Photocatalytic treatment of coking wastewater by cerium oxide loading with nitrogen-doping co-modified graphite carbon nitride

doi:10.19965/j.cnki.iwt.2023-1096

Abstract

Abstract:

Coking wastewater contains over 500 species toxic substances, and is recognized as the most intractable treated wastewater. Currently, most domestic coking twastewater is treated by biochemical-physicochemical method,and the final effluent water quality is still difficult to meet the “Discharge Standard for Coking Chemical Industry Pollutants”(GB 16171-2012). Thus, the deep treatment and reuse of coking wastewater has become a hot topic in the industry. In order to make up for the shortage of g-C₃N₄ monomer, CeO₂/N-doped g-C₃N₄(CeO₂/NGCN) composite photocatalysts co-modified with nitrogen doping and CeO₂ loading were designed and synthesized with expanding visible light absorption and promoting photogenerated carrier separation. The CeO₂/NGCN(mass fraction of 1%) exhibited excellent photodegradation performance, the removal rate of COD and UV₂₅₄ in the coking wastewater after biological treatment reached 49.79% and 69.37% within 120 min, respectively, which was much higher than that of g-C₃N₄ and N-doped g-C₃N₄. This work proved that N-doping and CeO₂ loading could effectively broaden the photoresponse range of g-C₃N₄, facilitate the separation of photogenerated electron-hole pairs, which provided a reference for the construction of g-C₃N₄-based photocatalyst with high-efficiency photodegradation activity.

Key words: graphite carbon nitride, coking wastewater, advanced treatment, photocatalytic

摘要：

焦化废水中毒性物质超过500种，是公认的难处理废水。国内多数焦化企业的生产废水采用生化-物化法处理，最终出水水质指标难以达到《炼焦化学工业污染物排放标准》（GB 16171—2012）。因此，对焦化废水进行深度处理回用成为行业热点。作为最受青睐的光催化材料，石墨相氮化碳（g-C₃N₄）被广泛用于去除水中有机污染物。采用二氧化铈（CeO₂）负载及氮掺杂来优化氮化碳，成功制备出具有良好吸光性能及光生载流子分离效率的CeO₂/N-g-C₃N₄（CeO₂/NGCN）复合光催化剂。CeO₂/NGCN（质量分数1%）展现了极佳的光催化性能，120 min内对焦化废水生化出水COD、UV₂₅₄的降解效率分别达到了49.79%、69.37%，远高于g-C₃N₄及氮掺杂g-C₃N₄。氮掺杂及二氧化铈负载可有效拓宽g-C₃N₄的光吸收范围，促进光生载流子分离效率，对构建高性能g-C₃N₄基光催化剂具有借鉴意义。

关键词: 氮化碳, 焦化废水, 深度处理, 光催化

CLC Number:

X703.1

Ning AN, Yuying HAO, Shaowei HU, Peng CHEN, Fei WANG, Yong WANG, Fang LIU, Hanfei LI. Photocatalytic treatment of coking wastewater by cerium oxide loading with nitrogen-doping co-modified graphite carbon nitride[J]. Industrial Water Treatment, 2024, 44(12): 184-191.

安宁, 郝玉莹, 胡绍伟, 陈鹏, 王飞, 王永, 刘芳, 李函霏. 二氧化铈/氮掺杂氮化碳光催化处理焦化废水[J]. 工业水处理, 2024, 44(12): 184-191.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-1096

https://www.iwt.cn/EN/Y2024/V44/I12/184

Figures/Tables 11

Fig.1 XRD and FT-IR patterns of obtained materials

Fig.2 The FE-SEM image of GCN（a）， NGCN（b） and CeO₂/NGCN（mass fraction of 1%）（c）， the TEM image of CeO₂/NGCN（mass fraction of 1%）（d-e）， the HTEM image of CeO₂/NGCN（mass fraction of 1%）（f）

Fig.3 XPS spectra of the GCN，NGCN， and CeO₂/NGCN（mass fraction of 1%）

Table 1 Element content of synthesized photocatalysts

光催化剂样品	质量分数/%				N/C物质的量比
光催化剂样品	C	N	O	Ce	N/C物质的量比
GCN	46.07	52.26	1.67	0	1.134
NGCN	42.12	55.92	1.96	0	1.328
CeO₂/NGCN（质量分数1%）	40.37	51.69	3.93	4.01	1.280

Fig.4 UV-vis diffuse reflectance spectra（a） and bandgap energy（b） of photocatalysts

Fig.5 Photocurrent responses of prepared photocatalysts

Fig.6 EIS Nyquist plots of prepared photocatalysts

Fig.7 PL spectra of prepared photocatalysts

Fig.8 Photodegradation curves of COD and UV₂₅₄by prepared photocatalysts

Fig.9 The free radical trapping experiments for degradation of UV₂₅₄ over CeO₂/NGCN（mass fraction of 1%） photocatalyst

Fig.10 The possible photocatalytic mechanism of CeO₂/NGCN（mass fraction of 1%）

References 29

1	夏立全，陈贵锋，李文博，等. 焦化废水处理技术进展与发展方向［J］. 洁净煤技术，2020，26（4）：56-63.
	XIA Liquan， CHEN Guifeng， LI Wenbo，et al. Progress and perspectives of coking wastewater treatment technology［J］. Clean Coal Technology，2020，26（4）：56-63.
2	张怡鸣，张玉秀，祖德彪，等. 焦化废水处理技术及其污泥细菌菌群结构功能研究进展［J］. 矿业科学学报，2020，5（2）：232-241.
	ZHANG Yiming， ZHANG Yuxiu， ZU Debiao，et al. Coking wastewater treatment technology and its bacterial community structure and function in sludge［J］. Journal of Mining Science and Technology，2020，5（2）：232-241.
3	刘宝河，王智，李政辉，等. TiO₂/MWCNTs光催化氧化法深度处理焦化废水生化尾水［J］. 环境科学与技术，2022，45（1）：92-100.
	LIU Baohe， WANG Zhi， LI Zhenghui，et al. Advanced treatment of biologically treated coking wastewater by TiO₂/MWCNTs photocatalytic oxidation［J］. Environmental Science & Technology，2022，45（1）：92-100.
4	LAI Cui， AN Ning， LI Bisheng，et al. Future roadmap on nonmetal-based 2D ultrathin nanomaterials for photocatalysis［J］. Chemical Engineering Journal，2021，406：126780. doi:10.1016/j.cej.2020.126780
5	HUANG Ying， CHEN Bo， DUAN Jian，et al. Graphitic carbon nitride（g-C₃N₄）：An interface enabler for solid-state lithium metal batteries［J］. Angewandte Chemie（International Ed.in English），2020，59（9）：3699-3704. doi:10.1002/anie.201914417
6	HUANG Yuanyong， LI Di， FANG Zhenyuan，et al. Controlling carbon self-doping site of g-C₃N₄ for highly enhanced visible-light-driven hydrogen evolution［J］. Applied Catalysis B：Environmental，2019，254：128-134. doi:10.1016/j.apcatb.2019.04.082
7	ONG W J， TAN L L， NG Y H，et al. Graphitic carbon nitride（g-C₃N₄）-based photocatalysts for artificial photosynthesis and environmental remediation：Are we a step closer to achieving sustainability？［J］. Chemical Reviews，2016，116（12）：7159-7329. doi:10.1021/acs.chemrev.6b00075
8	JIANG Longbo， YUAN Xingzhong， PAN Yang，et al. Doping of graphitic carbon nitride for photocatalysis：A review［J］. Applied Catalysis B： Environmental，2017，217：388–406. doi:10.1016/j.apcatb.2017.06.003
9	ZHENG Yun， LIN Lihua， WANG Bo，et al. Graphitic carbon nitride polymers toward sustainable photoredox catalysis［J］. Angewandte Chemie（International Ed.in English），2015，54（44）：12868-12884. doi:10.1002/anie.201501788
10	ZHOU Yajun， ZHANG Lingxia， HUANG Weimin，et al. N⁃doped graphitic carbon-incorporated g-C₃N₄ for remarkably enhanced photocatalytic H₂ evolution under visible light［J］. Carbon，2016，99：111-117. doi:10.1016/j.carbon.2015.12.008
11	ZHU Dandan， ZHOU Qixing. Nitrogen doped g-C₃N₄ with the extremely narrow band gap for excellent photocatalytic activities under visible light［J］. Applied Catalysis B：Environmental，2021，281：119474. doi:10.1016/j.apcatb.2020.119474
12	LAI Cui， XU Fuhang， ZHANG Mingming，et al. Facile synthesis of CeO₂/carbonate doped Bi₂O₂CO₃ Z-scheme heterojunction for improved visible-light photocatalytic performance：Photodegradation of tetracycline and photocatalytic mechanism［J］. Journal of Colloid and Interface Science，2021，588：283-294. doi:10.1016/j.jcis.2020.12.073
13	NAIDI S N， HARUNSANI M H， TAN Ai ling，et al. Green-synthesized CeO₂ nanoparticles for photocatalytic，antimicrobial，antioxidant and cytotoxicity activities［J］. Journal of Materials Chemistry B，2021，9（28）：5599-5620. doi:10.1039/d1tb00248a
14	JIANG Longbo， YUAN Xingzhong， ZENG Guangming，et al. Phosphorus- and sulfur-codoped g-C₃N₄：Facile preparation，mechanism insight，and application as efficient photocatalyst for tetracycline and methyl orange degradation under visible light irradiation［J］. ACS Sustainable Chemistry & Engineering，2017，5（7）：5831-5841. doi:10.1021/acssuschemeng.7b00559
15	HUMAYUN M， HU Zhewen， KHAN A，et al. Highly efficient degradation of 2，4-dichlorophenol over CeO₂/g-C₃N₄ composites under visible-light irradiation：Detailed reaction pathway and mechanism［J］. Journal of Hazardous Materials，2019，364：635-644. doi:10.1016/j.jhazmat.2018.10.088
16	JIANG Longbo， YUAN Xingzhong， ZENG Guangming，et al. Nitrogen self-doped g-C₃N₄ nanosheets with tunable band structures for enhanced photocatalytic tetracycline degradation［J］. Journal of Colloid and Interface Science，2019，536：17-29. doi:10.1016/j.jcis.2018.10.033
17	GUAN Zeyu， ZUO Shiyu， YANG Fan，et al. The p and d hybridization interaction in Fe-N-C boosts peroxymonosulfate non-radical activation［J］. Separation and Purification Technology，2021，258：118025. doi:10.1016/j.seppur.2020.118025
18	ZHOU Yajun， ZHANG Lingxia， LIU Jianjun，et al. Brand new P⁃doped g-C₃N₄：Enhanced photocatalytic activity for H₂ evolution and Rhodamine B degradation under visible light［J］. Journal of Materials Chemistry A，2015，3（7）：3862-3867. doi:10.1039/c4ta05292g
19	XU Fuhang， LAI Cui， ZHANG Mingming，et al. Facile one-pot synthesis of carbon self-doped graphitic carbon nitride loaded with ultra-low ceric dioxide for high-efficiency environmental photocatalysis：Organic pollutants degradation and hexavalent chromium reduction［J］. Journal of Colloid and Interface Science，2021，601：196-208. doi:10.1016/j.jcis.2021.05.124
20	KESARLA M K， FUENTEZ-TORRES M O， ALCUDIA-RAMOS M A，et al. Synthesis of g-C₃N₄/N-doped CeO₂ composite for photocatalytic degradation of an herbicide［J］. Journal of Materials Research and Technology，2019，8（2）：1628-1635. doi:10.1016/j.jmrt.2018.11.008
21	YANG Jian， LIANG Yujun， LI Kai，et al. One-step low-temperature synthesis of 0D CeO₂ quantum dots/2D BiOX（X=Cl，Br） nanoplates heterojunctions for highly boosting photo-oxidation and reduction ability［J］. Applied Catalysis B：Environmental，2019，250：17-30. doi:10.1016/j.apcatb.2019.03.017
22	LI Ling， LIU Shiyu， CHENG Min，et al. Improving the Fenton-like catalytic performance of MnO _x -Fe₃O₄/biochar using reducing agents：A comparative study［J］. Journal of Hazardous Materials，2021，406：124333. doi:10.1016/j.jhazmat.2020.124333
23	LI Hongchao， SHAN Chao， PAN Bingcai. Fe（Ⅲ）-doped g-C₃N₄ mediated peroxymonosulfate activation for selective degradation of phenolic compounds via high-valent iron-oxo species［J］. Environmental Science & Technology，2018，52（4）：2197-2205. doi:10.1021/acs.est.7b05563
24	FU Junwei， ZHU Bicheng， JIANG Chuanjia，et al. Hierarchical porous O-doped g-C₃N₄ with enhanced photocatalytic CO₂ reduction activity［J］. Small，2017，13（15）：1603938. doi:10.1002/smll.201603938
25	LIU Jinghai， ZHANG Tiekai， WANG Zhichao，et al. Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity［J］. Journal of Materials Chemistry，2011，21（38）：14398-14401. doi:10.1039/c1jm12620b
26	LIN Yan， WU Shaohua， LI Xiang，et al. Microstructure and performance of Z-scheme photocatalyst of silver phosphate modified by MWCNTs and Cr-doped SrTiO₃ for malachite green degradation［J］. Applide Catalysis B：Environmental，2018，227：557-570. doi:10.1016/j.apcatb.2018.01.054
27	CHEN Liuyun， XIE Xinling， SU Tongming，et al. Co₃O₄/CdS p-n heterojunction for enhancing photocatalytic hydrogen production：Co-S bond as a bridge for electron transfer［J］. Applied Surface Science，2021，567：150849. doi:10.1016/j.apsusc.2021.150849
28	LIU Jue， WANG Guowei， LI Bing，et al. A high-efficiency mediator-free Z-scheme Bi₂MoO₆/AgI heterojunction with enhanced photocatalytic performance［J］. The Science of the Total Environment，2021，784：147227. doi:10.1016/j.scitotenv.2021.147227
29	ZUO Weiyuan， LIANG Ling， YE Fanggui，et al. Construction of visible light driven silver sulfide/graphitic carbon nitride p-n heterojunction for improving photocatalytic disinfection［J］. Chemosphere，2021，283：131167. doi:10.1016/j.chemosphere.2021.131167

[1]	Shuang ZHANG, Haisong XIE, Yao TANG, Yitong TAO, Zhen LIANG. Pilot study on the treatment of coking wastewater with a three-stage upflow hydrolytic acidification sludge bioreactor [J]. Industrial Water Treatment, 2025, 45(3): 198-205.
[2]	Yang LI, Dongfang ZHANG, Jixian LIU, Haosheng DU, Xiaojie WANG. Case study on the comprehensive advanced treatment of PCB electroplating wastewater [J]. Industrial Water Treatment, 2025, 45(3): 212-218.
[3]	Ziang CHEN, Yiting YANG, Qian CHI, Jingjing YANG, Guangsen XIA, Juhong ZHAN. Effect of electrocatalytic ozone coupled with bioactived carbon process on removal of carbamazepine and microbial community in wastewater [J]. Industrial Water Treatment, 2024, 44(9): 91-97.
[4]	Jiaxi DAI, Jianhui JIANG, Yufan HAN, Wentao ZHANG, Mingxia TIAN, Yuan ZHANG. Preparation and photocatalytic performance of Cd(OH)₂/BiOCl composite materials [J]. Industrial Water Treatment, 2024, 44(9): 136-142.
[5]	Zheng LIU, Long YANG, Zuoxu ZHOU, Lei ZHANG, Xunsheng JI. An advanced treatment project of wastewater from PA66 salt producted by butadiene process [J]. Industrial Water Treatment, 2024, 44(7): 185-189.
[6]	Xiongqiang YANG. Exploration of process design for biochemical treatment of coking wastewater [J]. Industrial Water Treatment, 2024, 44(7): 197-202.
[7]	Mingjiao LANG, Zhaomei YANG, Guangyong ZENG. Construction of photocatalytic membrane separation materials and its research progress in wastewater treatment [J]. Industrial Water Treatment, 2024, 44(7): 47-56.
[8]	Yuhong ZHANG, Dunchao ZHANG, Xiulan SONG, Na HE. Advanced treatment of coking wastewater with peroxymonosulfate oxidation activated by base combined with SBBR [J]. Industrial Water Treatment, 2024, 44(6): 94-100.
[9]	Xufeng LI, Shaopo WANG, Yao ZHOU, Jing CHANG, Rongguang LI. Enhanced treatment technology for Yangtze River water in a water purification plant in Tianjin [J]. Industrial Water Treatment, 2024, 44(5): 132-140.
[10]	Qinqi FAN, Chun LIU, Situ MU, Jing ZHANG, Yankai GUO, Junjun MA. Operation performance of a pilot plant of microbubble ozonation and biological treatment for advanced treatment of chemical wastewater [J]. Industrial Water Treatment, 2024, 44(4): 120-126.
[11]	Zeyi LI, Changsheng LIAO, Yun CHAI, Qinghong WANG, Yali ZHAN, Chunmao CHEN, Fayuan CHEN. Characteristics of biochemical tail water from coking wastewater and current progress in advanced treatment technologies [J]. Industrial Water Treatment, 2024, 44(3): 10-23.
[12]	Lin HAN, Yongming CHENG, Dongmei WANG, Yajuan LI, Jie ZHANG. Problem diagnosis and analysis of advanced treatment system for reclaimed water in a power plant [J]. Industrial Water Treatment, 2024, 44(3): 206-210.
[13]	Man LI, Li QI, Jingbo PENG. Study on the treatment of coking wastewater biochemical effluent by Fenton-like system based on natural pyrite [J]. Industrial Water Treatment, 2024, 44(3): 81-88.
[14]	He XIE, Bin TANG, Bingbing CHEN, Jiali LI, Haijuan ZHAN. Synthesis of doped Co based perovskite and photocatalytic degradation of organic wastewater [J]. Industrial Water Treatment, 2024, 44(12): 131-137.
[15]	Jun WANG, Shuang FU, Peng HOU, Jun LIU, Chunxue SUN, Hongguang ZHANG. Construction of S-type TiO₂/CoPc heterojunction and photocatalytic degradation of tetracycline [J]. Industrial Water Treatment, 2024, 44(12): 118-122.

Please choose a citation manager

Content to export