基于N-掺杂碳包覆Fe3N复合材料的高效异相电芬顿降解有机物

doi:10.1016/S1872-2067(20)63719-6

催化学报 ›› 2021, Vol. 42 ›› Issue (6): 953-962.DOI: 10.1016/S1872-2067(20)63719-6

基于N-掺杂碳包覆Fe₃N复合材料的高效异相电芬顿降解有机物

肖娟, 陈军伟, 欧祖翘, 赖俊杭, 俞同文, 王毅^*()

中山大学化学工程与技术学院, 材料科学与工程学院, 广东省低碳化学与过程节能重点实验室, 广东广州510275

收稿日期:2020-07-30 接受日期:2020-09-09 出版日期:2021-06-18 发布日期:2021-01-30
通讯作者: 王毅
基金资助:
国家自然科学基金(21975292);国家自然科学基金(21978331);国家自然科学基金(21905311);催化基础国家重点实验室开放基金(N-20-02);广东省基础与应用基础研究基金(2020A1515010343);广州科技计划项目(2017A050501009);高校基本科研业务费青年教师重点培育项目(19lgpy116);中山大学百人计划启动基金.(76110-18841219)

N-doped carbon-coated Fe₃N composite as heterogeneous electro-Fenton catalyst for efficient degradation of organics

Juan Xiao, Junwei Chen, Zuqiao Ou, Junhang Lai, Tongwen Yu, Yi Wang^*()

The Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, School of Chemical Engineering and Technology, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2020-07-30 Accepted:2020-09-09 Online:2021-06-18 Published:2021-01-30
Contact: Yi Wang
About author:^*Tel/Fax: +86-20-84113253; E-mail: wangyi76@mail.sysu.edu.cn
Supported by:
National Natural Science Foundation of China(21975292);National Natural Science Foundation of China(21978331);National Natural Science Foundation of China(21905311);Open Fund of State Key Laboratory of Catalytic Foundation(N-20-02);Guangdong Fundamental and Applied Basic Research Foundation(2020A1515010343);Guangzhou Science and Technology Project(2017A050501009);Fundamental Science Research Fundation of Sun Yat-Sen University(19lgpy116);Hundred Talents Program Startup Grant of Sun Yat-sen University(76110-18841219)

摘要/Abstract

摘要：

水污染导致的缺水危机、水质恶化和生态环境破坏等问题, 严重影响人的健康及社会的和谐可持续发展. 异相电芬顿技术因催化剂可循环利用、宽pH适用范围等优点而广受关注. 常见的催化剂以铁、铁氧化物等铁基材料为主, 存在金属颗粒分布不均匀、铁元素易溶出、铁循环易受阻和H₂O₂选择性和转化效率低等问题, 严重制约该技术的发展. 尽管可以通过变价金属和非金属掺杂提高H₂O₂转化效率和选择性等, 但铁基催化剂的异相电芬顿性能仍有待提升. 因此, 亟待开发一种具有合金性质且宽pH响应的高H₂O₂选择性及转化效率、高稳定性的铁基催化剂. 本文利用具有高分散的金属位点和丰富碳源的铁基金属有机骨架材料, 采用同步高温煅烧和氨气刻蚀等手段, 制备N-掺杂碳包覆Fe₃N复合材料(Fe₃N@NG/NC), 并探究了该材料在异相电芬顿降解有机污染物体系中的应用前景.
XRD, SEM和TEM测试结果表明, Fe₃N@NG/NC催化剂是由N-掺杂的石墨化碳包覆的Fe₃N纳米颗粒(大小约为70 nm)均匀分散在N-掺杂碳骨架材料中组成的, 这一特殊结构有利于电荷的快速传输, 有助于电催化氧还原产H₂O₂及其转化至·OH反应的发生. 电化学测试结果表明, 该催化剂具有良好的两电子氧还原性能, 在电压范围为-0.3~0.1 V内的H₂O₂选择性为82.2%~74.5%, 电子转移数为2.35~2.50. 电子顺磁共振光谱结果表明, 该催化剂在异相电芬顿体系中主要的活性物质为·OH. XPS结果表明, 该催化剂中高含量的石墨N和吡啶N、Fe(II)有利于电催化合成H₂O₂和活化H₂O₂至·OH, 使其具有高效的异相电芬顿性能. 异相电芬顿降解评估结果表明, 该催化剂在pH 5.0体系中120 min内能高效去除罗丹明(RhB)、邻苯二甲酸二甲酯、亚甲基蓝和橙黄II等多种有机污染物(有机物去除率为97%~100%, TOC去除率为49%~65%), 不同RhB降解体对其去除率贡献程度依次为异相电芬顿 > 电催化 > 电生成H₂O₂氧化 > O₂氧化 > 吸附; 能实现宽pH范围内RhB的高效去除(在pH为3.0, 5.0, 7.0和9.0条件下, 在60 min内的RhB去除率分别为100%, 96%, 92%和81%); 在宽pH范围内呈现出高稳定性, 铁溶出量为0~0.03 mg/L; 经过6次循环使用后, 仍具有高的异相电芬顿性能(去除率达90%以上). 综上所述, Fe₃N@NG/NC复合材料能作为良好的异相电芬顿催化剂, 应用于污水处理领域.

关键词: Fe₃N@NG/NC复合材料, 异相电芬顿, 金属有机骨架, 降解, 有机污染物

Abstract:

Herein, the application of a N-doped graphitic-carbon-coated iron nitride composite dispersed in a N-doped carbon framework (Fe₃N@NG/NC) is investigated as a heterogeneous electro-Fenton ( HE-EF) catalyst for the efficient removal of organics. The simultaneous carbonization and ammonia etching of iron-based metal organic framework (Fe-MOF) materials yielded well-dispersed N-doped carbon-coated Fe₃N nanoparticles with a diameter of ~70 nm. The Fe₃N and pyridinic N endowed the composite with high HE-EF activity for decomposing the electrogenerated H₂O₂ to^•OH. The Fe₃N@NG/NC exhibited outstanding HE-EF performance in removing various organic pollutants with low iron leaching. A removal rate of 97-100% could be obtained for rhodamine B (RhB), dimethyl phthalate, methylene blue, and orange II in 120 min at a pH of 5.0. When the solution pH was set to 3.0, 5.0, 7.0, and 9.0, the removal rate of RhB reached 100%, 96%, 92%, and 81%, respectively, in 60 min at an optimum voltage of 0.0 V (vs. reversible hydrogen electrode (RHE)). Moreover, the concentration of leached iron was expected to be below 0.03 mg/L in a wide pH range of 3.0-9.0. In addition, the RhB removal efficiency remained as high as 90% after six cycles in the reusability experiments. This work highlights the MOF-derived Fe₃N composite as an efficient HE-EF catalyst and the corresponding catalytic mechanism, which facilitates its application in wastewater treatment.

Key words: Fe₃N@NG/NC composite, Heterogeneous electro-Fenton, Metal-organic frameworks, Degradation, Organic pollutants

肖娟, 陈军伟, 欧祖翘, 赖俊杭, 俞同文, 王毅. 基于N-掺杂碳包覆Fe₃N复合材料的高效异相电芬顿降解有机物[J]. 催化学报, 2021, 42(6): 953-962.

Juan Xiao, Junwei Chen, Zuqiao Ou, Junhang Lai, Tongwen Yu, Yi Wang. N-doped carbon-coated Fe₃N composite as heterogeneous electro-Fenton catalyst for efficient degradation of organics[J]. Chinese Journal of Catalysis, 2021, 42(6): 953-962.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63719-6

https://www.cjcatal.com/CN/Y2021/V42/I6/953

图/表 11

Fig. 1. (a) Schematic diagram of the synthesis procedure used for Fe3N@NG/NC; XRD patterns of MIL-101 (Fe) (b) and Fe3N@NG/NC (c).

Fig. 2. SEM (a) and corresponding elemental mapping (b-d) images of Fe3N@NG/NC.

Fig. 3. HAADF-STEM (a), TEM (b), HRTEM (c), and atomic-resolution HRTEM (d) images of Fe3N@NG/NC.

Fig. 4. Fe 2p (a), N 1s (b), C 1s (c) XPS spectra, and Raman spectrum (d) of Fe3N@NG/NC.

Fig. 5. RRDE polarization curves (a), n and H2O2 selectivity (b) of Fe3N@NG/NC at pH 5.0. Experimental conditions: scan rate of 10 mV/s, rotation rate of 1600 rpm, and [Na2SO4] = 0.1 M.

Fig. 6. RhB degradation efficiency (a) and corresponding k values (b) of different systems at a pH of 5.0. The effects of pH (c) and working potential (d) on RhB degradation. Experimental conditions: [RhB] = 10.0 mg/L, potential of 0.0 V, and [loaded catalyst] = 2.0 mg/cm2.

Fig. 7. Results of the recycling tests for HE-EF degradation of RhB at a pH of 5.0. Experimental conditions: [RhB] = 10.0 mg/L, potential of 0.0 V, and [loaded catalyst] = 2.0 mg/cm2.

Fig. 8. Removal efficiency for organics (a) and corresponding k values (b) in the HE-EF reaction at a pH of 5.0. Experimental conditions: [dimethyl phthalate] = [RhB] = [methylene blue] = [orange II] = 10.0 mg/L, potential of 0.0 V, and [loaded catalyst] = 2.0 mg/cm2.

Fig. 9. EPR spectra of ?OH in raw GF and Fe3N@NG/NC/GF systems.

Fig. 10. XRD patterns of the FeNC material (a) and k values for the RhB removal (b); (c,d) XPS spectra of Fe and corresponding Fe content of different Fe species; (e,f) N 1s XPS spectra and corresponding N content of different N species (FeNC materials).

Fig. 11. Possible HE-EF degradation mechanism for RhB with Fe3N@NG/NC/GF as the cathode.

参考文献

[1]	H. Q. He, Z. Zhou, Crit. Rev. Environ. Sci. Technol., 2017,47, 2100-2131.
[2]	Y. Wang, Y. H. Liu, T. F. Liu, S. Q. Song, X. C. Gui, H. Liu, Appl. Catal. B, 2014,156-157, 1-7.
[3]	J. L. Yu, T. F. Liu, H. Y. Liu, Y. Wang, Chin. J. Catal., 2016,37, 2079-2085.
[4]	F. X. Deng, S. X. Li, M. H. Zhou, Y. S. Zhu, S. Qiu, H. K. Li, F. Ma, J. Z. Jiang, Appl. Catal. B, 2019,256, 117796.
[5]	C. Zhang, G. B. Ren, W. Wang, X. M. Yu, F. K. Yu, Q. Z. Zhang, M. H. Zhou, Sep. Purif. Technol., 2019,208, 76-82.
[6]	V. Poza-Nogueiras, E. Rosales, M. Pazos, M. A Sanromán, Chemosphere, 2018,201, 399-416.
[7]	X. Ding, S. Y. Wang, W. Q. Shen, Y. Mu, L. Wang, H. Chen, L. Z. Zhang, Water Res., 2017,112, 9-18.
[8]	P. Xu, H. Xu, D. Y. Zheng, Chem. Eng. J., 2019,361, 968-974.
[9]	S. O. Ganiyu, M. Zhou, C. A. Martínez-Huitle, Appl. Catal. B, 2018,235, 103-129.
[10]	P. Dong, W. J. Liu, S. J. Wang, H. L. Wang, Y. Q. Wang, C. C. Zhao, Electrochim. Acta, 2019,308, 54-63.
[11]	Q. S. Peng, H. Y. Zhao, L. Qian, Y. B. Wang, G. H. Zhao, Appl. Catal. B, 2015, 174-175, 157-166.
[12]	Y. Z. Wang, H. M. Zhang, B. K. Li, M. C. Yu, R. Zhao, X. T. Xu, L. Cai, Chem. Eng. J., 2019,359, 914-923.
[13]	L. Z. Huang, M. T. Zhu, Z. Z. Liu, Z. P. Wang, H. C. B. Hansen, J. Hazard. Mater., 2019,364, 39-47.
[14]	F. K. Yu, Y. Wang, H. R. Ma, M. H. Zhou, Sep. Purif. Technol., 2020,248, 117022.
[15]	P. Xu, D. Y. Zheng, Z. Y. Xie, J. W. Ma, J. Yu, B. L. Hou, Sep. Purif. Technol., 2020,234, 116103.
[16]	H. Y. Zhao, Q. N. Wang, Y. Chen, Q. L. Tian, G. H. Zhao, Carbon, 2017,124, 112-122.
[17]	W. Chen, X. L. Yang, J. F. Huang, Y. H. Zhu, Y. Zhou, Y. F. Yao, C. Z. Li, Electrochim. Acta, 2016,200, 75-83.
[18]	Y. M. Zhang, Z. Chen, P. P. Wu, Y. X. Duan, L. C. Zhou, Y. X. Lai, F. Wang, S. Li, J. Hazard. Mater., 2020,393, 120448.
[19]	T. X, Huong Le, M. Drobek, M. Bechelany, J. Motuzas, A. Julbe, M. Cretin, Microporous Mesoporous Mater., 2019,278, 64-69.
[20]	A. Özcan, A. Atilir Özcan, Y. Demirci, E. Şener, Appl. Catal. B, 2017,200, 361-371.
[21]	H. Y. Zhao, L. Qian, Y. Chen, Q. N. Wang, G. H. Zhao, Chem. Eng. J., 2018,332, 486-498.
[22]	T. Luo, H. P. Feng, L. Tang, Y. Lu, W. W. Tang, S. Chen, J. F. Yu, Q. Q. Xie, X. L. Ouyang, Z. M. Chen, Chem. Eng. J., 2020,382, 122970.
[23]	X. L. Zhou, D. Xu, Y. C. Chen, Y. Y. Hu, Chem. Eng. J., 2020,384, 123324.
[24]	S. O. Ganiyu, T. X. Huong Le, M. Bechelany, G. Esposito, E. D. van Hullebusch, M. A. Oturan, M. Cretin, J. Mater. Chem. A, 2017,5, 3655-3666.
[25]	Y. Wang, M. Yi, K. Wang, S. Q. Song, Chin. J. Catal., 2019,40, 523-533.
[26]	K. Zhao, Y. Su, X. Quan, Y. M. Liu, S. Chen, H. T. Yu, J. Catal., 2018,357, 118-126.
[27]	V. Perazzolo, C. Durante, R. Pilot, A. Paduano, J. Zheng, G. A. Rizzi, A. Martucci, G. Granozzi, A. Gennaro, Carbon, 2015,95, 949-963.
[28]	K. Q. Li, J. M. Liu, J. Li, Z. Q. Wan, Chemosphere, 2018,193, 800-810.
[29]	M. Cheng, C. Lai, Y. Liu, G. M. Zeng, D. L. Huang, C. Zhang, L. Qin, L. Hu, C. Y. Zhou, W. P. Xiong, Coord. Chem. Rev., 2018,368, 80-92.
[30]	J. T. Tang, J. L. Wang, Chemosphere, 2020,241, 125002.
[31]	V. K. Sharma, M. B. Feng, J. Hazard. Mater., 2019,372, 3-16.
[32]	Z. H. Ye, J. A. Padilla, E. Xuriguera, E. Brillas, I. Sires, Appl. Catal. B, 2020,266, 118604.
[33]	Z. H. Ye, J. A. Padilla, E. Xuriguera, J. L. Beltran, F. Alcaide, E. Brillas, I. Sires, Environ. Sci. Technol., 2020,54, 4664-4674.
[34]	P. K. Cao, X. Quan, K. Zhao, S. Chen, H. T. Yu, J. F. Niu, J. Hazard. Mater., 2020,382, 121102.
[35]	P. K. Cao, K. Zhao, X. Quan, S. Chen, H. T. Yu, Sep. Purif. Technol., 2020,238, 116424.
[36]	Y. Wang, Y. H. Liu, K. Wang, S. Q. Song, P. Tsiakaras, H. Liu, Appl. Catal. B, 2015,165, 360-368.
[37]	J. Xiao, J. H. Lai, R. C. Li, X. Fang, D. F. Zhang, P. Tsiakaras, Y. Wang, Ind. Eng. Chem. Res., 2020,59, 12431-12440.
[38]	K. Wang, H. X. Chen, X. F. Zhang, Y. X. Tong, S. Q. Song, P. Tsiakaras, Y. Wang, Appl. Catal. B, 2020,264, 118468.
[39]	J. Xiao, C. Wang, H. Liu, J. Hazard. Mater., 2020,382, 121007.
[40]	S. Bauer, C. Serre, T. Devic, P. Horcajada, J. Marrot, G. Férey, N. Stock, Inorg. Chem., 2008,47, 7568-7576.
[41]	H. W. Song, J. Su, C. X. Wang, ACS Appl. Energy Mater., 2018,1, 5008-5015.
[42]	M. M. Wu, K. Wang, M. Yi, Y. X. Tong, Y. Wang, S.Q. Song, ACS Catal., 2017,7, 6082-6088.
[43]	H. W. Song, N. Li, H. Cui, C. X. Wang, Nano Energy, 2014,4, 81-87.
[44]	X. D. Ma, X. H. Xiong, J. Q. Zeng, P. J. Zou, Z. Lin, M. L. Liu, J. Mater. Chem. A, 2020,8, 6768-6775.
[45]	T. F. Li, M. Li, M. R. Zhang, X. Li, K. H. Liu, M. Y. Zhang, X. Liu, D. M. Sun, L. Xu, Y. W. Zhang, Y.W. Tang, Carbon, 2019,153, 364-371.
[46]	P. Su, M. H. Zhou, X. Y. Lu, W. L. Yang, G. B. Ren, J. J. Cai, Appl. Catal. B, 2019,245, 583-595.
[47]	M. R. Haider, W. L. Jiang, J. L. Han, H. M. A. Sharif, Y. C. Ding, H. Y. Cheng, A. J. Wang, Appl. Catal. B, 2019,256, 117774.
[48]	Y. Q. Hua, T. T. Jiang, K. Wang, M. M. Wu, S. Q. Song, Y. Wang, P. Tsiakaras, Appl. Catal. B, 2016,194, 202-208.
[49]	J. T. Tang, J. L. Wang, Chem. Eng. J., 2019,375, 122007.
[50]	Y. L. Yang, Y. Liu, X. Fang, W. Miao, X. Y. Chen, J. Sun, B. J. Ni, S. Mao, Chemosphere, 2020,243, 125423.
[51]	S. Cheng, C. Shen, H. Zheng, F. Q. Liu, A. Li, Appl. Catal. B, 2020,269, 118785.
[52]	J. T. Tang, J. L. Wang, Environ. Sci. Technol., 2018,52, 5367-5377.
[53]	P. Su, M. H. Zhou, G. Song, X. D. Du, X. Y. Lu, J. Hazard. Mater., 2020,397, 122681.
[54]	J. Y. Lu, Y. R. Yuan, X. Hu, W. J. Liu, C. X. Li, H. Q. Liu, W. W. Li, Ind. Eng. Chem. Res., 2020,59, 1800-1808.
[55]	C. Liu, Y. Feng, Z. T. Han, Y. Sun, X. Q. Wang, Q. F. Zhang, Z. G. Zou, Chin. J. Catal., 2021,42, 164-174.
[56]	X. Han, S. Y. Liu, X. T. Huo, F. Q. Cheng, M. Zhang, M. Guo, J. Hazard. Mater., 2020,392, 122295.
[57]	S. Sahar, A. Zeb, Y. N. Liu, N. Ullah, A. W. Xu, Chin. J. Catal., 2017,38, 2110-2119.
[58]	J. Wu, K. Zhu, H. Xu, W. Yan, Chin. J. Catal., 2019,40, 917-927.
[59]	L. X. Hu, G. H Deng, W. C. Lu, Y. S. Lu, Y. Y. Zhang, Chin. J. Catal., 2017,38, 1360-1372.

基于N-掺杂碳包覆Fe₃N复合材料的高效异相电芬顿降解有机物

N-doped carbon-coated Fe₃N composite as heterogeneous electro-Fenton catalyst for efficient degradation of organics

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

[1]	李世杰, 王春春, 董珂欣, 张鹏, 陈晓波, 李鑫. 新型MIL-101(Fe)/BiOBr S型异质催化剂用于高效光催化降解抗生素和还原六价铬: 光催化性能分析和光催化机理研究[J]. 催化学报, 2023, 51(8): 101-112.
[2]	李宁, 高雪云, 苏俊珲, 高旸钦, 戈磊. 类金属WO₂/g-C₃N₄复合光催化剂的构造及其优异的光催化性能[J]. 催化学报, 2023, 47(4): 161-170.
[3]	池海波, 王旺银, 马江平, 段睿智, 丁春梅, 宋睿, 李灿. 光电催化脱氟-氧化过程实现氟芳烃污染物的高效矿化[J]. 催化学报, 2023, 55(12): 171-181.
[4]	郑子叶, 田爽, 冯玉晓, 赵珊, 李鑫, 王曙光, 何作利. 光催化耦合技术在废水处理中的最新进展[J]. 催化学报, 2023, 54(11): 88-136.
[5]	邱春禹, 万里洋, 王宇成, Muhammad Rauf, 洪宇浩, 袁家寅, 周志有, 孙世刚. 工况表征方法揭示燃料电池催化层中过氧化氢浓度[J]. 催化学报, 2022, 43(7): 1918-1926.
[6]	赵振龙, 边辑, 赵丽娜, 吴红君, 徐帅, 孙磊, 李志君, 张紫晴, 井立强. 2D ZnMOF/BiVO₄ S型异质结的构建及其可见光催化还原CO₂性能[J]. 催化学报, 2022, 43(5): 1331-1340.
[7]	王兰, 公宁, 周洲, 张启成, 彭文朝, 李阳, 张凤宝, 范晓彬. MOF衍生的分层多孔三维N-CoP_x/Ni₂P大电流密度下加速析氢[J]. 催化学报, 2022, 43(4): 1176-1183.
[8]	张博禹, 石家福, 赵阳, 王涵, 储子仪, 陈裕, 吴振华, 姜忠义. 基于扩散强化的Pickering界面生物催化系统构建及CO₂矿化过程研究[J]. 催化学报, 2022, 43(4): 1184-1191.
[9]	张亚萍, 徐继香, 周洁, 王磊. 金属-有机框架衍生的多功能光催化剂[J]. 催化学报, 2022, 43(4): 971-1000.
[10]	王琳琳, 李欣, 郝磊端, 洪崧, Alex W. Robertson, 孙振宇. 超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯[J]. 催化学报, 2022, 43(4): 1049-1057.
[11]	赵英男, 覃星, 赵鑫宇, 王馨, 谭华桥, 孙慧颖, 闫刚, 李海玮, 何咏基, 李顺诚. 多酸掺杂Bi₂O_3-_x/Bi光催化剂用于高效可见光催化降解四溴双酚A和NO去除[J]. 催化学报, 2022, 43(3): 771-781.
[12]	黄俊敏, 陈健民, 刘望喜, 张静文, 陈俊英, 李映伟. 具有三维光催化活性表面的Cu掺杂ZnS纳米框架材料用于太阳能光催化产氢[J]. 催化学报, 2022, 43(3): 782-792.
[13]	范亿薇, 李赫龙, 苏世浩, 陈金磊, 刘春泉, 王水众, 徐向亚, 宋国勇. 钌碳耦合碱还原催化降解三倍体毛白杨[J]. 催化学报, 2022, 43(3): 802-810.
[14]	郑灵玲, 张龙帅, 陈颖, 田磊, 江训恒, 谌莉莎, 邢秋菊, 刘小真, 吴代赦, 邹建平. 原位配体功能化策略制备共价金属有机骨架促进其析氢反应[J]. 催化学报, 2022, 43(3): 811-819.
[15]	万俊, 杨玮洁, 刘佳庆, 孙凯龙, 刘琳, 付峰. 固溶体内电场调控增强Bi₂₄O₃₁Cl_xBr_10‒_x体相电荷流动和光催化活性[J]. 催化学报, 2022, 43(2): 485-496.