Oxidative degradation of tetracycline hydrochloride by persulfate catalyzed by nitrogen-doped mesoporous carbon

doi:10.19965/j.cnki.iwt.2021-0528

Abstract

Abstract:

A series of nitrogen-doped mesoporous carbons（NMCs）were prepared by using liquor grains as carbon source，nano-silica as template and different amount of melamine as nitrogen source. N₂ adsorption/desorption，XPS，XRD，FT-IR and Raman were used to characterize the structure and surface properties of NMCs，and NMCs were used to catalyze persulfate（PS）oxidation for treating tetracycline hydrochloride（TC）wastewater. The results showed that the difference in the amount of melamine had little effect on the pore structure of NMCs. The pore size was concentrated around 3.8 nm，and the specific surface area was 138-184 m²/g. The activity of NMCs increased with the increase of melamine，and this enhancement was closely related to the surface pyridine nitrogen and graphitic nitrogen. The reaction of PS activation to degrade TC met with the pseudo-second-order kinetic model，and the activation energy was 20.29 kJ/mol. When the added amount of melamine was 14.5%，its catalytic activity was the best. Under the conditions of 25 ℃，0.4 g/L catalyst，0.4 g/L PS， and wide pH range（4.0-11.0），the degradation efficiency of TC（50 mg/L）reached 82.9% after 60 min of reaction. The results of free radical masking indicated that surface free radical reactions played a major role. After 4th cycles，the catalytic activity recovered to 86.9% by high-temperature regeneration.

Key words: liquor grains, nitrogen-doping, mesoporous carbon, persulfate, antibiotics

摘要：

以白酒糟为碳源、纳米SiO₂为模板剂，通过调控三聚氰胺添加量一步法制备了系列氮掺杂介孔碳（NMCs）。采用N₂吸附/脱附、XPS、XRD、FT-IR、Raman等手段对NMCs的结构与表面性质进行表征，并将NMCs用于催化过硫酸盐（PS）处理盐酸四环素（TC）废水。结果表明，三聚氰胺投加量的不同，对NMCs的孔结构影响不大，孔径集中分布在3.8 nm附近，比表面积在138～184 m²/g之间；NMCs催化降解TC的活性随着三聚氰胺投加量的增大而增强，其增强与表面吡啶氮和石墨氮2种含氮官能团密切相关。NMCs活化PS降解TC符合准二级动力学，反应活化能为20.29 kJ/mol；当三聚氰胺添加量为白酒糟质量的14.5%时，其催化活性最好。在反应温度为25 ℃，催化剂投加量为0.4 g/L，PS投加量为0.4 g/L和较宽的pH范围（4.0~11.0）条件下，50 mg/L的TC溶液在反应60 min后，降解率可达82.9%。自由基掩蔽结果表明，表面自由基反应起主要作用。催化剂循环使用4次后，通过高温再生，催化活性可恢复至原来的86.9%。

关键词: 白酒糟, 氮掺杂, 介孔碳, 过硫酸盐, 抗生素

CLC Number:

X703.l

Chaoting FU, Qian ZHOU, Bo XING, Guo YANG, Xiang SONG, Xingyong LIU. Oxidative degradation of tetracycline hydrochloride by persulfate catalyzed by nitrogen-doped mesoporous carbon[J]. Industrial Water Treatment, 2022, 42(2): 136-142.

付朝庭, 周倩, 邢波, 杨郭, 宋翔, 刘兴勇. 氮掺杂介孔碳催化过硫酸盐氧化降解盐酸四环素[J]. 工业水处理, 2022, 42(2): 136-142.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0528

https://www.iwt.cn/EN/Y2022/V42/I2/136

Figures/Tables 10

Table 1 Pore structure parameters of NMCs

样品	S _BET/ （m²·g^-1）	V _t/ （cm³·g^-1）	V _meso/（cm³·g^-1）	V _meso/V _t	D _BJH/nm
MC	168.75	0.35	0.30	0.86	3.84
2.5%NMC	157.43	0.37	0.31	0.84	3.83
6.5%NMC	183.87	0.30	0.24	0.80	3.85
10.5%NMC	137.67	0.31	0.27	0.87	3.81
14.5%NMC	158.32	0.30	0.25	0.83	3.84

Fig. 1 XRD pattern of NMCs

Fig. 2 Raman spectra of NMCs

Fig. 3 FT-IR spectra of NMCs

Fig. 4 XPS spectra of N 1s

Table 2 Surface elemental composition of NMCs and atom fraction of different nitrogen structures

试样	C	O	N	N 1s
试样	C	O	N	N-py	N-pyr	N-g	N-O _x
MC	93.94	4.99	1.07	0.23	0.50	0.21	0.12
2.5%NMC	93.83	4.49	1.68	0.41	0.69	0.36	0.22
6.5%NMC	93.15	4.48	2.37	0.61	0.89	0.53	0.33
10.5%NMC	92.78	4.67	2.55	0.71	1.03	0.45	0.36
14.5%NMC	91.89	5.11	3.00	0.88	1.02	0.63	0.47

Fig. 5 Degradation of TC by NMCs and corresponding kinetic model fitting curves

Fig. 6 Correlation between k _app and atom fraction of N-py，N-g，N-py in catalyzing PS oxidation to remove TC

Fig. 7 The effect of different reaction temperature on TC degradation（a） and Arrhenius fitting（b）

Fig. 8 Effect of free radical quenching agent on TC removal by 14.5%NMC

References 25

1	张凌星，肖鹏飞. 活化过硫酸盐氧化处理抗生素废水的研究进展［J］. 工业水处理，2021，41（5）：29-35. doi:10.11894/iwt.2020-0650
	ZHANG Lingxing， XIAO Pengfei. Research progress on treatment of antibiotic wastewater by activated persulfate oxidation［J］. Industrial Water Treatment，2021，41（5）：29-35. doi:10.11894/iwt.2020-0650
2	AO Xiuwei， LIU Wenjun. Degradation of sulfamethoxazole by medium pressure UV and oxidants：Peroxymonosulfate，persulfate，and hydrogen peroxide［J］. Chemical Engineering Journal，2017，313：629-637. doi:10.1016/j.cej.2016.12.089
3	XU Lijie， WANG Xiaotian， SUN Yang，et al. Mechanistic study on the combination of ultrasound and peroxymonosulfate for the decomposition of endocrine disrupting compounds［J］. Ultrasonics Sonochemistry，2020，60：104749. doi:10.1016/j.ultsonch.2019.104749
4	DENG Jing， SHAO Yisheng， GAO Naiyun，et al. Thermally activated persulfate（TAP） oxidation of antiepileptic drug carbamazepine in water［J］. Chemical Engineering Journal，2013，228：765-771. doi:10.1016/j.cej.2013.05.044
5	HUANG Ying， YANG Fei， AI Luoyan，et al. On the kinetics of organic pollutant degradation with Co²⁺/peroxymonosulfate process：When ammonium meets chloride［J］. Chemosphere，2017，179：331-336. doi:10.1016/j.chemosphere.2017.03.110
6	LI Yangju， ZHAO Xiuge， YAN Yan，et al. Enhanced sulfamethoxazole degradation by peroxymonosulfate activation with sulfidemodified microscale zero⁃valent iron （S-mFe⁰）：Performance，mechanisms，and the role of sulfur species［J］. Chemical Engineering Journal，2019，376：121302. doi:10.1016/j.cej.2019.03.178
7	ZHOU Peng， ZHANG Jing， ZHANG Yongli，et al. Degradation of 2，4-dichlorophenol by activating persulfate and peroxomonosulfate using micron or nanoscale zero⁃valent copper［J］. Journal of Hazardous Materials，2018，344：1209-1219. doi:10.1016/j.jhazmat.2017.11.023
8	LIU Ying， MIAO Wei， FANG Xian，et al. MOF⁃derived metal⁃free N⁃doped porous carbon mediated peroxydisulfate activation via radical and non‑radical pathways：Role of graphitic N and CO［J］. Chemical Engineering Journal，2020，380：122584. doi:10.1016/j.cej.2019.122584
9	DUAN Xiaoguang， SUN Hongqi， KANG Jian，et al. Insights into heterogeneous catalysis of persulfate activation on dimensional-structured nanocarbons［J］. ACS Catalysis，2015，5（8）：4629-4636. doi:10.1021/acscatal.5b00774
10	WANG Jun， DUAN Xiaoguang， DONG Qi，et al. Facile synthesis of N⁃doped 3D graphene aerogel and its excellent performance in catalytic degradation of antibiotic contaminants in water［J］. Carbon，2019，144：781-790. doi:10.1016/j.carbon.2019.01.003
11	DUAN Xiaoguang， AO Zhimin， SUN Hongqi，et al. Nitrogen⁃doped graphene for generation and evolution of reactive radicals by metal‑free catalysis［J］. ACS Applied Materials & Interfaces，2015，7（7）：4169-4178. doi:10.1021/am508416n
12	HEILMANN S M， JADER L R， SADOWSKY M J，et al. Hydrothermal carbonization of distiller’s grains［J］. Biomass and Bioenergy，2011，35（7）：2526-2533. doi:10.1016/j.biombioe.2011.02.022
13	DUAN Xiaoguang， SUN Hongqi， WANG Yuxian，et al. N⁃doping⁃induced nonradical reaction on single⁃walled carbon nanotubes for catalytic phenol oxidation［J］. ACS Catalysis，2015，5（2）：553-559. doi:10.1021/cs5017613
14	JIA Nengqin， WANG Zhiyong， YANG Guofeng，et al. Electrochemical properties of ordered mesoporous carbon and its electroanalytical application for selective determination of dopamine［J］. Electrochemistry Communications，2007，9（2）：233-238. doi:10.1016/j.elecom.2006.08.050
15	郭晓娜. 氮掺杂活性炭材料的制备及性能研究［D］. 贵州：贵州大学，2016.
	GUO Xiaona.Preparation and properties of nitrogen⁃doped activated carbon material［D］. Guizhou：Guizhou University，2016.
16	PUZIY A M， PODDUBNAYA O I， MARTÍNEZ⁃ALONSO A，et al. Surface chemistry of phosphorus⁃containing carbons of lignocellulosic origin［J］. Carbon，2005，43（14）：2857-2868. doi:10.1016/j.carbon.2005.06.014
17	SONG Xiang， XING Bo， FENG Jing，et al. Degradation of organic dyes by persulfate using liquor grain⁃derived N，P⁃codoped mesoporous carbon as metal⁃free catalyst［J］. Journal of Water Process Engineering，2020，37：101407. doi:10.1016/j.jwpe.2020.101407
18	徐赞，于薛刚，单妍，等. 一步法合成磷掺杂石墨相氮化碳及其光催化性能［J］. 无机材料学报，2017，32（2）：155-162. doi:10.15541/jim20160256
	XU Zan， YU Xuegang， SHAN Yan，et al. One⁃pot synthesis of phosphorus doped G-C₃N₄ with enhanced visible-light photocatalytic activity［J］. Journal of Inorganic Materials，2017，32（2）：155-162. doi:10.15541/jim20160256
19	WANG Na， MA Wenjie， REN Ziqiu，et al. Prussian blue analogues derived porous nitrogen⁃doped carbon microspheres as high‑performance metal⁃free peroxymonosulfate activators for non⁃radical⁃dominated degradation of organic pollutants［J］. Journal of Materials Chemistry A，2018，6（3）：884-895. doi:10.1039/c7ta08472b
20	HUO Xiaowei， ZHOU Peng， ZHANG Jing，et al. N，S‑doped porous carbons for persulfate activation to remove tetracycline：Nonradical mechanism［J］. Journal of Hazardous Materials，2020，391：122055. doi:10.1016/j.jhazmat.2020.122055
21	SUN Hongqi， KWAN C， SUVOROVA A，et al. Catalytic oxidation of organic pollutants on pristine and surface nitrogen⁃modified carbon nanotubes with sulfate radicals［J］. Applied Catalysis B：Environmental，2014，154/155：134-141. doi:10.1016/j.apcatb.2014.02.012
22	李玲. 纳米铁基材料的制备及其催化降解有害污染物机理的研究［D］.广东：华南理工大学，2018. doi:10.15541/jim20170394
	LI Ling. Preparation of nanosized iron⁃based materials and their catalytic degradation performance of harmful pollutants［D］.Guangdong：South China University of Technology，2018. doi:10.15541/jim20170394
23	王莹，魏成耀，黄天寅，等. 氮掺杂碳纳米管活化过一硫酸盐降解酸性橙AO7［J］. 中国环境科学，2017，37（7）：2583-2590.
	WANG Ying， WEI Chengyao， HUANG Tianyin，et al.Activation of peroxymonosulfate by nitrogen⁃doped carbon nanotubes to decolorize acid orange 7［J］.China Environmental Science，2017，37（7）：2583-2590.
24	FOROUZESH M， EBADI A， AGHAEINEJAD⁃MEYBODI A. Degradation of metronidazole antibiotic in aqueous medium using activated carbon as a persulfate activator［J］. Separation and Purification Technology，2019，210：145-151. doi:10.1016/j.seppur.2018.07.066
25	YANG Shiying， XIAO Tuo， ZHANG Jun，et al. Activated carbon fiber as heterogeneous catalyst of peroxymonosulfate activation for efficient degradation of acid orange 7 in aqueous solution［J］. Separation and Purification Technology，2015，143：19-26. doi:10.1016/j.seppur.2015.01.022

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