Z型CN/NGBO/BV催化剂体系的构筑及光类芬顿降解四环素性能

doi:10.16085/j.issn.1000-6613.2024-0108

摘要/Abstract

摘要：

环境中残留的四环素会对水生生物产生慢性影响，四环素随着生活水体排入景区水体，影响景区水中的水质，本研究采用煅烧法和水热法以橘子皮粉末为原材料制备类石墨烯（GBO），通过氮掺杂优化GBO（NGBO）提高其电子传输速率，将NGBO作为固态电子介质在g-C₃N₄/BiVO₄界面构建Z型三元光催化剂。通过在光催化基础上引入氧化剂H₂O₂，构建Z型催化剂/光类芬顿催化复合体系，将类芬顿催化降解技术和光催化技术相耦合。将10mg的催化剂和5mmol/L的H₂O₂加入50mL的10mg/L四环素溶液中，结果表明Z型催化剂光类芬顿催化降解TC的性能，在光照90min后，所制备的CN/NGBO/BV复合材料的光类芬顿催化降解TC能力最强。降解TC的催化能力得到提升的原因是光照和H₂O₂会促进催化降解TC体系中生成更多的·OH和·O₂^-，同时实验结果表明光催化技术与类芬顿催化技术存在相互协同作用。

关键词: Z型催化剂, 光芬顿, 四环素, 催化降解

Abstract:

Tetracycline residue in the environment will have chronic effects on aquatic organisms. Tetracycline is discharged into scenic water along with living water, affecting the water quality of scenic water. In this study, graphene-like (GBO) was prepared from orange peel powder as raw material and the electron transfer rate was increased by nitrogen doping optimization of GBO (NGBO). Using NGBO as solid state electron medium, Z-type ternary photocatalyst was constructed at g-C₃N₄/BIVO₄ interface. H₂O₂ oxide was introduced as oxidant on the basis of photocatalysis and the Z catalyst/photo-Fenton catalyst system was established. The photocatalytic degradation of TC over Z-type catalyst was studied by adding 10mg catalyst and 5mmol/L H₂O₂ into 50mL of 10mg/L tetracycline solution. The results indicated that the CN/NGBO/BV composite had the strongest photo-Fenton-like catalytic degradation ability of TC. Catalytic degradation of TC was enhanced as light and H₂O₂ contribute to the formation of more ·OH and ·O₂^- during catalytic degradation of TC systems, while experimental results showed synergy between photocatalysis and fenton-like catalysis.

Key words: Z-scheme catalyst, photo-Fenton, tetracycline, catalytic degradation

中图分类号:

TQ127.11

游小银, 汪楚乔, 刘才华, 彭小明. Z型CN/NGBO/BV催化剂体系的构筑及光类芬顿降解四环素性能[J]. 化工进展, 2025, 44(1): 286-296.

YOU Xiaoyin, WANG Chuqiao, LIU Caihua, PENG Xiaoming. Z-scheme CN/NGBO/BV catalytic system and its photo-like Fenton degradation performance of tetracycline[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 286-296.

图/表 12

图1 GBO-900（100nm）、GBO-900（20nm）和GBO-900（5nm）的TEM图及OPB-400和GBO-900的Raman光谱

图2 CN/BV的扫描电镜[(a)、(b)]；CN/NGBO/BV的扫描电镜[(c)、(d)]和CN/NGBO/BV光催化剂的EDS图谱和各元素的空间分布[(e)~(k)]

图3 制备样品的表征分析结果

图4 不同H2O2浓度下CN/NGBO/BV复合材料对TC去除效率和反应动力学常数变化的比较（TC=10mg/L，催化剂投加量=0.2g/L和0.1g/L，H2O2浓度=10mmol/L、5mmol/L、4mmol/L、2mmol/L、1mmol/L、0.5mmol/L、0，初始pH=6.5）

图5 不同复合材料对TC催化降解的影响（TC=10mg/L，催化剂投加量=0.2g/L，初始pH=6.5）

图6 不同复合材料在H2O2浓度为5mmol/L时对TC类芬顿催化降解的影响（TC=10mg/L，催化剂投加量=0.2g/L，H2O2浓度=5mmol/L，初始pH=6.5）

图7 不同催化剂光芬顿降解TC的比较以及相对应的反应速率大小（TC=10mg/L，催化剂投加量=0.2g/L，H2O2浓度=5mmol/L，初始pH=6.5）

图8 初始pH对CN/NGBO/BV/H2O2光类芬顿体系中TC降解的影响（TC=10mg/L，催化剂用量=0.2g/L，H2O2浓度=5mmol/L，初始pH为4、5、6、6.5、7、8、9和10）

图9 不同水质对催化剂CN/NGBO/BV光芬顿降解TC的影响及HA、Cl-、NO3-、HCO3-和H2PO4-阴离子下对TC的降解

图10 不同污染物的降解效率、拟一阶动力学曲线拟合及CN/NGBO/BV光催化剂中DMPO捕获的·O2-和·OH自由基的ESR谱图

图11 反应前后水中TOC、BOD、COD含量的比较

表1 制备样品的光催化、非均相类芬顿和光类芬顿反应速率

样品	光催化		类芬顿		光类芬顿		协同指数k_S
样品	k_P	k²	k_F	R²	k_PF	R²	协同指数k_S
g-C₃N₄	0.0036	0.9350	0.0035	0.9905	0.0104	0.9704	1.465
BiVO₄	0.0076	0.9861	0.0038	0.9988	0.0109	0.9851	0.956
CN/BV	0.0079	0.9897	0.0039	0.9362	0.0129	0.9939	1.093
CN/NGBO/BV	0.0125	0.9952	0.0065	0.9997	0.0249	0.9203	1.311

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