基于富氧空位LiYScGeO4: Bi3+长余辉光催化剂的自激活余辉驱动有机污染物芬顿降解

doi:10.15541/jim20240495

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 481-488.DOI: 10.15541/jim20240495

基于富氧空位LiYScGeO₄: Bi³⁺长余辉光催化剂的自激活余辉驱动有机污染物芬顿降解

范小暄(), 郑永炅, 徐丽荣, 姚子敏, 曹硕, 王可心(), 王绩伟()

辽宁大学物理学院, 沈阳 110036

收稿日期:2024-11-27 修回日期:2025-01-24 出版日期:2025-05-20 网络出版日期:2025-02-13
通讯作者: 王可心, 讲师. E-mail: wyf93jl@163.com;
王绩伟, 教授. E-mail: wangjiwei@lnu.edu.cn
作者简介:范小暄(1997-), 女, 博士研究生. E-mail: fanxiaoxuan0314@163.com
基金资助:
国家自然科学基金(12374181);辽宁省属本科高校基本科研业务费专项资金(LJ212410140035);沈阳市自然科学基金(基础研究)专项项目(22-315-6-06);辽宁大学青年科研基金(LDYBJC2401)

Organic Pollutant Fenton Degradation Driven by Self-activated Afterglow from Oxygen-vacancy-rich LiYScGeO₄: Bi³⁺ Long Afterglow Phosphor

FAN Xiaoxuan(), ZHENG Yonggui, XU Lirong, YAO Zimin, CAO Shuo, WANG Kexin(), WANG Jiwei()

College of Physics, Liaoning University, Shenyang 110036, China

Received:2024-11-27 Revised:2025-01-24 Published:2025-05-20 Online:2025-02-13
Contact: WANG Kexin, lecturer. E-mail: wyf93jl@163.com;
WANG Jiwei, professor. E-mail: wangjiwei@lnu.edu.cn
About author:FAN Xiaoxuan (1997-), female, PhD candidate. E-mail: fanxiaoxuan0314@163.com
Supported by:
National Natural Science Foundation of China(12374181);Fundamental Research Funds for Public Universities in Liaoning(LJ212410140035);Natural Science Foundation of Shenyang(22-315-6-06);Youth Research Fund in Liaoning University(LDYBJC2401)

摘要/Abstract

摘要：

自激活长余辉光催化剂在全天候污水处理方面表现出巨大的潜力, 即使在黑暗条件下也具有持续的光催化活性。然而, 由于余辉发光的辐射复合与光催化降解反应对光生载流子的竞争性利用会降低余辉持续时间, 并引起空穴过量积累, 这极大地限制了长余辉驱动的光催化降解反应。本研究制备了一种基于氧空位(V_O)LiYGeO₄: Bi³⁺的长余辉光催化剂(V_O-LiYScGeO₄: Bi³⁺), 该催化剂被紫外光辐照激活后, 能够在无光照环境中持续释放紫外余辉, 并在自身释放余辉激活下光催化降解有机污染物。结果表明, 利用氧空位工程和晶体场工程可增大V_O-LiYScGeO₄: Bi³⁺陷阱浓度, 进而延长余辉衰减时间并增强余辉发光强度。通过构建芬顿反应体系, 增大了活性物种浓度, 进一步提升了V_O-LiYScGeO₄: Bi³⁺在余辉持续时间内的光降解效率。经过10 min光辐照激活后, V_O-LiYScGeO₄: Bi³⁺在无光照环境中能持续释放紫外余辉1 h并光催化降解罗丹明B(RhB), 在芬顿环境中的最大降解率可达63%。相较于无芬顿环境中的LiYScGeO₄: Bi³⁺, 芬顿环境中的V_O-LiYScGeO₄: Bi³⁺对RhB的降解率提升了3.5倍。本工作为长余辉光催化剂的设计及其在污水处理领域中的应用提供了新的思路。

关键词: 光催化, 光芬顿, 氧空位, 长余辉, 荧光粉

Abstract:

Self-activated long afterglow photocatalysts show great potential for all-weather wastewater treatment, with sustained photocatalytic activity even under dark conditions. However, the radiative combination of afterglow luminescence and photocatalytic degradation reaction has competitive utilization for photogenerated carriers, reducing afterglow duration and generating excessive hole accumulation, which significantly limits the efficiency of long afterglow driven photocatalytic degradation. Here, a long afterglow photocatalyst LiYGeO₄: Bi³ based on oxygen vacancy (V_O) was prepared, which released ultraviolet afterglow after activation by ultraviolet light irradiation and degraded organic pollutants via photocatalytic degradation driven by its own afterglow in dark condition. The trap concentration was improved by engineering oxygen vacancies and crystal fields, significantly enhancing the afterglow duration and intensity of V_O-LiYScGeO₄: Bi³⁺. A Fenton reaction system was constructed to further increase the concentration of active species, which maximized the photocatalytic degradation efficiency of V_O-LiYScGeO₄: Bi³⁺ during the afterglow duration. After 10 min UV irradiation to activate V_O-LiYScGeO₄: Bi³⁺ continuously released ultraviolet afterglow for photocatalytic degradation of Rhodamine B (RhB), reaching a degradation efficiency of 63% within 1 h in Fenton environment, which increased by 3.5 folds when compared to that of LiYScGeO₄: Bi³⁺ in the initial environment. This work provides a new approach for the design of afterglow photocatalysts and their application in wastewater treatment.

Key words: photocatalysis, photo-Fenton, oxygen vacancy, long afterglow, phosphor

中图分类号:

O643

范小暄, 郑永炅, 徐丽荣, 姚子敏, 曹硕, 王可心, 王绩伟. 基于富氧空位LiYScGeO₄: Bi³⁺长余辉光催化剂的自激活余辉驱动有机污染物芬顿降解[J]. 无机材料学报, 2025, 40(5): 481-488.

FAN Xiaoxuan, ZHENG Yonggui, XU Lirong, YAO Zimin, CAO Shuo, WANG Kexin, WANG Jiwei. Organic Pollutant Fenton Degradation Driven by Self-activated Afterglow from Oxygen-vacancy-rich LiYScGeO₄: Bi³⁺ Long Afterglow Phosphor[J]. Journal of Inorganic Materials, 2025, 40(5): 481-488.

图/表 8

图1 催化剂的物相与形貌分析

Fig. 1 Phase and morphology analyses of catalysts (a) XRD patterns of LiYGeO4: Bi3+, LiYScGeO4: Bi3+, and VO-LiYScGeO4: Bi3+; (b) EDS elemental mappings of VO-LiYScGeO4: Bi3+; (c) SEM image of VO-LiYScGeO4: Bi3+; (d) EDS spectrum of VO-LiYScGeO4: Bi3+

图2 LiYScGeO4: Bi3+和VO-LiYScGeO4: Bi3+的光学性质分析

Fig. 2 Optical properties of LiYScGeO4: Bi3+ and VO-LiYScGeO4: Bi3+ (a) Long afterglow decay curves of LiY0.997-xScxGeO4: 0.003Bi3+ phosphors recorded at 355 nm after irradiation with 254 nm UV lamp for 10 min; (b) Fitted O1s XPS spectra; (c) UV-Vis DRS spectra with inset showing Tauc plots; (d) Emission spectra under 254 nm excitation; (e) TL spectra; (f) Afterglow decay curves Colorful figures are available on website

图3 LiYScGeO4: Bi3+和Vo-LiYScGeO4: Bi3+的电化学性能

Fig. 3 Electrochemical performance of LiYScGeO4: Bi3+ and Vo-LiYScGeO4: Bi3+ (a) Afterglow photocurrent; (b) Steady-state photocurrent response; (c) Electrochemical impedance spectra; (d) Mott-Schottky plots

图4 LiYScGeO4: Bi3+和VO-LiYScGeO4: Bi3+对RhB的(a)光催化降解率和(b)动力学曲线

Fig. 4 (a) Photocatalytic degradation efficiency and (b) kinetic curves of LiYScGeO4: Bi3+ and VO-LiYScGeO4: Bi3+on RhB

图5 LiYScGeO4: Bi3+和VO-LiYScGeO4: Bi3+在芬顿环境下对RhB的(a)光催化降解率和(b)动力学曲线

Fig. 5 (a) Photocatalytic degradation efficiency and (b) kinetic curves of LiYScGeO4: Bi3+ and VO-LiYScGeO4: Bi3+on RhB in Fenton environment

图6 光催化降解机制分析

Fig. 6 Analysis of photocatalytic degradation mechanism (a) Degradation efficiency of VO-LiYScGeO4: Bi3+ on RhB with addition of reactive species scavengers BQ, EDTA and IPA, with inset showing degradation curves; (b) Schematic diagram of degradation process of long afterglow luminescence photocatalyst VO-LiYScGeO4: Bi3+ in dark environment

表S1 LiYScGeO4: Bi3+和VO-LiYScGeO4: Bi3+的余辉衰减参数

Table S1 Afterglow decay parameters of LiYScGeO4: Bi3+ and VO-LiYScGeO4: Bi3+

Sample	A₁	τ₁/s	A₂	τ₂/s	R²
LiYScGeO₄: Bi³⁺	1.59×10⁵	592	1.17×10⁹	283	0.9834
V_O-LiYScGeO₄: Bi³⁺	4.11×10⁴	518	1.69×10⁵	573	0.9967

图S1 LiYScGeO4: Bi3+和VO-LiYScGeO4: Bi3+光催化剂的紫外长余辉发光机制示意图

Fig. S1 Schematic illustration of UV long afterglow luminescence mechanism for LiYScGeO4: Bi3+ and VO-LiYScGeO4: Bi3+ photocatalysts

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基于富氧空位LiYScGeO₄: Bi³⁺长余辉光催化剂的自激活余辉驱动有机污染物芬顿降解

Organic Pollutant Fenton Degradation Driven by Self-activated Afterglow from Oxygen-vacancy-rich LiYScGeO₄: Bi³⁺ Long Afterglow Phosphor

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