SCIENCE CHINA Materials, Volume 64 , Issue 12 : 2926-2937(2021) https://doi.org/10.1007/s40843-021-1700-5

Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells

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  • ReceivedMar 4, 2021
  • AcceptedMay 7, 2021
  • PublishedJul 5, 2021


Funded by

the National Natural Science Foundation of China(51976143)

the National Key Research and Development Program of China(2018YFA0702001)

and Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XHD2020-002)


This work was supported by the National Natural Science Foundation of China (51976143), the National Key Research and Development Program of China (2018YFA0702001), and Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory (XHD2020-002).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Tang H conceived the idea of the subject and supervised the progress of the research. Chen N performed the experiments with support from Meng Z, Wang R, Cai S, and Guo W. Chen N wrote the manuscript, and Tang H revised the manuscript. All authors contributed to the general discussion.

Author information

Neng Chen obtained his bachelor’s degree from Guangdong University of Petroleum and Chemical Technology in 2015. He obtained a master’s degree from China University of Petroleum, Beijing in 2018. And he has been a scientific research assistant at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing at Wuhan University of Technology until now. His research interests focus on electrocatalysts, fuel cells and metal-air batteries.

Haolin Tang earned his PhD degree in materials science from Wuhan University of Technology in 2007. Then he worked as a research fellow at Nanyang Technological University for one year, and in 2011 he was appointed as a full professor of the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing at Wuhan University of Technology. His research interests include fuel cells, electrochemistry of nanomaterials, and self-assembly of nanocomposites.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Li WW, Yu HQ, He Z. Towards sustainable wastewater treatment by using microbial fuel cells-centered technologies. Energy Environ Sci, 2014, 7: 911-924 CrossRef Google Scholar

[2] Logan BE. Exoelectrogenic bacteria that power microbial fuel cells. Nat Rev Microbiol, 2009, 7: 375-381 CrossRef PubMed Google Scholar

[3] Santoro C, Arbizzani C, Erable B, et al. Microbial fuel cells: From fundamentals to applications. A review. J Power Sources, 2017, 356: 225-244 CrossRef PubMed ADS Google Scholar

[4] Sun M, Zhai LF, Li WW, et al. Harvest and utilization of chemical energy in wastes by microbial fuel cells. Chem Soc Rev, 2016, 45: 2847-2870 CrossRef PubMed Google Scholar

[5] Pant D, Van Bogaert G, Diels L, et al. A review of the substrates used in microbial fuel cells (MFCs) for sustainable energy production. Bioresource Tech, 2010, 101: 1533-1543 CrossRef PubMed Google Scholar

[6] Wang H, Park JD, Ren ZJ. Practical energy harvesting for microbial fuel cells: A review. Environ Sci Technol, 2015, 49: 3267-3277 CrossRef PubMed ADS Google Scholar

[7] Zhao F, Slade RCT, Varcoe JR. Techniques for the study and development of microbial fuel cells: An electrochemical perspective. Chem Soc Rev, 2009, 38: 1926-1939 CrossRef PubMed Google Scholar

[8] Martinez U, Komini Babu S, Holby EF, et al. Progress in the development of Fe-based PGM-free electrocatalysts for the oxygen reduction reaction. Adv Mater, 2019, 31: 1806545 CrossRef PubMed Google Scholar

[9] Wang Q, Astruc D. State of the art and prospects in metal-organic framework (MOF)-based and MOF-derived nanocatalysis. Chem Rev, 2019, 120: 1438-1511 CrossRef PubMed Google Scholar

[10] Santoro C, Serov A, Gokhale R, et al. A family of Fe-N-C oxygen reduction electrocatalysts for microbial fuel cell (MFC) application: Relationships between surface chemistry and performances. Appl Catal B-Environ, 2017, 205: 24-33 CrossRef PubMed Google Scholar

[11] You S, Gong X, Wang W, et al. Enhanced cathodic oxygen reduction and power production of microbial fuel cell based on noble-metal-free electrocatalyst derived from metal-organic frameworks. Adv Energy Mater, 2016, 6: 1501497 CrossRef Google Scholar

[12] Cai S, Meng Z, Tang H, et al. 3D Co-N-doped hollow carbon spheres as excellent bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction. Appl Catal B-Environ, 2017, 217: 477-484 CrossRef Google Scholar

[13] Cai S, Wang R, Yourey WM, et al. An efficient bifunctional electrocatalyst derived from layer-by-layer self-assembly of a three-dimensional porous Co-N-C@graphene. Sci Bull, 2019, 64: 968-975 CrossRef ADS Google Scholar

[14] Meng Z, Cai S, Wang R, et al. Bimetallic-organic framework-derived hierarchically porous Co-Zn-N-C as efficient catalyst for acidic oxygen reduction reaction. Appl Catal B-Environ, 2019, 244: 120-127 CrossRef Google Scholar

[15] Tang H, Cai S, Xie S, et al. Metal-organic-framework-derived dual metal- and nitrogen-doped carbon as efficient and robust oxygen reduction reaction catalysts for microbial fuel cells. Adv Sci, 2016, 3: 1500265 CrossRef PubMed Google Scholar

[16] Tang H, Zeng Y, Liu D, et al. Dual-doped mesoporous carbon synthesized by a novel nanocasting method with superior catalytic activity for oxygen reduction. Nano Energy, 2016, 26: 131-138 CrossRef Google Scholar

[17] Tang H, Zeng Y, Zeng Y, et al. Iron-embedded nitrogen doped carbon frameworks as robust catalyst for oxygen reduction reaction in microbial fuel cells. Appl Catal B-Environ, 2017, 202: 550-556 CrossRef Google Scholar

[18] Wang R, Cao J, Cai S, et al. MOF@cellulose derived Co-N-C nanowire network as an advanced reversible oxygen electrocatalyst for rechargeable zinc-air batteries. ACS Appl Energy Mater, 2018, 1: 1060-1068 CrossRef Google Scholar

[19] Mamtani K, Jain D, Zemlyanov D, et al. Probing the oxygen reduction reaction active sites over nitrogen-doped carbon nanostructures (CNx) in acidic media using phosphate anion. ACS Catal, 2016, 6: 7249-7259 CrossRef Google Scholar

[20] Yin P, Yao T, Wu Y, et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew Chem, 2016, 128: 10958-10963 CrossRef Google Scholar

[21] Xia BY, Yan Y, Li N, et al. A metal-organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy, 2016, 1: 15006 CrossRef ADS Google Scholar

[22] Dang S, Zhu QL, Xu Q. Nanomaterials derived from metal-organic frameworks. Nat Rev Mater, 2018, 3: 17075 CrossRef ADS Google Scholar

[23] Lu XF, Xia BY, Zang SQ, et al. Metal-organic frameworks based electrocatalysts for the oxygen reduction reaction. Angew Chem Int Ed, 2020, 59: 4634-4650 CrossRef PubMed Google Scholar

[24] Shui J, Chen C, Grabstanowicz L, et al. Highly efficient nonprecious metal catalyst prepared with metal-organic framework in a continuous carbon nanofibrous network. Proc Natl Acad Sci USA, 2015, 112: 10629-10634 CrossRef PubMed ADS Google Scholar

[25] Shang L, Yu H, Huang X, et al. Well-dispersed ZIF-derived Co,N-Co-doped carbon nanoframes through mesoporous-silica-protected calcination as efficient oxygen reduction electrocatalysts. Adv Mater, 2016, 28: 1668-1674 CrossRef PubMed Google Scholar

[26] Liang HW, Zhuang X, Brüller S, et al. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat Commun, 2014, 5: 4973 CrossRef PubMed ADS Google Scholar

[27] Lai Q, Zhao Y, Liang Y, et al. In situ confinement pyrolysis transformation of ZIF-8 to nitrogen-enriched meso-microporous carbon frameworks for oxygen reduction. Adv Funct Mater, 2016, 26: 8334-8344 CrossRef Google Scholar

[28] Li Z, Shao M, Zhou L, et al. Directed growth of metal-organic frameworks and their derived carbon-based network for efficient electrocatalytic oxygen reduction. Adv Mater, 2016, 28: 2337-2344 CrossRef PubMed Google Scholar

[29] Li Y, Fu ZY, Su BL. Hierarchically structured porous materials for energy conversion and storage. Adv Funct Mater, 2012, 22: 4634-4667 CrossRef Google Scholar

[30] Li F, Ding XB, Cao QC, et al. A ZIF-derived hierarchically porous Fe-Zn-N-C catalyst synthesized via a two-stage pyrolysis for the highly efficient oxygen reduction reaction in both acidic and alkaline media. Chem Commun, 2019, 55: 13979-13982 CrossRef PubMed Google Scholar

[31] Ren Q, Wang H, Lu XF, et al. Recent progress on MOF-derived heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction. Adv Sci, 2018, 5: 1700515 CrossRef PubMed Google Scholar

[32] Ye L, Chai G, Wen Z. Zn-MOF-74 derived N-doped mesoporous carbon as pH-universal electrocatalyst for oxygen reduction reaction. Adv Funct Mater, 2017, 27: 1606190 CrossRef Google Scholar

[33] Yang L, Zeng X, Wang W, et al. Recent progress in MOF-derived, heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells. Adv Funct Mater, 2018, 28: 1704537 CrossRef Google Scholar

[34] Zhou H, Yang T, Kou Z, et al. Negative pressure pyrolysis induced highly accessible single sites dispersed on 3D graphene frameworks for enhanced oxygen reduction. Angew Chem, 2020, 132: 20645-20649 CrossRef Google Scholar

[35] Zhu M, Zhao C, Liu X, et al. Single atomic cerium sites with a high coordination number for efficient oxygen reduction in proton-exchange membrane fuel cells. ACS Catal, 2021, 11: 3923-3929 CrossRef Google Scholar

[36] Zhou S, Lin M, Zhuang Z, et al. Biosynthetic graphene enhanced extracellular electron transfer for high performance anode in microbial fuel cell. Chemosphere, 2019, 232: 396-402 CrossRef PubMed ADS Google Scholar

[37] Qiao Y, Bao SJ, Li CM, et al. Nanostructured polyaniline/titanium dioxide composite anode for microbial fuel cells. ACS Nano, 2008, 2: 113-119 CrossRef PubMed Google Scholar

[38] Hu H, Guan BY, Lou XWD. Construction of complex CoS hollow structures with enhanced electrochemical properties for hybrid supercapacitors. Chem, 2016, 1: 102-113 CrossRef Google Scholar

[39] You B, Jiang N, Sheng M, et al. Bimetal-organic framework self-adjusted synthesis of support-free nonprecious electrocatalysts for efficient oxygen reduction. ACS Catal, 2015, 5: 7068-7076 CrossRef Google Scholar

[40] Pan Y, Heryadi D, Zhou F, et al. Tuning the crystal morphology and size of zeolitic imidazolate framework-8 in aqueous solution by surfactants. CrystEngComm, 2011, 13: 6937-6940 CrossRef Google Scholar

[41] Yao J, He M, Wang H. Strategies for controlling crystal structure and reducing usage of organic ligand and solvents in the synthesis of zeolitic imidazolate frameworks. CrystEngComm, 2015, 17: 4970-4976 CrossRef Google Scholar

[42] Hou X, Zhang Y, Dong Q, et al. Metal organic framework derived core-shell structured Co9S8@N-C@MoS2 nanocubes for supercapacitor. ACS Appl Energy Mater, 2018, 1: 3513-3520 CrossRef Google Scholar

[43] Liu H, Guan J, Yang S, et al. Metal-organic framework-derived Co2P nanoparticle/multi-doped porous carbon as a trifunctional electrocatalyst. Adv Mater, 2020, 32: 2003649 CrossRef PubMed Google Scholar

[44] Wang J, Huang Z, Liu W, et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J Am Chem Soc, 2017, 139: 17281-17284 CrossRef PubMed Google Scholar

[45] Mi JL, Liang JH, Yang LP, et al. Effect of Zn on size control and oxygen reduction reaction activity of Co nanoparticles supported on N-doped carbon nanotubes. Chem Mater, 2019, 31: 8864-8874 CrossRef Google Scholar

[46] Chen YZ, Wang C, Wu ZY, et al. From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater, 2015, 27: 5010-5016 CrossRef PubMed Google Scholar

[47] Li JS, Li SL, Tang YJ, et al. Nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrids derived from MOFs: Efficient bifunctional electrocatalysts for ORR and OER. Chem Commun, 2015, 51: 2710-2713 CrossRef PubMed Google Scholar

[48] Amiinu IS, Liu X, Pu Z, et al. From 3D ZIF nanocrystals to Co–Nx/C nanorod array electrocatalysts for ORR, OER, and Zn-air batteries. Adv Funct Mater, 2018, 28: 1704638 CrossRef Google Scholar

[49] Deng Y, Tian X, Chi B, et al. Hierarchically open-porous carbon networks enriched with exclusive Fe–Nx active sites as efficient oxygen reduction catalysts towards acidic H2–O2 PEM fuel cell and alkaline Zn-air battery. Chem Eng J, 2020, 390: 124479 CrossRef Google Scholar

[50] Wang J, Lu H, Hong Q, et al. Porous N,S-codoped carbon architectures with bimetallic sulphide nanoparticles encapsulated in graphitic layers: Highly active and robust electrocatalysts for the oxygen reduction reaction in Al-air batteries. Chem Eng J, 2017, 330: 1342-1350 CrossRef Google Scholar

[51] Li G, Mu Y, Huang Z, et al. Poly-active centric Co3O4-CeO2/Co-N-C composites as superior oxygen reduction catalysts for Zn-air batteries. Sci China Mater, 2021, 64: 73-84 CrossRef Google Scholar

[52] Chen Y, Gao R, Ji S, et al. Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal-organic frameworks: Enhanced oxygen reduction performance. Angew Chem Int Ed, 2021, 60: 3212-3221 CrossRef PubMed Google Scholar

[53] Hu Y, Zhu M, Luo X, et al. Coplanar Pt/C nanomeshes with ultrastable oxygen reduction performance in fuel cells. Angew Chem Int Ed, 2021, 60: 6533-6538 CrossRef PubMed Google Scholar

  • Figure 1

    (a) Diagram showing the synthesis of the 3D hierarchically porous Co-N-C skeleton; (b) XRD patterns of Zn(100−x)Cox(MeIM)@SiO2 (x = 0, 5, 10, 20, 50, 100), Zn90Co10(MeIM), simulated ZIF-8 and ZIF-67; (c) XRD patterns of Mes-C-N-Zn(100−x)Cox (x = 0, 5, 10, 20, 50, 100) and Mic-C-N-Zn90Co10.

  • Figure 2

    Physical characterizations. SEM images: (a, b) Mic-Zn90Co10(MeIM) nanocubes, (c, d) Mic-C-N-Zn90Co10 nanocubes and (e, f) Mes-C-N-Zn90Co10 nanocubes. TEM images: (g) HRTEM and (h) TEM images of the Mes-C-N-Zn90Co10 nanocubes. (i) Elemental mapping of the Mes-C-N-Zn90Co10 nanocubes.

  • Figure 3

    (a) N2 adsorption/desorption isotherms and (b) corresponding pore size distributions of Mes-C-N-Zn(100−x)Cox and Mic-C-N-Zn90Co10.

  • Figure 4

    XPS survey spectra of the (a) full spectrum; (b) Zn 2p; (c) N 1s; and (d) Co 2p of the Mes-C-N-Zn100, Mes-C-N-Zn90Co10, and Mes-C-N-Co100 catalysts.

  • Figure 5

    LSV curves of Mes-C-N-Co100, Mic-C-N-Zn90Co10, and commercial Pt/C at 1600 r min−1 in O2-saturated (a) 0.01 mol L−1 PBS, (b) 0.1 mol L−1 HClO4, and (c) 0.1 mol L−1 KOH. (d) LSV curves of Mes-C-N-Zn(100−x)Cox at 1600 r min−1 in 0.01 mol L−1 PBS. Methanol resistance curves of Pt/C and Mes-C-N-Zn90Co10 in (e) 0.1 mol L−1 HClO4 and (f) 0.1 mol L−1 KOH. Durability curves of Pt/C and Mes-C-N-Zn90Co10 in (g) 0.01 mol L−1 PBS, (h) 0.1 mol L−1 HClO4, and (i) 0.1 mol L−1 KOH.

  • Figure 6

    (a) Diagram showing the working principle of MFCs. (b) Polarization curves and discharge power densities of the 3D CoNC-MFC and Pt/C–MFC devices. (c) Voltage trend recorded for 192 h for the MFCs equipped with Mes-C-N-Zn90Co10 and Pt/C. The voltage was recorded across a 1000-Ω resistor.


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