Citation: YANG Gai-xiu, WANG Ke-xin, ZHANG Ze-zhen, ZHEN Feng, SUN Yong-ming. Preparation of MnO₂ catalyst by electrochemical deposition and its application in the microbial fuel cells[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(7): 889-896. shu

Preparation of MnO₂ catalyst by electrochemical deposition and its application in the microbial fuel cells

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, CAS Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Corresponding author: SUN Yong-ming, sunym@ms.giec.ac.cn
Received Date: 31 March 2020
Revised Date: 3 June 2020

Fund Project: the Natural Science Foundation of Guangdong Province 2017A030310280the Strategic Priority Research Program of Chinese Academy of Sciences XDA 21050400National Natural Science Foundation of China 51806224the Natural Science Foundation of Guangdong Province 2019A1515011971The project was supported by the Natural Science Foundation of Guangdong Province (2017A030310280, 2019A1515011971), National Natural Science Foundation of China (51806224) and the Strategic Priority Research Program of Chinese Academy of Sciences (XDA 21050400)

Figures(8)

As a green and clean renewable energy technology, microbial fuel cells (MFCs) have attracted extensive attention. The electrocatalysts with high activity and low-cost towards oxygen reduction reaction (ORR) are of great importance for the large-scale commercial applications of MFCs. Among multifarious cathode catalysts, manganese-based oxides showed high catalytic activity close to that of the precious metals. In this work, a sponge-like manganese dioxide (MnO₂) electro-catalyst was successfully prepared by the electrodeposition method. The surface morphology and composition of as-prepared MnO₂ catalyst were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and so on; the electrocatalytic activity of the obtained MnO₂ material towards ORR were evaluated by the linear sweep voltammetry (LSV) in a neutral phosphate buffer solution. The results demonstrate that the as-prepared MnO₂ catalyst appears as crystalline γ-MnO₂ and has a high Mn³⁺/Mn⁴⁺ ratio, which is beneficial to improving the catalytic activity in ORR. The as prepared γ-MnO₂ catalyst exhibits superior activity for the ORR under neutral conditions to the commercial MnO₂ catalyst. An MFC coupled with as-prepared catalyst generates an open circuit voltage of 0.52 V, with a maximum power density of 975.6 mW/m², about 1.7 times of that achieved with the MFC using commercial MnO₂ as cathode catalyst, which suggests that the MnO₂ catalyst prepared by the electrodeposition could be an economical alternative for Pt free catalysts in practical application of MFC.
- electrodeposition,
- MnO₂,
- cathode catalyst,
- oxygen reduction reaction,
- microbial fuel cell
1. [1]
  SLATE A J, WHITEHEAD K A, BROWNSON D A C, BANKS C E. Microbial fuel cells:An overview of current technology[J]. Renewable Sustainable. Energy Rev, 2019,101:60-81. doi: 10.1016/j.rser.2018.09.044
2. [2]
  CAI T, HUANG Y, HUANG M, XI Y, PANG D, ZHANG W. Enhancing oxygen reduction reaction of supercapacitor microbial fuel cells with electrospun carbon nanofibers composite cathode[J]. Chem Eng J, 2019,371:544-553. doi: 10.1016/j.cej.2019.04.025
3. [3]
  GUO D, TIAN Z, WANG J, KE X, ZHU Y. Co₂N nanoparticles embedded N-doped mesoporous carbon as efficient electrocatalysts for oxygen reduction reaction[J]. Appl Surf Sci, 2019,473:555-563. doi: 10.1016/j.apsusc.2018.12.204
4. [4]
  GUO Y Y, YUAN P F, ZHANG J N, HU Y F, AMIINU I S, WANG X, ZHOU J G, XIA H C, SONG Z B, XU Q, MU S C. Carbon nanosheets containing discrete Co-N_x-B_y-C active sites for efficient oxygen electrocatalysis and rechargeable Zn-Air Batteries[J]. ACS Nano, 2018,12(2):1894-1901. doi: 10.1021/acsnano.7b08721
5. [5]
  ZHUANG Lin. P, N-doped carbon as an efficient anti-poisoning catalyst against SO_x, NO_x and PO_x during oxygen reduction in acidic media[J]. Acta Phys-Chim Sin, 2019,35(7):659-660.
6. [6]
  JING B, YOU S, MA Y, XING Z, CHEN H, DAI Y, ZHANG C, REN N, ZOU J. Fe₃Se₄/FeSe heterojunctions in cornstalk-derived N-doped carbon framework enhance charge transfer and cathodic oxygen reduction reaction to boost bio-electricity generation[J]. Appl Catal B:Environ, 2019,244:465-474. doi: 10.1016/j.apcatb.2018.11.074
7. [7]
  LIU D, WU C, CHEN S, DING S, XIE Y, WANG C, WANG T, HALEEM Y A, REHMAN Z U, SANG Y, LIU Q, ZHENG X, WANG Y, GE B, XU H, SONG L. In situ trapped high-density single metal atoms within graphene:Iron-containing hybrids as representatives for efficient oxygen reduction[J]. Nano Res, 2018,11(4):2217-2228.
8. [8]
  BURKITT R, WHIFFEN T R, YU E H. Iron phthalocyanine and MnO_x composite catalysts for microbial fuel cell applications[J]. Appl Catal B:Environ, 2016,181:279-288. doi: 10.1016/j.apcatb.2015.07.010
9. [9]
  WANG Jun, WEI Zi-Dong. Recent progress in non-precious metal catalysts for oxygen reduction reaction[J]. Acta Phys-Chim Sin, 2017,33(5):886-902.
10. [10]
  LU X, ZHAI T, ZHANG X, SHEN Y, YUAN L, HU B, GONG L, CHEN J, GAO Y, ZHOU J. WO_3-x@Au@MnO₂ core-shell nanowires on carbon fabric for high-performance flexible supercapacitors[J]. Adv Mater, 2012,24(7):938-944. doi: 10.1002/adma.201104113
11. [11]
  GORLIN Y, CHUNG C-J, NORDLUND D, CLEMENS B M, JARAMILLO T F. Mn₃O₄ supported on glassy carbon:An active non-precious metal catalyst for the oxygen reduction reaction[J]. ACS Catal, 2012,2(12):2687-2694. doi: 10.1021/cs3004352
12. [12]
  CHENG F, SHEN J, PENG B, PAN Y, TAO Z, CHEN J. Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts[J]. Nat Chem, 2011,3(1):79-84. doi: 10.1038/nchem.931
13. [13]
  YU S, LIU R, YANG W, HAN K, WANG Z, ZHU H. Synthesis and electrocatalytic performance of MnO₂-promoted Ag@Pt/MWCNT electrocatalysts for oxygen reduction reaction[J]. J Mater Chem:A, 2014,2(15):5371-5378. doi: 10.1039/C3TA14564F
14. [14]
  LIU X W, SUN X F, HUANG Y X, SHENG G P, ZHOU K, ZENG R J, DONG F, WANG S G, XU A W, TONG Z H, YU H Q. Nano-structured manganese oxide as a cathodic catalyst for enhanced oxygen reduction in a microbial fuel cell fed with a synthetic wastewater[J]. Water Res, 2010,44(18):5298-5305. doi: 10.1016/j.watres.2010.06.065
15. [15]
  MENG Y, SONG W, HUANG H, REN Z, CHEN S-Y, SUIB S L. Structure-property relationship of bifunctional MnO₂ nanostructures:highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media[J]. J Am Chem Soc, 2014,136(32):11452-11464. doi: 10.1021/ja505186m
16. [16]
  CLAUWAERT P, VAN DER HA D, BOON N, VERBEKEN K, VERHAEGE M, RABAEY K, VERSTRAETE W. Open air biocathode enables effective electricity generation with microbial fuel cells[J]. Environ Sci Technol, 2007,41(21):7564-7569. doi: 10.1021/es0709831
17. [17]
  MAJIDI M R, FARAHANI F S, HOSSEINI M, AHADZADEH I. Low-cost nanowired alpha-MnO₂/C as an ORR catalyst in air-cathode microbial fuel cell[J]. Bioelectrochem, 2019,125:38-45. doi: 10.1016/j.bioelechem.2018.09.004
18. [18]
  KUMAR G G, AWAN Z, NAHM K S, XAVIER J S. Nanotubular MnO₂/graphene oxide composites for the application of open air-breathing cathode microbial fuel cells[J]. Biosens Bioelectron, 2014,53:528-534. doi: 10.1016/j.bios.2013.10.012
19. [19]
  LU Na, ZHOU Ben, DENG Li-fang, ZHOU Shun-gui. Starch processing wastewater treatment using a continuous microbial fuel cell with MnO₂ cathodic catalyst[J]. J Basic Sci Eng, 2009,17(Supplement):62-73.
20. [20]
  ZHANG L, LIU C, ZHUANG L, LI W, ZHOU S, ZHANG J. Manganese dioxide as an alternative cathodic catalyst to platinum in microbial fuel cells[J]. Biosens Bioelectron, 2009,24(9):2825-2829. doi: 10.1016/j.bios.2009.02.010
21. [21]
  LU M, KHARKWAL S, NG H Y, LI S F Y. Carbon nanotube supported MnO₂ catalysts for oxygen reduction reaction and their applications in microbial fuel cells[J]. Biosens Bioelectron, 2011,26(12):4728-4732. doi: 10.1016/j.bios.2011.05.036
22. [22]
  ROCHE I, CHAINET E, CHATENET M, VONDRAK J. Carbon-supported manganese oxide nanoparticles as electrocatalysts for the Oxygen Reduction Reaction (ORR) in alkaline medium:Physical characterizations and ORR mechanism[J]. J Phys Chem C, 2007,111(3):1434-1443.
23. [23]
  GAO F, TANG X, YI H, CHU C, LI N, LI J, ZHAO S. In-situ DRIFTS for the mechanistic studies of NO oxidation over alpha-MnO₂, beta-MnO₂ and gamma-MnO₂ catalysts[J]. Chem Eng J, 2017,322:525-537. doi: 10.1016/j.cej.2017.04.006
24. [24]
  PENG R, ZHENG Y, GUI L, ZHU Y, YU P, LUO Y. Template free synthesize mesoporous manganese dioxides for nater treatment[J]. J Alloys Compd, 2018,753:130-137. doi: 10.1016/j.jallcom.2018.04.144
25. [25]
  JU J, ZHAO H, KANG W, TIAN N, DENG N, CHENG B. Designing MnO₂ & carbon composite porous nanofiber structure for supercapacitor applications[J]. Electrochim Acta, 2017,258:116-123. doi: 10.1016/j.electacta.2017.10.094
26. [26]
  YANG H, ZHANG C, MENG Q, CAO B, TIAN G. Pre-lithiated manganous oxide/graphene aerogel composites as anode materials for high energy density lithium ion capacitors[J]. J Power Sources, 2019,431:114-124. doi: 10.1016/j.jpowsour.2019.05.060
27. [27]
  ZHANG P, LI K, LIU X. Carnation-like MnO₂ modified activated carbon air cathode improve power generation in microbial fuel cells[J]. J Power Sources, 2014,264:248-253. doi: 10.1016/j.jpowsour.2014.04.098
28. [28]
  Mo Guang-quan.Application of functinalized carbon nanotube materials in microbial fuel cell[D]. Guangzhou: South China University of Technology, 2010.
29. [29]
  LIU Y, LIU Z-M. Promoted activity of nitrogen-doped activated carbon as a highly efficient oxygen reduction catalyst in microbial fuel cells[J]. J Appl Electrochem, 2019,49(2):119-133. doi: 10.1007/s10800-018-1263-6
30. [30]
  YANG G, CHEN D, LV P, KONG X, SUN Y, WANG Z, YUAN Z, LIU H, YANG J. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications[J]. Sci Rep-UK, 2016,635252. doi: 10.1038/srep35252
31. [31]
  LIU Y, FAN Y S, LIU Z M. Pyrolysis of iron phthalocyanine on activated carbon as highly efficient non-noble metal oxygen reduction catalyst in microbial fuel cells[J]. Chem Eng J, 2019,361:416-427. doi: 10.1016/j.cej.2018.12.105
32. [32]
  QIAN Fan. MnO₂ Prepared by electrochemical deposition for supercapacitor applications[D]. Dalian: Dalian University of Technology, 2018.
33. [33]
  YAN L, SHEN C, NIU L, LIU M-C, LIN J, CHEN T, GONG Y, LI C, LIU X, XU S. Experimental and theoretical investigation of the effect of oxygen vacancies on the electronic structure and pseudocapacitance of MnO₂[J]. ChemSusChem, 2019,1215.
34. [34]
  STOERZINGER K A, RISCH M, HAN B, SHAO-HORN Y. Recent insights into manganese oxides in catalyzing oxygen reduction kinetics[J]. ACS Catal, 2015,5(10):6021-6031. doi: 10.1021/acscatal.5b01444
35. [35]
  SELVAKUMAR K, KUMAR S M S, THANGAMUTHU R, RAJPUT P, BHATTACHARYYA D, JHA S N. 2D and 3D silica-template-derived MnO₂ electrocatalysts towards enhanced oxygen evolution and oxygen reduction activity[J]. ChemElectroChem, 2018,5(24):3980-3990. doi: 10.1002/celc.201801143
36. [36]
  CHEN Su-yi. Synthesis of Transition Metals dopedManganese Dioxides and the oxygen reduction activities[D]. Guangzhou: Guangdong university of technology, 2015.
37. [37]
  SHAO M, CHANG Q, DODELET J-P, CHENITZ R. Recent advances in electrocatalysts for oxygen reduction reaction[J]. Chem Rev, 2016,3594.
1. [1]
  Qinjin DAI , Shan FAN , Pengyang FAN , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Yong ZHANG . Performance of oxygen vacancy-rich V-doped MnO₂ for high-performance aqueous zinc ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 453-460. doi: 10.11862/CJIC.20240326
2. [2]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
3. [3]
  Shilong Li , Ming Zhao , Yefei Xu , Zhanyi Liu , Mian Li , Qing Huang , Xiang Wu . Performance optimization of aqueous Zn/MnO₂ batteries through the synergistic effect of PVP intercalation and GO coating. Chinese Chemical Letters, 2025, 36(3): 110701-. doi: 10.1016/j.cclet.2024.110701
4. [4]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
5. [5]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
6. [6]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
7. [7]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
8. [8]
  Yulian Hu , Xin Zhou , Xiaojun Han . A Virtual Simulation Experiment on the Design and Property Analysis of CO₂ Reduction Photocatalyst. University Chemistry, 2025, 40(3): 30-35. doi: 10.12461/PKU.DXHX202403088
9. [9]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
10. [10]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
11. [11]
  Zelong LIANG , Shijia QIN , Pengfei GUO , Hang XU , Bin ZHAO . Synthesis and electrocatalytic CO₂ reduction performance of metal-organic framework catalysts loaded with silver particles. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 165-173. doi: 10.11862/CJIC.20240409
12. [12]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
13. [13]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
14. [14]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
15. [15]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
16. [16]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
17. [17]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
18. [18]
  Yiqian Jiang , Zihan Yang , Xiuru Bi , Nan Yao , Peiqing Zhao , Xu Meng . Mediated electron transfer process in α-MnO₂ catalyzed Fenton-like reaction for oxytetracycline degradation. Chinese Chemical Letters, 2024, 35(8): 109331-. doi: 10.1016/j.cclet.2023.109331
19. [19]
  Kun Chen , Huimin Lin , Xin Peng , Ziying Wu , Jingyue Dai , Yi Sun , Yaxuan Feng , Ziyi Huang , Zhiqiang Yu , Meng Yu , Guangyu Yao , Jigang Wang . In situ synthesis of MnO₂ micro/nano-adjuvants for enhanced immunotherapy of breast tumors. Chinese Chemical Letters, 2025, 36(5): 110045-. doi: 10.1016/j.cclet.2024.110045
20. [20]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081

Get Citation

PDF

XML

Metrics

PDF Downloads(27)
Abstract views(1712)
HTML views(385)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Preparation of MnO2 catalyst by electrochemical deposition and its application in the microbial fuel cells

Metrics

通讯作者: 陈斌, bchen63@163.com

Preparation of MnO₂ catalyst by electrochemical deposition and its application in the microbial fuel cells