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

doi:10.11949/j.issn.0438-1157.20181233

Abstract

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

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

CLC Number:

TQ 426.8

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.

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.

Figures/Tables 10

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

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

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

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

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

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

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

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

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

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

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

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