Document Type : Research Article

Authors

1 Catalysis Research Division, Research Institute of Petroleum Industry (RIPI), Tehran, Tehran, Iran.

2 Energy Technology Research Division, Research Institute of Petroleum Industry (RIPI), Tehran, Tehran, Iran.

Abstract

In the present work, natural biomass and chemical materials were applied as the heteroatom resources for modifying the Porous Graphene (PG) structure by pyrolysis method at 900 ºC. The physical and chemical characterizatons were performed by means of Scanning Electron Microscopy (SEM), Brunauer–Emmett–Teller (BET), Raman Spectroscopy, N2 Adsorption-Desorption, and X-ray Photo-electron Spectroscopy (XPS). Furthemore, the behavior of the prepared materials was investigated by Cyclic Voltammetry (CV) and Rotating Disk Electrode (RDE). The obtained results indicated that doping of heteroatoms into the graphene framework was possible using a low-cost and environment-friendly biomass material as well as chemical sources. Moreover, one-step quarternary and tersiary co-doped graphene could be acheived using natural biomass. The prepared electrocatalysts using grape leaves and sulfur trioxide pyridine complex exhibit higher electrocatalytic performance as exampled which conducted the electrocatalyst in 4e- pathway and showed high stability in methanol solutions during the process, confirming their considerable potential to Oxygen Reduction Reaction (ORR) as an electro-catalyst. Moreover, the onset potential of Gl300G-900 and GSP 900 (0.93 V vs RHE) is almost equal to the Pt/C 20 wt % (0.99 V vs RHE). These optimal prepared cathodes (Gl300G-900 and GSP 900) in the Microbial Fuel Cell (MFC) test lead to considerable power densities of 31.5 mW m-2 and 30.9.mW m-2, which are close to 38.6 mW m-2 for the Pt/C 20 wt % cathode.

Keywords

Main Subjects

1.     Zhang, H., Wang, Y., Wang, D., Li, Y., Liu, X., Liu, P., Yang, H., An, T., Tang, Z. and Zhao, H., "Hydrothermal transformation of dried grass into graphitic carbon based high performance electrocatalyst for oxygen reduction reaction", Small, Vol. 10, (2014), 3371-3378. (https://doi.org/10.1002/smll.201400781).
2.     Li, Y., Zhou, W., Wang, H., Xie, L., Liang, Y., Wei, F., Pennycook, S.J. and Dai, H., "An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes", Nature Nanotechnology, Vol. 7, (2012), 394-400. (https://doi.org/10.1038/nnano.2012.72).
3.     Sui, S., Wang, X., Zhou, X., Su ,Y., Riffat, S. and Liu, C.J., "A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: Nanostructure, activity, mechanism and carbon support in PEM fuel cells", Journal of Material Chemistry A, Vol. 5, (2017), 1808-1825. (https://doi.org/10.1039/C6TA08580F).
4.     Gupta, C., Maheshwari, P.H. and Dhakate, S.R., "Development of multiwalled carbon nanotubes platinum nanocomposite as efficient PEM fuel cell catalyst", Materials for Renewable and Sustainable Energy, Vol. 5, (2016), 1-11. (https://doi.org/10.1007/s40243-015-0066-5).
5.     Workman, M.J., Dzara, M., Ngo, C., Pylypenko, S., Serov, A., McKinney, S., Gordon, J., Atanassov, P. and Artyushkov, K., "Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes", Journal of Power Sources, Vol. 384, (2017), 30-39. (https://doi.org/10.1016/j.jpowsour.2017.02.067).
6.     Venkateswara Rao, C., Cabrera, C.R. and Ishikawa, Y., "In search of the active site in nitrogen-doped carbon nanotube electrodes for the oxygen reduction reaction", Journal of Physical Chemistry Letters, Vol. 1, (2010), 2622-2627. (https://doi.org/10.1021/jz100971v).
7.     Cheon, J.Y., Ahn, C., You, D.J., Pak, C., Hur, S.H., Kim, J. and Joo, S.H., "Ordered mesoporous carbon–carbon nanotube nanocomposites as highly conductive and durable cathode catalyst supports for polymer electrolyte fuel cells", Journal of Material Chemistry A, Vol. 1, No. 4, (2012), 1270-1283. (https://doi.org/10.1039/C2TA00076H).
8.     Jafri, R.I., Rajalakshmi, N. and Ramaprabhu, S., "Nitrogen-doped multi-walled carbon nanocoils as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell", Journal of Power Sources, Vol. 195, (2010), 8080-8083. (https://doi.org/10.1016/j.jpowsour.2010.06.109).
9.     Zhang, H., Chen, J., Li, Y., Liu, P., Wang, Y., An, T. and Zhao, H., "Nitrogen-doped carbon nanodots@nanospheres as an efficient electrocatalyst for oxygen reduction reaction", Electrochimica Acta, Vol. 65, (2015), 7-13. (https://doi.org/10.1016/j.electacta.2015.02.240).
10.   Qiao, X., Liao, S., You, C. and Chen, R., "Phosphorus and nitrogen dual doped and simultaneously reduced graphene oxide with high surface area as efficient metal-free electrocatalyst for oxygen reduction", Catalysts, Vol. 5, (2015), 981-991. (https://doi.org/10.3390/catal5020981).
11.   Sadegh Hassani, S. and Samiee, L., Carbon nanostructured catalysts as high efficient materials for low temperature fuel cells, Hanbook of ecomaterials, Springer International Publishing, (2018). (https://doi.org/10.1007/978-3-319-48281-1_79-1)..
12.   Arjmandi-Tash, H., Belyaeva, L.A. and Schneider, G.F., "Single molecule detection with graphene and other two-dimensional materials: nanopores and beyond", Chemical Society Reviews, Vol. 45, (2015), 476-493. (https://doi.org/10.1039/C5CS00512D).
13.   Palaniselvam, T., Valappil, M.O., Illathvalappil, R. and Kurungot, S., "Nanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping", Energy & Environmental Sciences, Vol. 7, No. 3, (2014), 1059-1067. (https://doi.org/10.1039/c3ee43648a).
14.   Rivera, L.M., Fajardo, S., Arévalo, M.D.C., García, G. and Pastor, E., "S and N-doped graphene nanomaterials for the oxygen reduction reaction", Catalysts, Vol. 7, No. 9, (2017), 278-290. (https://doi.org/10.3390/catal7090278).
15.   Wang, X., Sun, G., Routh, P., Kim, D.H., Huang, W. and Chen, P., "Heteroatom-doped graphene materials: Syntheses, properties and applications", Chemical Society Reviews, Vol. 43, (2014), 7067-7098. (https://doi.org/10.1039/C4CS00141A).
16.   Daems, N., Sheng, X., Vankelecom Ivo, F.J. and Pescarmona, P.P., "Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction", Journal of Material Chemistry A, Vol. 2, (2014), 4085-4110. (https://doi.org/10.1039/C3TA14043A).
17.   Guo, C., Liao, W., Li, Z., Sun, L. and Chen, C., "Easy conversion of protein-rich enoki mushroom biomass to nitrogen-doped carbon nanomaterial as a promising metal-free catalyst for oxygen reduction reaction", Nanoscale, Vol. 7, No. 38, (2015), 15990-15998. (https://doi.org/10.1039/C5NR03828F).
18.   Guo, C., Sun, L., Liao, W. and Li, Z., "The use of an edible mushroom-derived renewable carbon material as a highly stable electrocatalyst towards four-electron oxygen reduction", Materials, Vol. 9, No. 1, (2016), 1-11. (https://doi.org: 10.3390/ma9010001).
19.   Sadegh Hassani, S., Ziaedini, A., Samiee, L., Dehghani, M., Mashyekhi, M. and Faramarzi, M.A., "One step synthesis of tertiary co-doped graphene electrocatalyst using microalgae synechococcus elangatus for applying in microbial fuel cell", Fuel Cells, Vol. 19, No. 5, (2019), 623-634. (https://doi.org/10.1002/fuce.201800167).
20.   Sadegh Hassani, S., Ganjali, M.R., Samiee, L., Rashidi, A.M., Tasharrofi, S., Yadegari, A., Shoghi, F. and Martel, R., "Comparative study of various types of metal free N and S co-doped porous graphene for high performance oxygen reduction reaction in alkaline solution", Journal of Nanoscience and Nanotechnology, Vol. 18, (2018), 4565-4579. (https://doi.org/10.1166/jnn.2018.15316).
21.   Pourmand, S., Abdouss, M. and Rashidi, A.M., "Preparation of via nanoporous zinc oxide and its application as a nano adsorbent for benzene, toluene and xylenes removal", International Journal of Environmental Research, Vol. 9, (2015), 1269-1276. (https://doi.org/10.22059/IJER.2015.1018).
22.   Qu, L.T., Liu, Y., Baek, J.B. and Dai, L.M., "Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells", ACS Nano, Vol. 4, (2010), 1321-1326. (https://doi.org/10.1021/nn901850u).
23.   Lin, Z., Waller, G., Liu, Y. and Wong, C.P., "3D nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction", Nano Energy, Vol. 2. (2013), 241-248. (https://doi.org/10.1016/j.nanoen.2012.09.002).
24.   Xing, Z., Ju, Z., Zhao, Y., Wan, J., Zhu, Y., Qiang, Y. and Qian, Y., "One-pot hydrothermal synthesis of nitrogen-doped graphene as high-performance anode materials for lithium ion batteries", Scientific Reports, Vol. 6, (2016), 26146-26158. (https://doi.org/10.1038/srep26146).
25.   Ai, W., Luo, Z., Jiang, J., Zhu, J., Du, Z., Fan, Z., Xie, L., Zhang, H., Huang, W. and Yu, T., "Nitrogen and sulfur codoped graphene: multifunctional electrode materials for high performance Li ion batteries and oxygen reduction reaction", Advanced Materials, Vol. 26, (2014), 6186-6192. (https://doi.org/10.1002/adma.201401427).
26.   Sun, Z., Masa, J., Weide, P., Fairclough, S.M., Robertson, A.W., Ebbinghaus, P., Warner, F.H., Tsang, S.C.E., Muhlerb, M. and Schuhmann, W., "High-quality functionalized few-layer graphene: facile fabrication and doping with nitrogen as a metal-free catalyst for the oxygen reduction reaction", Journal of Material Chemistry A, Vol. 3, (2015), 15444-15450. (https://doi.org/10.1039/C5TA02248G).
27.   Brunauer, S., Deming, L.S., Deming ,W.E. and Teller, E., "On a theory of the van der Waals adsorption of gases", Journal of the American Chemical Society, Vol. 62, No. 7, (1940), 1723-1732. (https://doi.org/10.1021/ja01864a025).
28.   Ma, C.B., Zhu, Z.T., Wang, H.X., Huang, X., Zhang, X., Qi, X., Zhang, H.L., Zhu, Y., Deng, X., Peng, Y., Hand, Y., Zhang, H. and Lu, L., "Covalent entrapment of cobalt–iron sulfides in N-doped mesoporous carbon: Extraordinary bifunctional electrocatalysts for oxygen reduction and evolution reactions", ACS Applied Materials & Interfaces, Vol. 7, (2015), 1207-1218. (https://doi.org/10.1021/am507033x).
29.   Wu, Z.S., Yang, S., Sun, Y., Parvez, K., Feng, X. and Mullen, K., "3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction", Journal of the American Chemical Society, Vol. 134, (2012), 9082-9085. (https://doi.org/10.1021/ja3030565).
30.   Bag, S., Mondal, B., Das, A.K. and Raj, C.R., "Nitrogen and sulfur dual-doped reduced graphene oxide: Synergistic effect of dopants towards oxygen reduction reaction", Electrochimica Acta, Vol. 163, (2015), 16-23. (https://doi.org/10.1016/j.electacta.2015.02.130).
32.   Dou, S., Huang, X., Ma, Z., Wu, J. and Wang, S., "A simple approach to the synthesis of BCN graphene with high capacitance", Nanotechnology, Vol. 26, (2015), 045402. (https://doi.org/10.1088/0957-4484/26/4/045402).
33.   Chen, X., Chen, X., Xu, X., Yang, Z., Liu, Z., Zhang, L., Xu, X., Chen, Y. and Huang, S., "Sulfur doped porous reduced graphene oxide hollow nanosphere frameworks as metal free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials", Nanoscale, Vol. 6, No. 22, (2014), 13740-13747. (https://doi.org/10.1039/C4NR04783D).
34.   Dong, Y., Pang, H., Yang, H.B., Guo, C., Shao, J., Chi, Y., Li, C.M. and Yu, T., "Carbon based dots co-doped with nitrogen and sulfur for high quantum yield and excitation independent emission", Angewandte Chemie International Edition, Vol. 52, (2013), 7800-7804. (https://doi.org/10.1002/anie.201301114).
35.   Wang, Y., Zhang, B., Xu, M. and He, X., "Tunable ternary (P,S,N) –doped graphene as an efficient electrocatalyst for oxygen reduction reaction in an alkaline medium", RSC Advances, Vol. 5, No. 105, (2015), 86746-86753. (https://doi.org/10.1039/C5RA18251D).
36.   Lin, H., Chu, L., Wang, X., Yao, Z., Liu, F., Ai, Y., Zhuang, X. and Han, S., "Boron, nitrogen and phosphorous ternary doped graphene aerogel with hierarchically porous structures as highly efficient electrocatalysts for oxygen reduction reaction", New Journal of Chemistry, Vol. 40, (2016), 6022-6029. (https://doi.org/10.1039/C5NJ03390J).