CNT-Co/Bi2O3催化剂光催化协同过硫酸盐活化高效降解四环素

doi:10.11949/0438-1157.20240178

摘要/Abstract

摘要：

在过硫酸盐高级氧化技术中，Co²⁺的再生效率低是Co高效活化过一硫酸盐（PMS）的主要问题。成功制备了富含氧缺陷氧化铋负载碳纳米管（x%CNT-Co/Bi₂O₃）光催化剂，用于光催化协同过硫酸盐活化降解污染物。在紫外线照射下，催化剂添加量为20 mg/L、PMS浓度为0.5 mmol/L和初始pH为4.68时，70%CNT-Co/Bi₂O₃对四环素（TC）的降解率高达91.3%，具有优异的可重复利用性和稳定性。其降解活性的提高归因于CNT-Co具有极大的比表面积，有利于TC吸附，光生电子加速Co²⁺→Co³⁺→Co²⁺的循环速率，既促进光生电荷的分离与迁移，又促进PMS的活化，实现TC的快速降解。此外，Bi₂O₃均匀分散在CNT-Co外管壁上，避免了Bi₂O₃纳米颗粒的团聚，CNT-Co具有较大的比表面积，有利于污染物吸附于催化剂表面，增加吸附效果。该体系产生多种活性物种，其贡献度为¹O₂>·SO $4 -$ >·OH>·O $2 -$ ，可实现自由基和非自由基双通路高效降解污染物。

关键词: 活化, 催化, 降解, 四环素, CNT-Co, Bi₂O₃

Abstract:

In the persulfate advanced oxidation process, the low regeneration efficiency of Co²⁺ is the main problem of Co efficient activation of peroxymonosulfate ( PMS ). The photocatalyst of carbon nanotubes loaded with oxygen defect-rich bismuth oxide (x%CNT-Co/Bi₂O₃) was successfully prepared for photocatalytic synergistic persulfate activation and degradation of pollutants. When the initial pH is 4.68 and PMS concentration is 0.5 mmol/L, the degradation of tetracycline(TC) is up to 91.3% under UV light (λ=254 nm) irradiation with 20 mg/L 70%CNT-Co/Bi₂O₃ as catalyst. It has excellent reusability and stability. The improved degradation activity is attributed to the great specific surface area of carbon nanotubes which is favorable to the adsorption of TC. Besides, the photogenerated electrons accelerate the cycle rate of Co²⁺→Co³⁺→Co²⁺, which promotes the separation and migration of photogenerated charges and the activation of PMS, so that a rapid degradation of TC is realized. In addition, Bi₂O₃ is uniformly dispersed on the outer tube wall of CNT-Co, which avoids the agglomeration of Bi₂O₃ nanoparticles. CNT-Co has a large specific surface area, which is conducive to the adsorption of pollutants on the surface of the catalyst and increases the adsorption effect. The system produces a variety of active species, and its contribution is ¹O₂>·SO $4 -$ >·OH>·O $2 -$ , which can realize the efficient degradation of pollutants by free radical and non-free radical.

Key words: activation, catalysis, degradation, tetracycline, CNT-Co, Bi₂O₃

中图分类号:

TQ 032.4

张佳颖, 王聪, 王雅君. CNT-Co/Bi₂O₃催化剂光催化协同过硫酸盐活化高效降解四环素[J]. 化工学报, 2024, 75(9): 3163-3175.

Jiaying ZHANG, Cong WANG, Yajun WANG. CNT-Co/Bi₂O₃ catalyst photocatalytic synergistic activation of persulfate for efficient degradation of tetracycline[J]. CIESC Journal, 2024, 75(9): 3163-3175.

图/表 12

图1 CNT-Co(a)，BiPO4、Bi2O3、15%CNT-Co/BiPO4和19%CNT-Co/BiPO4+Bi2O3(b)，BiPO4、Bi2O3、60%CNT-Co/Bi2O3、70%CNT-Co/Bi2O3和80%CNT-Co/Bi2O3(c)的XRD谱图；CNT-Co、BiPO4、15%CNT-Co/BiPO4和70%CNT-Co/Bi2O3的红外光谱(d)

Fig.1 XRD patterns of CNT-Co (a), BiPO4, Bi2O3, 15%CNT-Co/BiPO4 and 19%CNT-Co/BiPO4+Bi2O3 (b)， BiPO4, Bi2O3, 60%CNT-Co/Bi2O3, 70%CNT-Co/Bi2O3 and 80%CNT-Co/Bi2O3 (c)； FTIR spectra of CNT-Co, BiPO4, 15%CNT-Co/BiPO4 and 70%CNT-Co/Bi2O3 (d)

图2 CNT-Co(a)、BiPO4(b)、15%CNT-Co/BiPO4(c)、19%CNT-Co/BiPO4+Bi2O3(d)和70%CNT-Co/Bi2O3[(e)~(f)]的SEM图

Fig.2 SEM images of CNT-Co (a), BiPO4 (b), 15%CNT-Co/BiPO4 (c), 19%CNT-Co/BiPO4+Bi2O3 (d) and 70%CNT-Co/Bi2O3 [(e)—(f)]

图3 CNT-Co(a)、BiPO4(b)和70%CNT-Co/BiPO4[(c)~(e)]的HRTEM图像；70%CNT-Co/Bi2O3的元素扫描图像(f)

Fig.3 HRTEM images of CNT-Co (a), BiPO4 (b), and 70%CNT-Co/BiPO4 [(c)—(e)]； EDX mapping of the 70%CNT-Co/Bi2O3 (f)

图4 BiPO4和70%CNT-Co/Bi2O3的EPR光谱(a)；CNT-Co、BiPO4、Bi2O3、15%CNT-Co/BiPO4、19%CNT-Co/BiPO4+Bi2O3、60%CNT-Co/Bi2O3、70%CNT-Co/Bi2O3和80%CNT-Co/Bi2O3的UV-Vis DRS光谱(b)；CNT-Co、BiPO4和70%CNT-Co/Bi2O3的N2吸附-脱附等温线(c)

Fig.4 EPR spectra of BiPO4 and 70%CNT-Co/Bi2O3(a)； UV-Vis DRS spectra of CNT-Co, BiPO4, Bi2O3, 15%CNT-Co/BiPO4, 19%CNT-Co/BiPO4+Bi2O3, 60%CNT-Co/Bi2O3, 70%CNT-Co/Bi2O3 and 80%CNT-Co/Bi2O3(b)； N2 adsorption-desorption isotherms of CNT-Co, BiPO4 and 70%CNT-Co/Bi2O3(c)

图5 CNT-Co，BiPO4，Bi2O3和70%CNT-Co/Bi2O3的XPS谱图

Fig.5 XPS spectra of CNT-Co, BiPO4, Bi2O3 and 70%CNT-Co/Bi2O3

图6 紫外线（λ=254 nm）照射下TC在不同反应体系中的降解曲线(a)和降解率(b)；可见光（λ≥420 nm）照射下TC在不同反应体系中的降解曲线(c)和降解率(d)

Fig.6 The degradation curve (a) and degradation rate (b) of TC in different reaction systems under ultraviolet light irradiation (λ=254 nm)； The degradation curve (c) and degradation rate (d) of TC in different reaction systems under visible light irradiation (λ≥420 nm)

图7 与文献报道的四环素的降解效率的对比

Fig.7 Comparison with the degradation efficiency of tetracycline reported in literatures

图8 CNT-Co/Bi2O3质量分数(a)、催化剂投加量(b)、PMS浓度(c)和pH(d)对TC降解效能的影响

Fig.8 Eeffect of mass fraction of CNT-Co/Bi2O3 (a)， catalyst dosages (b)， PMS concentration（c） and pH (d) on degradation of TC

图9 70%CNT-Co/Bi2O3样品循环活性(a)；70%CNT-Co/Bi2O3反应前后XRD谱图(b)

Fig.9 Cycle activity of 70%CNT-Co/Bi2O3 sample(a); XRD patterns of 70%CNT-Co/Bi2O3 before and after reaction(b)

图10 70%CNT-Co/Bi2O3的活性物种捕获实验(a)和降解率(b)；70%CNT-Co/Bi2O3体系中DMPO-·OH，·SO4-和·O2-(c)， TEMP-1O2(d)的EPR谱

Fig.10 Active species capture experiment of 70%CNT-Co/Bi2O3(a) and degradation rate(b)； EPR spectra of DMPO-·OH, ·SO4- and ·O2- (c), TEMP-1O2 adducts (d) of 70%CNT-Co/Bi2O3 system

图11 70%CNT-Co/Bi2O3降解TC的可能路径

Fig.11 Possible degradation pathway of TC by 70%CNT-Co/Bi2O3

图12 70%CNT-Co/Bi2O3降解TC的机理

Fig.12 Mechanism of TC degradation by 70%CNT-Co/Bi2O3

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CNT-Co/Bi₂O₃催化剂光催化协同过硫酸盐活化高效降解四环素

CNT-Co/Bi₂O₃ catalyst photocatalytic synergistic activation of persulfate for efficient degradation of tetracycline

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