Page 178 - 《精细化工》2022年第10期

第 39 卷第 10 期 精 细 化 工 Vol.39, No.10
2022 年 10 月 FINE CHEMICALS Oct. 2022

水处理技术与环境保护
Zr 掺杂 g-C N 光催化降解有机污染物
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张仰全 ，李龙飞 ，周 峰 ，苑兴洲 ，胡绍争 ，张 健
（1. 辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001；2. 中国石油化工股份有限公司 大连石油化
工研究院，辽宁 大连 116000）
摘要：以盐酸胍为前驱体、Zr(NO 3 ) 4 •5H 2 O 为锆源，通过热聚合法制备了 Zr 掺杂 g-C 3 N 4 光催化剂（Zr/g-C 3 N 4 ）。
采用 XRD、SEM、UV-Vis DRS、PL、XPS、N 2 吸附-脱附对催化剂的结构、形貌、光学性能进行了表征与分析。
结果表明，掺杂后的 Zr/g-C 3 N 4 光催化剂拓宽了可见光的吸收，增大了比表面积，且降低了光生电子-空穴的复
合，具有较好的光催化活性。在可见光照射下，60 min 内，5Zr/g-C 3 N 4 〔即 Zr(NO 3 ) 4 •5H 2 O 质量为盐酸胍质量的
5%〕对罗丹明 B（RhB）的光催化降解率达 99.29%，光催化降解过程符合一级动力学方程，其速率常数为
–1
0.08647 min ，约是纯 g-C 3 N 4 的 8.3 倍。此外，5Zr/g-C 3 N 4 对甲基橙和盐酸四环素也表现出良好的光催化性能，
在 60 min 内对二者的降解率分别为 98.02%和 84.47%（5Zr/g-C 3 N 4 降解 RhB、MO 及 TC-HCl 的投加量均为 0.05 g，
且均未调整溶液 pH）。降解 RhB 的主要活性物种为超氧自由基，并推测了可能的反应机理。
关键词：氮化碳；锆掺杂；光催化；降解；水处理技术
中图分类号：X703.5 文献标识码：A 文章编号：1003-5214 (2022) 10-2112-10

Zr-doped g-C 3N 4 photocatalytic degradation of organic pollutants

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ZHANG Yangquan , LI Longfei , ZHOU Feng , YUAN Xingzhou ,
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HU Shaozheng , ZHANG Jian
（1. School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China;
2. Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian 116000, Liaoning, China）
Abstract: Zr-doped g-C 3N 4 photocatalysts (Zr/g-C 3N 4) were prepared by thermal polymerization of
guanidine hydrochloride and Zr(NO 3) 4•5H 2O. The structure, morphology, and optical properties of the
catalysts synthesized were then characterized and analyzed by XRD, SEM, UV-Vis DRS, PL, XPS and N 2
adsorption-desorption. The results showed that the doped Zr/g-C 3N 4 photocatalysts, leading to wider
visible-light absorption range, increasing the specific surface area, and reducing the recombination of
photogenerated electron-hole pairs, demonstrated good photocatalytic activity. The photocatalytic
degradation rate of rhodamine B (RhB) by 5Zr/g-C 3N 4 [Zr(NO 3) 4•5H 2O was 5% of the mass of guanidine
hydrochloride] reached 99.29% within 60 min under visible-light irradiation. Furthermore, the
photocatalytic degradation process conformed to the first-order kinetic equation, and the rate constant was
–1
0.08647 min , 8.3-fold that of pure g-C 3N 4. Meanwhile, 5Zr/g-C 3N 4 also exhibited excellent photocatalytic
performance for methyl orange(MO) and tetracycline hydrochloride(TC-HCl) degradation, with degradation
rates of 98.02% and 84.47% within 60 min, respectively (the dosage of 5Zr/g-C 3N 4 for the degradation of
RhB, MO and TC-HCl was 0.05 g, and the pH of the solution was not adjusted). It was found that the main
active species involved in RhB degradation was superoxide radical, based on which the possible reaction
mechanism was speculated.
Key words: carbon nitride; zirconium doping; photocatalysis; degradation; water treatment technology

目前，光催化被公认是处理环境污染物及制氢 的理想技术之一 [1-2] 。最近，非金属半导体石墨相氮

收稿日期：2022-03-28; 定用日期：2022-06-01; DOI: 10.13550/j.jxhg.20220243
作者简介：张仰全（1999—），男，硕士生，E-mail：2939993094@qq.com。联系人：胡绍争（1981—），男，教授，E-mail：hushaozhenglnpu@
163.com；张 健（1983—），男，教授，E-mail：zhangjian2011@lnpu.edu.cn。