CuO/CN催化过一硫酸盐降解四环素性能及机理研究

doi:10.19964/j.issn.1006-4990.2023-0605

摘要/Abstract

摘要：

利用室温合成和高温热解法制备了不同负载量的CuO/CN非均相催化剂，用于活化过一硫酸盐（PMS）降解四环素（TC）。通过傅里叶变换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、能量色散X射线荧光光谱仪（EDS）、X射线粉末衍射仪（XRD）等表征仪器对材料进行了详细表征，评价了CuO/CN材料的表面形貌和物质状态。结果表明，铜以CuO的形式均匀地负载在CN上，并对PMS降解四环素表现出高效的催化性能。在四环素初始质量浓度为20 mg/L、pH=5.5、PMS浓度为0.3 mmol/L、2.5%CuO/CN投加量为0.2 g/L的条件下，处理120 min后TC降解率达93.72%。采用猝灭实验和电子自旋共振（EPR）技术分析降解过程的活性物质，结果表明¹O₂是TC降解过程的主要活性物种。催化剂历经5次循环实验后，TC降解率仍能够达到86.39%，表明催化剂具有较好的稳定性和重复使用性。因此，CuO/CN在催化PMS降解TC等抗生素方面具有良好的应用前景。

关键词: CuO/CN, 高级氧化, 四环素, 过一硫酸盐

Abstract:

Non⁃homogeneous CuO/CN catalysts with different loadings were prepared by synthesis at room temperature and pyrolysis at high temperature for the degradation of tetracycline（TC） by activated peroxynitrite（PMS）.The materials were characterised in detail and the surface morphology and state of matter of the CuO/CN materials were evaluated by Fourier transform infrared spectroscopy（FT-IR），scanning electron microscopy（SEM），energy dispersive X-ray fluorescence spectrometry（EDS），X-ray powder diffractometry（XRD） and other characterisation techniques.The results showed that for the degradation of tetracycline by PMS，copper was uniformly loaded on CN in the form of CuO，which exhibited efficient catalytic performance.Under the conditions of tetracycline initial mass concentration of 20 mg/L，pH=5.5，PMS concentration of 0.3 mmol/L and 2.5% CuO/CN dosage of 0.2 g/L，the TC degradation rate reached 93.72% after 120 min of treatment.The active substances of the degradation process were analysed by bursting experiment and electron spin resonance（EPR） technique，and the results showed that ¹O₂ was the main active species in the TC degradation process.The TC degradation rate could still reach 86.39% after five cycling experiments，indicating that the catalyst had good stability and reusability.Therefore，CuO/CN had good application prospects in catalyzing the degradation of antibiotics such as TC by PMS.

Key words: CuO/CN, advanced oxidation, tetracycline, peroxymonosulfate

中图分类号:

O643

项伟, 景燕娜, 陈铮华, 陈晓, 金延超. CuO/CN催化过一硫酸盐降解四环素性能及机理研究[J]. 无机盐工业, 2024, 56(8): 123-130.

XIANG Wei, JING Yanna, CHEN Zhenghua, CHEN Xiao, JIN Yanchao. Study on performance and mechanism of CuO/CN catalysed peroxynitrite degradation of tetracycline[J]. Inorganic Chemicals Industry, 2024, 56(8): 123-130.

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参考文献 31

1	李钲，王国栋，陈日耀，等.椰壳炭吸附去除四环素性能及机理研究［J］.福建师范大学学报（自然科学版），2023，39（5）：117-123.
	LI Zheng， WANG Guodong， CHEN Riyao，et al.Study on the adsorption performance and mechanism of coconut shell carbon on tetracycline in water［J］.Journal of Fujian Normal University （Natural Science Edition），2023，39（5）：117-123.
2	ZHANG Xiao， REN Bin， LI Xi，et al.High⁃efficiency removal of tetracycline by carbon⁃bridge⁃doped g-C₃N₄/Fe₃O₄ magnetic heterogeneous catalyst through photo⁃Fenton process［J］.Journal of Hazardous Materials，2021，418：126333.
3	ZHANG Wei， ZHANG Gaosheng， LIU Caihong，et al.Enhanced removal of arsenite and arsenate by a multifunctional Fe-Ti-Mn composite oxide：Photooxidation，oxidation and adsorption［J］.Water Research，2018，147：264-275.
4	叶鹭婷，王心如，陈隋晓辰，等.紫外光电芬顿降解四环素性能研究［J］.福建师范大学学报（自然科学版），2023，39（1）：21-27.
	YE Luting， WANG Xinru， CHEN Suixiaochen，et al.Study on the degradation of tetracycline by UV photoelectro⁃Fenton process［J］.Journal of Fujian Normal University（Natural Science Edition），2023，39（1）：21-27.
5	WANG Anqi， ZHENG Zhikeng， WANG Hui，et al.3D hierarchical H₂-reduced Mn-doped CeO₂ microflowers assembled from nanotubes as a high⁃performance Fenton⁃like photocatalyst for tetracycline antibiotics degradation［J］.Applied Catalysis B：Environmental，2020，277：119171.
6	周紫荆，陈隋晓辰，杨星雨，等.石墨阴极电芬顿降解诺氟沙星的研究［J］.福建师范大学学报（自然科学版），2021，37（5）：30-33.
	ZHOU Zijing， CHEN Suixiaochen， YANG Xingyu，et al.Experimental study on the degradation of norfloxacin by electro⁃Fenton with graphite cathode［J］.Journal of Fujian Normal University（Na⁃tural Science Edition），2021，37（5）：30-33.
7	ASGARI E， HASHEMZADEH B， HASSANI G，et al.Enhancement the BuP photo⁃catalytic degradability by UVC/ZnO through adding exogenous oxidant：Mechanism，kinetic，energy consumption［J］.Journal of Environmental Chemical Engineering，2020， 8（1）：103576.
8	ZHANG Jin， ZENG Hanxuan， BU Lingjun，et al.Cu⁰ incorporated cobalt/nitrogen doped carbonaceous frameworks derived from ZIF-67（Cu@Co-NC） as PMS activator for efficient degradation of naproxen：Direct electron transfer and ¹O₂ dominated nonradical mechanisms［J］.Chemical Engineering Journal，2023，454：139989.
9	ZHANG Haojie， ZHOU Chan， ZENG Hanxuan，et al.Novel sulfur vacancies featured MIL-88A（Fe）@CuS rods activated peroxymonosulfate for coumarin degradation：Different reactive oxygen species generation routes under acidic and alkaline pH［J］.Process Safety and Environmental Protection，2022，166：11-22.
10	ZHU Lei， SHI Zhou， DENG Lin，et al.Fabrication of epigallocatechin-3-gallate（EGCG） functionalized Mn₃O₄ for enhanced degradation of carbamazepine with peroxymonosulfate activation［J］.Process Safety and Environmental Protection，2022，158：42- 54.
11	DING Yaobin， WANG Xueru， FU Libin，et al.Nonradicals induced degradation of organic pollutants by peroxydisulfate（PDS） and peroxymonosulfate（PMS）：Recent advances and perspecti⁃ve［J］.The Science of the Total Environment，2021，765：142794.
12	WANG Qi， LIU Cun， ZHOU Dongmei，et al.Degradation of bisphenol a using peroxymonosulfate activated by single⁃atomic cobalt catalysts：Different reactive species at acidic and alkalinepH［J］.Chemical Engineering Journal，2022，439：135002.
13	WANG Meimei， CUI Yunke， CAO Hongyang，et al.Activating peroxydisulfate with Co₃O₄/NiCo₂O₄ double⁃shelled nanocages to selectively degrade bisphenol A-A nonradical oxidation proce⁃ss［J］.Applied Catalysis B：Environmental，2021，282：119585.
14	FENG Yijie， SANG Wenjiao， DENG Zhiyi，et al.Co-N-C@SiO₂ core@shell architectures enhanced stability to activate peroxymonosulfate（PMS） for efficient sulfamethoxazole degradation［J］.Separation and Purification Technology，2022，280：119783.
15	GAO Yaowen， CHEN Zhenhuan， ZHU Yue，et al.New insights into the generation of singlet oxygen in the metal⁃free peroxymonosulfate activation process：Important role of electron⁃deficient carbon atoms［J］.Environmental Science & Technology，2020，54（2）：1232-1241.
16	CHEN Mingming， NIU Huaiyuan， NIU Chenggang，et al.Metal⁃organic framework⁃derived CuCo/carbon as an efficient magnetic heterogeneous catalyst for persulfate activation and ciprofloxacin degradation［J］.Journal of Hazardous Materials，2022，424：127196.
17	XUE Yudong， PHAM N N T，NAM G，et al.Persulfate activation by ZIF-67-derived cobalt/nitrogen⁃doped carbon composites：Kinetics and mechanisms dependent on persulfate precursor［J］.Chemical Engineering Journal，2021，408：127305.
18	CHEN Xiongjian， JIN Yanchao， HUANG Peiwen，et al.Solar driven photocatalytic disinfection by Z-scheme heterojunction of In₂O₃/g-C₃N₄：Performance，mechanism and application［J］.Applied Catalysis B：Environmental，2024，340：123235.
19	KANG Yuyang， YANG Yongqiang， YIN Lichang，et al.An amorphous carbon nitride photocatalyst with greatly extended visible⁃light⁃responsive range for photocatalytic hydrogen generation［J］.Advanced Materials，2015，27（31）：4572-4577.
20	LIANG Qinghua， LI Zhi， HUANG Zhenghong，et al.Holey graphitic carbon nitride nanosheets with carbon vacancies for highly improved photocatalytic hydrogen production［J］.Advanced Func⁃ tional Materials，2015，25（44）：6885-6892.
21	GAO Yaowen， ZHU Yue， Lai LYU，et al.Electronic structure modulation of graphitic carbon nitride by oxygen doping for enhanced catalytic degradation of organic pollutants through peroxymonosulfate activation［J］.Environmental Science & Technology，2018，52（24）：14371-14380.
22	LI Dongya， ZAN Jie， WU Liping，et al.Heterojunction tuning and catalytic efficiency of g-C₃N₄-Cu₂O with glutamate［J］.Industri⁃al & Engineering Chemistry Research，2019，58（10）：4000-4009.
23	ZHANG Jinshui， ZHANG Mingwen， ZHANG Guigang，et al.Synthesis of carbon nitride semiconductors in sulfur flux for water photoredox catalysis［J］.ACS Catalysis，2012，2（6）：940-948.
24	YUAN Xiaohong， LUO Kun， ZHANG Keqin，et al.Combinatorial vibration⁃mode assignment for the FT-IR spectrum of crystalline melamine：A strategic approach toward theoretical IR vibrational calculations of triazine⁃based compounds［J］.The Journal of Phy⁃ sical Chemistry A，2016，120（38）：7427-7433.
25	SURESH R， KARTHIKEYAN N S， GNANASEKARAN L，et al.Facile synthesis of CuO/g-C₃N₄ nanolayer composites with superior catalytic reductive degradation behavior［J］.Chemosphere，2023，315：137711.
26	LIANG Chenju， WANG Z S， BRUELL C J.Influence of pH on persulfate oxidation of TCE at ambient temperatures［J］.Chemosphere，2007，66（1）：106-113.
27	QIAN Jin， MI Xiaohui， CHEN Zhijie，et al.Efficient emerging contaminants（EM） decomposition via peroxymonosulfate（PMS） activation by Co₃O₄/carbonized polyaniline（CPANI） composite：Characterization of tetracycline（TC） degradation property and application for the remediation of EM-polluted water body［J］.Journal of Cleaner Production，2023，405：137023.
28	ZENG Qingyi， WANG Yumei， ZHANG Qingyan，et al.Activity and mechanism of vanadium sulfide for organic contaminants oxidation with peroxymonosulfate［J］.Journal of Colloid and Interface Science，2023，635：358-369.
29	ZENG Qingyi， TAN Jing， GAO Beibei，et al.Embedding Co in perovskite MoO₃ for superior catalytic oxidation of refractory organic pollutants with peroxymonosulfate［J］.Chemosphere，2023，314：137726.
30	HUANG Na， WANG Tong， WU Yingxuan，et al.Preparation of magnetically recyclable hierarchical porous sludge⁃pine needle derived biochar loaded CoFe₂O₄ nanoparticles for rapid degradation of tetracycline by activated PMS［J］.Materials Today Communications，2023，35：106313.
31	YANG Jingren， ZHANG Yanhe， ZENG Deqian，et al.Enhanced catalytic activation of photo⁃Fenton process by Cu_0.5Mn_0.5Fe₂O₄ for effective removal of organic contaminants［J］.Chemosphere，2020，247：125780.

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