硫掺杂石墨烯作为MFC阴极性能和生物毒性检测

doi:10.16085/j.issn.1000-6613.2023-0799

化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3430-3439.DOI: 10.16085/j.issn.1000-6613.2023-0799

• 资源与环境化工 • 上一篇

硫掺杂石墨烯作为MFC阴极性能和生物毒性检测

蓝瑞嵩¹^,²(), 刘丽华³, 张倩¹^,², 陈博彦⁴, 洪俊明¹^,²()

^1.华侨大学化工学院，福建厦门 361021
^2.福建省工业废水生化处理工程技术研究中心，福建厦门 361021
^3.福建省厦门环境监测中心站，福建厦门 361102
^4.台湾宜兰大学工学院化工与材料工程学系，台湾宜兰 26047

收稿日期:2023-05-12 修回日期:2023-06-27 出版日期:2024-06-15 发布日期:2024-07-02
通讯作者: 洪俊明
作者简介:蓝瑞嵩（2000—），男，硕士研究生，主要研究方向为掺杂氧化石墨烯。E-mail：lanruisong2022@163.com。
基金资助:
福建省科技项目(2022I0030);国家自然科学基金(51978291);厦门市科技计划(3502Z20226012)

Performance and biotoxicity evaluation of sulfur-doped graphene as a cathode for MFC

LAN Ruisong¹^,²(), LIU Lihua³, ZHANG Qian¹^,², CHEN Boyan⁴, HONG Junming¹^,²()

^1.College of Chemical Engineering, Huaqiao University, Xiamen 361021, Fujian, China
^2.Fujian Province Engineering Research Center of Industrial Wastewater Biochemical Treatment, Xiamen 361021, Fujian, China
^3.Fujian Xiamen Environmental Monitoring Central Station, Xiamen 361102, Fujian, China
^4.Department of Chemical and Materials Engineering, National I-Lan University, I -Lan 26047, Taiwan, China

Received:2023-05-12 Revised:2023-06-27 Online:2024-06-15 Published:2024-07-02
Contact: HONG Junming

摘要/Abstract

摘要：

采用水热法制备了硫掺杂还原氧化石墨烯（S-rGO），表征发现S原子的掺杂会导致结构缺陷的形成，这些结构缺陷会增加活性位点。通过电化学测试，S-rGO的氧还原反应（ORR）性能优于rGO，其极限电流密度为4.08mA/cm²，高出rGO（3.48mA/cm²）17.3%，这表明S原子的掺杂能够有效提高rGO的ORR活性。将S-rGO与活性炭（AC）、炭黑（CB）以0.1∶0.25∶1的质量比混合作为微生物燃料电池阴极催化剂。结果表明，S-rGO催化的微生物燃料电池反应器每个周期可持续27h，输出电压为0.33V，而rGO催化的反应器每个周期可持续24h，输出电压为0.30V；CB催化的反应器每个周期可持续23h，输出电压为0.26V。以苯扎氯铵（BAC）为生物毒性物质，探讨了S-rGO修饰的微生物燃料电池作为毒性传感器的相关性能，根据电压与BAC浓度的线性拟合结果，发现S-rGO具有更高的毒性检测灵敏度和稳定性（相关系数为0.996），而传统的Pt/C阴极催化剂的相关系数为0.932，表明S-rGO在毒性检测领域具有巨大的应用潜力。

关键词: 微生物燃料电池, 阴极催化剂, 硫掺杂还原氧化石墨烯, 毒性检测, 苯扎氯铵

Abstract:

Sulfur-doped reduced graphene oxide (S-rGO) materials were prepared by hydrothermal method. The characterization revealed that doping of S atoms led to the formation of structural defects in the rGO, which increased the active site of the material. Electrochemical tests revealed that S-rGO exhibited better oxygen reduction reaction (ORR) performance than rGO. The limited current density of S-rGO was 4.08mA/cm², which was 17.3% higher than that of rGO (3.48mA/cm²). This indicates that the S atom doping can effectively improve the ORR activity of rGO. S-rGO was mixed with activated carbon (AC) and carbon black (CB) at a mass ratio of 0.1∶0.25∶1 to prepare the cathode catalyst for microbial fuel cells. The results showed that the S-rGO-catalyzed microbial fuel cell reactor could operate for 27h per cycle and generate an output voltage of 0.33V, while the rGO-catalyzed reactor could run for 24h per cycle with an output voltage of 0.30V. The reactor catalyzed by CB could last for 23h per cycle and had an output voltage of 0.26V. Benzalammonium chloride (BAC) was used as a biotoxic substance to test the toxicity sensing performance of the S-rGO-modified microbial fuel cells. The linear fitting results of voltage and BAC concentration revealed that S-rGO had higher sensitivity and stability for toxicity detection (correlation coefficient was 0.996), whereas the correlation coefficient of the traditional Pt/C cathode catalyst was 0.932. All the above results indicates that S-rGO has great potential for application in the field of toxicity detection.

Key words: microbial fuel cell, cathode catalyst, sulfur-doped reduced graphene oxide, toxicity detection, benzalchloramine

中图分类号:

TM911.45

蓝瑞嵩, 刘丽华, 张倩, 陈博彦, 洪俊明. 硫掺杂石墨烯作为MFC阴极性能和生物毒性检测[J]. 化工进展, 2024, 43(6): 3430-3439.

LAN Ruisong, LIU Lihua, ZHANG Qian, CHEN Boyan, HONG Junming. Performance and biotoxicity evaluation of sulfur-doped graphene as a cathode for MFC[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3430-3439.

图/表 9

图1 S-rGO的SEM与TEM照片

图2 S-rGO和rGO的FTIR图谱

图3 S-rGO和rGO的Raman谱图

图4 S-rGO的XPS能谱图

图5 不同阴极催化剂的 CV、LSV、EIS曲线

表1 S-rGO、rGO和CB交流阻抗数据拟合结果

阴极催化剂	内阻/Ω	R_ct/Ω	物质转移电阻/Ω
S-rGO	10.97	8.15	42.20
rGO	10.88	11.99	50.93
CB	12.08	14.60	57.20

图6 不同阴极催化剂修饰的MFC功率密度曲线、极化曲线、输出电压曲线

图7 S-rGO、CB、rGO和Pt/C四种催化剂反应器的COD去除率

图8 不同阴极催化剂修饰的MFC对于不同浓度BAC的电信号变化、IRv与BAC浓度的关系和在不同BAC浓度下的峰值电压线性拟合

参考文献 41

1	LIU Hong, LOGAN Bruce E. Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane[J]. Environmental Science & Technology, 2004, 38(14): 4040-4046.
2	CUI Yang, LAI Bin, TANG Xinhua. Microbial fuel cell-based biosensors[J]. Biosensors, 2019, 9(3): 92.
3	WANG Qiuying, ZHANG Xiaoyuan, Ruitao LYU, et al. Binder-free nitrogen-doped graphene catalyst air-cathodes for microbial fuel cells[J]. Journal of Materials Chemistry A, 2016, 4(32): 12387-12391.
4	YANG Wei, CHATA Gustavo, ZHANG Yudong, et al. Graphene oxide-supported zinc cobalt oxides as effective cathode catalysts for microbial fuel cell: High catalytic activity and inhibition of biofilm formation[J]. Nano Energy, 2019, 57: 811-819.
5	XIAO Li, DAMIEN Jacqueline, LUO Jiayan, et al. Crumpled graphene particles for microbial fuel cell electrodes[J]. Journal of Power Sources, 2012, 208: 187-192.
6	PAPIYA Farhan, PATTANAYAK Prasanta, BISWAS Abul Kalam, et al. Polyaniline and sulfonated graphene oxide supported bimetallic Manganese cobalt oxides as an eﬀective and non-precious cathode catalyst in air-cathode microbial fuel cells[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 105992.
7	SABAA HANAA M, EL-KHATIB K M, El-Kady MOHAMED Y, et al. Spinel structure of activated carbon supported MFe₂O₄ composites as an economic and efficient electrocatalyst for oxygen reduction reaction in neutral media[J]. Journal of Solid State Electrochemistry, 2022, 26(12): 2749-2763.
8	XING Zhenyu, GAO Ningshengjie, QI Yitong, et al. Influence of enhanced carbon crystallinity of nanoporous graphite on the cathode performance of microbial fuel cells[J]. Carbon, 2017, 115: 271-278.
9	XU Meng, WU Ling, ZHU Meiwen, et al. Self-supporting nitrogen-doped reduced graphene oxide@carbon nanofiber hybrid membranes as high-performance integrated air cathodes in microbial fuel cells[J]. Carbon, 2022, 193: 242-257.
10	WANG Xin, GAO Ningshengjie, ZHOU Qixing, et al. Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells[J]. Bioresource Technology, 2013, 144: 632-636.
11	WU Yining, WANG Ling, JIN Min, et al. Reduced graphene oxide and biofilms as cathode catalysts to enhance energy and metal recovery in microbial fuel cell[J]. Bioresource Technology, 2019, 283: 129-137.
12	SUN Dan, XIE Bin, LI Jiahao, et al. A low-cost microbial fuel cell based sensor for in situ monitoring of dissolved oxygen for over half a year[J]. Biosensors and Bioelectronics, 2023, 220: 114888.
13	DU Yue, MA Feixiang, XU Chengyan, et al. Nitrogen-doped carbon nanotubes/reduced graphene oxide nanosheet hybrids towards enhanced cathodic oxygen reduction and power generation of microbial fuel cells[J]. Nano Energy, 2019, 61: 533-539.
14	KLINGELE Matthias, PHAM Chuyen, VUYYURU Koteswara Rao, et al. Sulfur doped reduced graphene oxide as metal-free catalyst for the oxygen reduction reaction in anion and proton exchange fuel cells[J]. Electrochemistry Communications, 2017, 77: 71-75.
15	YOU Shujie, LUZAN Serhiy M, Tamás SZABÓ, et al. Effect of synthesis method on solvation and exfoliation of graphite oxide[J]. Carbon, 2013, 52: 171-180.
16	LU Yue, HU Xingxin, TANG Lin, et al. Effect of CuO/ZnO/FTO electrode properties on the performance of a photo-microbial fuel cell sensor for the detection of heavy metals[J]. Chemosphere, 2022, 302: 134779.
17	XING Fei, XI Hongbo, YU Yin, et al. A sensitive, wide-ranging comprehensive toxicity indicator based on microbial fuel cell[J]. Science of The Total Environment, 2020, 703: 134667.
18	TIAN Zhengshan, LI Jitao, ZHU Gangyi, et al. Facile synthesis of highly conductive sulfur-doped reduced graphene oxide sheets[J]. Physical Chemistry Chemical Physics, 2016, 18(2): 1125-1130.
19	ZHANG Qian, WANG Bing xin, YU Yong bo, et al. Sulfur doped-graphene for enhanced acetaminophen degradation via electro-catalytic activation: Efficiency and mechanism[J]. The Science of the Total Environment, 2020, 715: 136730.
20	CHEN Wenwen, LIU Zhongliang, LI Yanxia, et al. High electricity generation achieved by depositing rGO@MnO₂ composite catalysts on three-dimensional stainless steel fiber felt for preparing the energy-efficient air cathode in microbial fuel cells[J]. Energy, 2021, 222: 119971.
21	BEGUM Halima, AHMED Mohammad Shamsuddin, JEON Seungwon. δ-MnO₂ nanoflowers on sulfonated graphene sheets for stable oxygen reduction and hydrogen evolution reaction[J]. Electrochimica Acta, 2019, 296: 235-242.
22	Thuy-Duong NGUYEN-PHAN, PHAM Viet Hung, SHIN Eun Woo, et al. The role of graphene oxide content on the adsorption-enhanced photocatalysis of titanium dioxide/graphene oxide composites[J]. Chemical Engineering Journal, 2011, 170(1): 226-232.
23	GUO Yaoping, ZENG Zequan, ZHU Youcai, et al. Catalytic oxidation of aqueous organic contaminants by persulfate activated with sulfur-doped hierarchically porous carbon derived from thiophene[J]. Applied Catalysis B: Environmental, 2018, 220: 635-644.
24	Hwee Ling POH, Petr ŠIMEK, SOFER Zdeněk, et al. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H₂S, SO₂, or CS₂ gas[J]. ACS Nano, 2013, 7(6): 5262-5272.
25	WEI Dacheng, LIU Yunqi, WANG Yu, et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties[J]. Nano Letters, 2009, 9(5): 1752-1758.
26	Wojciech KICIŃSKI, SZALA Mateusz, BYSTRZEJEWSKI Michał. Sulfur-doped porous carbons: Synthesis and applications[J]. Carbon, 2014, 68: 1-32.
27	WEI Maoping, CHAI Hui, CAO Yali, et al. Sulfonated graphene oxide as an adsorbent for removal of Pb²⁺ and methylene blue[J]. Journal of Colloid and Interface Science, 2018, 524: 297-305.
28	KANNAN Aravindaraj G, ZHAO Jinxing, Sung Geun JO, et al. Nitrogen and sulfur co-doped graphene counter electrodes with synergistically enhanced performance for dye-sensitized solar cells[J]. Journal of Materials Chemistry A, 2014, 2(31): 12232-12239.
29	GUO Yaoping, ZENG Zequan, LI Yulin, et al. In-situ sulfur-doped carbon as a metal-free catalyst for persulfate activated oxidation of aqueous organics[J]. Catalysis Today, 2018, 307: 12-19.
30	ZHANG Zhibin, HUANG Jian, DONG Zhimin, et al. Ultralight sulfonated graphene aerogel for efficient adsorption of uranium from aqueous solutions[J]. Journal of Radioanalytical and Nuclear Chemistry, 2019, 321(3): 1045-1055.
31	XIONG Bin, ZHOU Yingke, Ryan O’HAYRE, et al. Facile single-step ammonia heat-treatment and quenching process for the synthesis of improved Pt/N-graphene catalysts[J]. Applied Surface Science, 2013, 266: 433-439.
32	BUCKEL F, EFFENBERGER F, YAN C, et al. Influence of aromatic groups incorporated in long-chain alkanethiol self-assembled monolayers on gold[J]. Advanced Materials, 2000, 12(12): 901-905.
33	SEVILLA Marta, FUERTES Antonio B. Highly porous S-doped carbons[J]. Microporous and Mesoporous Materials, 2012, 158: 318-323.
34	XIN Shuaishuai, SHEN Jianguo, LIU Guocheng, et al. Electricity generation and microbial community of single-chamber microbial fuel cells in response to Cu₂O nanoparticles/reduced graphene oxide as cathode catalyst[J]. Chemical Engineering Journal, 2020, 380: 122446.
35	GU Yuxing, CHEN Zhigang, TANG Juanjuan, et al. Sulfur doped reduced graphene oxides with enhanced catalytic activity for oxygen reduction via molten salt redox-sulfidation[J]. Physical Chemistry Chemical Physics, 2016, 18(48): 32653-32657.
36	耿元昊, 林小秋, 孙亚昕, 等. 双金属导电金属有机框架材料Ni/Co-CAT的制备及其氧还原催化性能研究[J]. 化学学报, 2022, 80(6): 748-755.
	GENG Yuanhao, LIN Xiaoqiu, SUN Yaxin, et al. Preparation of bimetallic conductive metal-organic framework material Ni/Co-CAT for electrocatalytic oxygen reduction[J]. Acta Chimica Sinica, 2022, 80(6): 748-755.
37	Bonyoung KOO, LEE Seung-Mok, Sang-Eun OH, et al. Addition of reduced graphene oxide to an activated-carbon cathode increases electrical power generation of a microbial fuel cell by enhancing cathodic performance[J]. Electrochimica Acta, 2019, 297: 613-622.
38	Minh Hang DO, Huu Hao NGO, GUO Wenshan, et al. Performance of a dual-chamber microbial fuel cell as a biosensor for in situ monitoring Bisphenol A in wastewater[J]. The Science of the Total Environment, 2022, 845: 157125.
39	ADEKUNLE Ademola, RAGHAVAN Vijaya, TARTAKOVSKY Boris. On-line monitoring of heavy metals-related toxicity with a microbial fuel cell biosensor[J]. Biosensors and Bioelectronics, 2019, 132: 382-390.
40	CARBAJO Jose B, PERDIGÓN-MELÓN Jose A, PETRE Alice L, et al. Personal care product preservatives: Risk assessment and mixture toxicities with an industrial wastewater[J]. Water Research, 2015, 72: 174-185.
41	KHAN Nishat, ANWER Abdul Hakeem, SULTANA Saima, et al. Effective toxicity assessment of synthetic dye in microbial fuel cell biosensor with spinel nanofiber anode[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 107313.

[1]	蒋博龙, 崔艳艳, 史顺杰, 常嘉城, 姜楠, 谭伟强. 过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能[J]. 化工进展, 2023, 42(6): 3066-3076.
[2]	潘文政, 纪志永, 汪婧, 李淑明, 黄智辉, 郭小甫, 刘杰, 赵颖颖, 袁俊生. 微生物燃料电池处理偶氮含盐废水的产电性能和降解过程[J]. 化工进展, 2022, 41(6): 3306-3313.
[3]	陈诗雨, 许志成, 杨婧, 徐浩, 延卫. 微生物燃料电池在废水处理中的研究进展[J]. 化工进展, 2022, 41(2): 951-963.
[4]	刘婷婷, 徐大勇, 王璐, 杨伟伟, 夏宇扬. 电极间距对CW-MFC处理污泥中Zn和Ni的效果及其产电性能的影响[J]. 化工进展, 2021, 40(7): 4074-4082.
[5]	陈妹琼, 郭文显, 肖红飞, 张燕, 蔡志泉, 张敏, 程发良. 自支撑活化三维分级多孔碳阳极的制备及其在MFCs的应用[J]. 化工进展, 2020, 39(9): 3494-3501.
[6]	杨杰男, 付乾, 李俊, 张亮, 熊珂睿, 廖强, 朱恂. 3D打印微生物燃料电池阳极及其性能特性[J]. 化工进展, 2020, 39(10): 3987-3994.
[7]	夏函青,伍永钢,江文亭,付成林. 人工湿地-微生物燃料电池系统的发展及展望[J]. 化工进展, 2019, 38(12): 5548-5556.
[8]	陆圆,顾霞,陆勇泽,黄珊,朱光灿. 外电阻值对3A-MFC产电和脱氮性能的影响[J]. 化工进展, 2019, 38(08): 3910-3916.
[9]	李文英, 刘玉香, 任瑞鹏, 吕永康. 微生物燃料电池在水与废水脱氮方面的研究进展[J]. 化工进展, 2019, 38(02): 1097-1106.
[10]	顾霞, 黄珊, 陆圆, 孔赟, 朱光灿, 陆勇泽. 不同运行方式对多阳极型微生物燃料电池反硝化及产电性能的影响[J]. 化工进展, 2018, 37(10): 3818-3825.
[11]	林家瑾, 姚燕彤, 陈嘉缘, 张志明, 陈妹琼, 张敏, 程发良. 基于木薯秸秆制备三维多孔碳及其在微生物燃料电池中的应用[J]. 化工进展, 2017, 36(10): 3815-3819.
[12]	范功端, 林茹晶, 苏昭越, 林修咏, 许仁星, 陈薇. 利用藻类构建微生物燃料电池研究进展[J]. 化工进展, 2016, 35(12): 3841-3847.
[13]	郭文显, 陈妹琼, 张敏, 柳鹏, 张燕, 蔡志泉, 程发良. α-MoC/石墨烯复合材料的氧还原性能及其在微生物燃料电池中的应用[J]. 化工进展, 2016, 35(11): 3558-3562.
[14]	赵慧敏, 赵剑强. 不同运行方式对微生物燃料电池处理氨氮废水的影响[J]. 化工进展, 2016, 35(05): 1549-1554.
[15]	赵慧敏, 李晓玲, 赵剑强. 微生物燃料电池在污水生物脱氮中的研究进展[J]. 化工进展, 2016, 35(04): 1216-1222.

硫掺杂石墨烯作为MFC阴极性能和生物毒性检测

Performance and biotoxicity evaluation of sulfur-doped graphene as a cathode for MFC

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 41

相关文章 15

编辑推荐

Metrics

本文评价