Supplementary Information

Enabling fast electron transfers through both bacterial outer-membrane redox centers and endogenous electron mediators by polyaniline hybridized large-mesoporous carbon anode for high-performance microbial fuel cells

Long Zou a,b,c, Yan Qiao a,c, Canyu Zhong a,c, and Chang Ming Li a,c,d,*

a Institute for Clean Energy & Advanced Materials, Faculty of Materials and Energy, Southwest University, Chongqing 400715, China

b College of Life Science, Jiangxi Normal University, Nanchang 330022, China

c Chongqing Key Laboratory for Advanced Materials & Technologies of Clean Energies, Southwest University, Chongqing 400715, China

d Institute of Materials Science and Devices, Suzhou University of Science and Technology, Suzhou 215011, China

*Corresponding authors: ecmli@swu.edu.cn (C.M. Li)

6

Fig. S1. SEM image of the commercial CaCO3 nanoparticles with average size of 40－60 nm. The scale bare is 100 nm.

Fig. S2. SEM images of bulk carbon pyrolyzed from plant leaves extractive without CaCO3 nanoparticles as templates.

Fig. S3. (a) Cyclic voltammograms at a scan speed of 5 mV s-1 of PANI-LMC hybrid with different proportions in three-electrode cells filled with anaerobic suspensions of S. putrefaciens CN32, (b) polarization curves and output power density plots in dual-chamber MFCs.

Fig. S4. SEM images of LMC (a) and 40% PANI-LMC (b).

Fig. S5. Nitrogen adsorption-desorption isotherms of bulk carbon (a) and carbon cloth (b).

Fig. S6. The standard relationship line between fluorescent intensity at emission wavelength of 525 nm and concentration of riboflavin with an excitation 440 nm (a), and the fluorescent emission spectrum of the supernate of S. putrefaciens CN32 culture.

Fig. S7. Water contact angle measurements of LMC (a) and PANI-LMC hybrid (b).

Figure S8 First cycle output voltage plots of the dual-chamber MFCs equipped with different anodes.

Table S1. Summary of the recently reported performance of MFCs inoculated with Shewanella species (pure culture) with similar experimental setup and operating level.

Anode

MFC type

Bacterial strain

Power density (mW m-2)

Ref.

PANI-LMC

Dual chamber

S. putrefaciens CN32

1280

This work

LMC

Dual chamber

S. putrefaciens CN32

878

MWCNT/rGO

Dual chamber

S. putrefaciens CN32

789

[1]

NiO/carbon cloth

Dual chamber

S. putrefaciens CN32

1024

[2]

CNT-IL

Dual chamber

S. putrefaciens CN32

1076

[3]

CNF

Dual chamber

S. putrefaciens CN32

1747

[4]

GCF

Dual chamber

S. putrefaciens

786

[5]

PEDOT/carbon cloth

Dual chamber

S. loihica PV-4

140

[6]

CNT/PANI/GF

Dual chamber

S. putrefaciens

257

[7]

PANI-TA

Dual chamber

S. oneidensis MR-1

490

[8]

CP/GNRs/PANI

Dual chamber

S. oneidensis MR-1

856

[9]

PPy/GO-GF

Dual chamber

S. oneidensis MR-1

1320

[10]

PPy-GF

Dual chamber

S. oneidensis MR-1

1110

[10]

IL-GNS

Dual chamber

S. oneidensis MR-1

601

[11]

Graphene/PANI

Dual chamber

S. oneidensis MR-1

768

[12]

References

[1] L. Zou, Y. Qiao, X.-S. Wu, C.M. Li, Tailoring hierarchically porous graphene architecture by carbon nanotube to accelerate extracellular electron transfer of anodic biofilm in microbial fuel cells, Journal of Power Sources, 328 (2016) 143-150.

[2] Y. Qiao, X.-S. Wu, C.M. Li, Interfacial electron transfer of Shewanella putrefaciens enhanced by nanoflaky nickel oxide array in microbial fuel cells, Journal of Power Sources, 266 (2014) 226-231.

[3] H. Wei, X.-S. Wu, L. Zou, G.-Y. Wen, D.-Y. Liu, Y. Qiao, Amine-terminated ionic liquid functionalized carbon nanotubes for enhanced interfacial electron transfer of Shewanella putrefaciens anode in microbial fuel cells, Journal of Power Sources, 315 (2016) 192-198.

[4] L. Zou, Y. Qiao, Z.-Y. Wu, X.-S. Wu, J.-L. Xie, S.-H. Yu, J. Guo, C.M. Li, Tailoring Unique Mesopores of Hierarchically Porous Structures for Fast Direct Electrochemistry in Microbial Fuel Cells, Advanced Energy Materials, 6 (2016).

[5] L. Yang, S. Wang, S. Peng, H. Jiang, Y. Zhang, W. Deng, Y. Tan, M. Ma, Q. Xie, Facile Fabrication of Graphene-Containing Foam as a High-Performance Anode for Microbial Fuel Cells, Chemistry – A European Journal, 21 (2015) 10634-10638.

[6] X. Liu, W. Wu, Z. Gu, Poly (3,4-ethylenedioxythiophene) promotes direct electron transfer at the interface between Shewanella loihica and the anode in a microbial fuel cell, Journal of Power Sources, 277 (2015) 110-115.

[7] H.-F. Cui, L. Du, P.-B. Guo, B. Zhu, J.H.T. Luong, Controlled modification of carbon nanotubes and polyaniline on macroporous graphite felt for high-performance microbial fuel cell anode, Journal of Power Sources, 283 (2015) 46-53.

[8] Z.-H. Liao, J.-Z. Sun, D.-Z. Sun, R.-W. Si, Y.-C. Yong, Enhancement of power production with tartaric acid doped polyaniline nanowire network modified anode in microbial fuel cells, Bioresource Technology, 192 (2015) 831-834.

[9] C. Zhao, P. Gai, C. Liu, X. Wang, H. Xu, J. Zhang, J.-J. Zhu, Polyaniline networks grown on graphene nanoribbons-coated carbon paper with a synergistic effect for high-performance microbial fuel cells, Journal of Materials Chemistry A, 1 (2013) 12587-12594.

[10] Z. Lv, Y. Chen, H. Wei, F. Li, Y. Hu, C. Wei, C. Feng, One-step electrosynthesis of polypyrrole/graphene oxide composites for microbial fuel cell application, Electrochimica Acta, 111 (2013) 366-373.

[11] C. Zhao, Y. Wang, F. Shi, J. Zhang, J.-J. Zhu, High biocurrent generation in Shewanella-inoculated microbial fuel cells using ionic liquid functionalized graphene nanosheets as an anode, Chemical Communications, 49 (2013) 6668-6670.

[12] Y.-C. Yong, X.-C. Dong, M.B. Chan-Park, H. Song, P. Chen, Macroporous and Monolithic Anode Based on Polyaniline Hybridized Three-Dimensional Graphene for High-Performance Microbial Fuel Cells, Acs Nano, 6 (2012) 2394-2400.