磁性Ag2S/Ag/CoFe1.95Sm0.05O4 Z型异质结的制备及光催化降解性能

doi:10.15541/jim20220166

摘要/Abstract

摘要：

光催化降解水体中的有机污染物具有广阔的应用前景。本研究以CoFe_1.95Sm_0.05O₄作为载体, 通过原位沉积法和光还原法制备了Z型异质结Ag₂S/Ag/CoFe_1.95Sm_0.05O₄, 采用不同表征手段对样品的微观形貌、物相结构、光学和磁学性能进行表征分析。Ag₂S/Ag/CoFe_1.95Sm_0.05O₄复合物催化活性最高, 其光催化降解动力学常数(k)分别是Ag₂S/Ag, Ag₂S和CoFe_1.95Sm_0.05O₄的2.96, 3.71和8.24倍。引入CoFe_1.95Sm_0.05O₄可以有效地促进Ag₂S/Ag中光生载流子的分离效率。•O₂^-和 •OH^-是光催化过程中的主要活性物。此外, 在光催化反应后, 外加磁场可以将制备的Ag₂S/Ag/CoFe_1.95Sm_0.05O₄复合材料快速从溶液中分离出来。循环降解实验显示, Ag₂S/Ag/CoFe_1.95Sm_0.05O₄复合材料在光降解过程中具有稳定的降解能力和晶体结构。本研究为进一步开发高效、窄带隙和磁性的光催化剂提供了有效的解决思路。

关键词: Ag₂S/Ag/CoFe_1.95Sm_0.05O₄, Z型异质结, 光催化降解, 回收

Abstract:

Photocatalytic degradation of organic pollutants from water bodies can efficiently reduce the organic pollutants in wastewater, which has broad application prospects. In this study, using CoFe_1.95Sm_0.05O₄as a support, the Z-scheme heterojunction Ag₂S/Ag/CoFe_1.95Sm_0.05O₄was synthesized through a facile in situ deposition method followed by photo-reduction. Microstructure, phase structure, optical and magnetic properties of the samples were analyzed. Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ composite exhibited the highest catalytic activity, which dynamic constant (k) was 1.96, 2.71 and 7.24 times higher than those of Ag₂S/Ag, Ag₂S and CoFe_1.95Sm_0.05O₄, respectively. Introduction of CoFe_1.95Sm_0.05O₄ could efﬁciently promote the separation efﬁciency of photogenerated charge carriers in Ag₂S/Ag. And •O₂^-and •OH^- were proved to be the main active substances in the photocatalytic process. In addition, the as-prepared Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ composite could be quickly separated from the solution by an extra magnetic field after the photocatalytic reaction. Cyclic photodegradation test showed that the Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ hybrid materials had the stable degradation ability and crystal structures in the photodegradation process. This research provides a useful approach to develop photocatalysts with high efficiency, narrow band gap and magnetism.

Key words: Ag₂S/Ag/CoFe_1.95Sm_0.05O₄, Z-scheme heterojunction, photocatalytic degradation, recycling

中图分类号:

TB333

陈士昆, 王楚楚, 陈晔, 李莉, 潘路, 文桂林. 磁性Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ Z型异质结的制备及光催化降解性能[J]. 无机材料学报, 2022, 37(12): 1329-1336.

CHEN Shikun, WANG Chuchu, CHEN Ye, LI Li, PAN Lu, WEN Guilin. Magnetic Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ Z-scheme Heterojunction: Preparation and Its Photocatalytic Degradation Property[J]. Journal of Inorganic Materials, 2022, 37(12): 1329-1336.

图/表 7

图1 不同样品的XRD谱图(a)和Ag2S/Ag/CoFe1.95Sm0.05O4 的EDS能谱图(b)

Fig. 1 XRD patterns of different samples (a) and EDS pattern of Ag2S/Ag/CoFe1.95Sm0.05O4 (b)

图2 Ag2S/Ag/CoFe1.95Sm0.05O4 的TEM 照片(a)及其HRTEM照片 (b, c)

Fig. 2 TEM (a) and HRTEM (b,c) images of Ag2S/Ag/CoFe1.95Sm0.05O4

图3 不同样品的XPS全谱图(a); Ag2S/Ag/CoFe1.95Sm0.05O4复合材料Ag3d(b), S2p(c), Co2p(d), Fe2p(e), Sm3d(f)和O2p(g)的XPS谱图

Fig. 3 XPS survey spectra of different materials (a); Ag3d(b); S2p(c); Co2p (d); Fe2p(e); Sm3d (f) and O2p (g) XPS spectra of Ag2S/Ag/CoFe1.95Sm0.05O4

图4 样品的紫外-可见吸收光谱(a)和(αhv)2-hv关系图(b)

Fig. 4 UV-Vis absorption spectra (a) and plots of (αhν)2 versus hv (b) of samples

图5 不同样品可见光催化降解MO(a, c)和一级动力学曲线(b, d)

Fig. 5 Degradation curves of MO by different samples under visible light irradiation (a, c) and corresponding first-order kinetics (b, d)

图6 样品的磁化曲线 (插图为外部磁场分离后的溶液的照片) (a), 样品对甲基橙降解的循环性能曲线(b)和循环试验前后Ag2S/Ag/CoFe1.95Sm0.05O4的XRD谱图(c)

Fig. 6 Magnetization curves of samples with inset showing the pictures of the solution after magnetic separation using an external magnetic (a), five cycling runs of the sample for MO degradation (b) and XRD patterns of Ag2S/Ag/CoFe1.95Sm0.05O4 before and after cyclic test (c)

图7 Ag2S/Ag/CoFe1.95Sm0.05O4光催化自由基捕获降解(a), 样品的莫特-肖特基曲线(b), Ag2S, CoFe1.95Sm0.05O4的XPS价带谱图 (c,d), 制备样品的EIS图谱(e) 和Ag2S/Ag/CoFe1.95Sm0.05O4光催化MO降解机理图(f)

Fig. 7 Photocatalytic degradation of Ag2S/Ag/CoFe1.95Sm0.05O4 by free radical capture (a), Mott-Schottky curves of samples (b), Valence-band XPS spectra of Ag2S, CoFe1.95Sm0.05O4 (c,d), EIS spectra of as-prepared samples (e), and the proposed photocatalytic degradation mechanism of MO over Ag2S/Ag/CoFe1.95Sm0.05O4(f)

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磁性Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ Z型异质结的制备及光催化降解性能

Magnetic Ag₂S/Ag/CoFe_1.95Sm_0.05O₄ Z-scheme Heterojunction: Preparation and Its Photocatalytic Degradation Property

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