	35.6	0
0.5	65.7	84.6
1.0	71.8	101.6
3.0	69.4	94.9
5.0	60.6	70.2

图9 Fe0.01Zn0.99O和纯ZnO催化剂在可见光照射下催化降解RhB的循环稳定性

Fig.9 Fe0.01Zn0.99O and ZnO for photodegradation of RhB under visible light( [RhB] = 10 mg/L, catalyst suspended = 3 g/L, pH = 9, T = 25℃)

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反溶剂沉淀法合成Fe³⁺掺杂ZnO纳米结构及其可见光催化性能

Synthesis of Fe³⁺-doped ZnO nanostructures by antisolvent precipitation method and their visible photocatalytic activity

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