POLİMER ELEKTROLİT MEMBRANLI (PEM) YAKIT PİLLERİ İÇİN İNDİRGENMİŞ GRAFEN OKSİT - KARBON NANOFİBER HİBRİT DESTEKLİ PLATİN ELEKTROKATALİZÖRLERİNİN GELİŞTİRİLMESİ

Öz

Polimer elektrolit membranlı (PEM) yakıt pillerinde elektrot yapısında kullanılan elektrokatalizörün verimliliğinin artırılması, maliyetinin düşürülmesi ve ticarileşmesi açısından oldukça önemlidir. Son
yıllarda, ticari olarak kullanılan karbon siyahı destekli platin (Pt/C) elektrokatalizörün aktivite ve performans gibi dezavantajlarından dolayı yeni nesil elektrokatalizörlerin kullanımı oldukça dikkat
çekmektedir. Bu sebeple, bu çalışmada indirgenmiş grafen oksit (rGO) ve karbon nanofiber (KNF) esaslı hibrit karbon yapısı katalizör destek malzemesi olarak kullanılmıştır ve bu destekler üzerine Pt nanoparçacıkları sentezlenmiştir. KNF ve rGO/KNF destekli Pt elektrokatalizörlerin (Pt/KNF ve Pt/rGOKNF) sentezi için basit, çevre dostu ve düşük maliyetli bir teknik olan mikrodalga destekli (MW) sentez tekniği kullanılmıştır. Mikrodalga tekniği ile sentez sayesinde tek basamakta, hızlı ve verimli bir sentez geliştirilmiştir. Sentezlenen elektrokatalizörün fiziksel karakterizasyonu için X-ışını difraktometresi (XRD), RAMAN spektroskopisi ve geçirimli elektron mikroskopisi (TEM) teknikleri kullanılmıştır. Elektrokimyasal aktivite analizi için döngüsel voltametri (CV) ve doğrusal taramalı voltametri (LSV) tekniği kullanılmıştır. Bunun dışında, yakıt pili içinde performans testleri gerçekleştirilmiştir. Pt/rGOKNF Pt/KNF ile kıyaslandığında daha yüksek katalitik aktivite ve yakıt pili performansı (maksimum güç yoğunluğu: 447 mW.cm-2) göstermiştir. Elde edilen sonuçlar, Pt/rGO-KNF hibrit katalizörlerin oldukça umut vaat eden PEM yakıt pili elektrot malzemeleri olduğunu göstermektedir.

Anahtar Kelimeler

• Karbon nanolifler
• grafen
• elektrokatalizör
• PEM yakıt pilleri

Development of Reduced Graphene Oxide - Carbon Nanofiber Hybrid Supported Platinum Electrocatalysts for Polymer Electrolyte Membrane (PEM) Fuel Cells

Öz

Increasing the efficiency of the electrocatalyst for polymer electrolyte membrane (PEM) fuel cell’s electrode is very important in terms of lower the cost and commercialization. In recent years, the
use of next generation electrocatalysts has received great attention due to the disadvantages such as low activity and performance of commercial carbon black supported platinum (Pt/C) electrocatalysts. Therefore, here, a hybrid carbon structure based on reduced graphene oxide (rGO) and carbon nanofiber (CNF) was used as a catalyst support and Pt nanoparticles were synthesized on these supports. The simple, environmentally friendly, and cheap microwave-assisted (MW) synthesis technique was used for the synthesis of Pt nanoparticles on rGO /CNF electrocatalysts (Pt/CNF and Pt/rGO-CNF). By means of microwave assisted synthesis, one-step, fast and efficient synthesis has been designed. Physical characterization of electrocatalysts have been performed by using X-ray diffraction (XRD), RAMAN spectroscopy, transmission electron microscopy (TEM) techniques. Electrochemical activity of electrocatalysts were investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Additionally, performance tests were carried out in the fuel cell. Pt/rGO-CNF showed higher catalytic activity and fuel cell performance (maximum power density: 449 mW.cm-2) compared to Pt/CNF. The obtained results show that the Pt/rGO-CNF hybrid catalysts are highly promising PEM fuel cell electrode materials.

Anahtar Kelimeler

• Carbon nanofibers
• graphene
• electrocatalyst
• PEM fuel cells

Kaynakça

1. Acres, G.J.K. (2001) Recent advances in fuel cell technology and its applications, Journal of Power Sources, 100, 60–66. doi: 10.1016/S0378-7753(01)00883-7
2. Álvarez, G., Alcaide, F., Cabot, P.L., Lázaro, M.J., Pastor, E., Solla‐Gullón, J. (2012) Electrochemical performance of low temperature PEMFC with surface tailored carbon nanofibers as catalyst support, International Journal of Hydrogen Energy, 37, 393‐404. doi:10.1016/j.ijhydene.2011.09.055
3. Andersen, S.M., Borghei, M., Lund, P., ve diğ. (2013) Durability of carbon nanofiber (CNF) & carbon nanotube (CNT) as catalyst support for Proton Exchange Membrane Fuel Cells, Solid State Ionics, 23, 94‐101. doi: 10.1016/j.ssi.2012.11.020
4. Arici, E., Kaplan, B. Y., Mert, A. M., Gursel, S. A., & Kinayyigit, S. (2019) An effective electrocatalyst based on platinum nanoparticles supported with graphene nanoplatelets and carbon black hybrid for PEM fuel cells, International Journal of Hydrogen Energy, 44(27), 14175-14183.
5. Daş, E., Gürsel, S.A., Şanlı, L.I., Yurtcan, A.B. (2017) Thermodynamically controlled Pt deposition over graphene nanoplatelets: effect of Pt loading on PEM fuel cell performance. International Journal of Hydrogen Energy, 42, 19246‐19256. doi: 10.1016/j.ijhydene.2018.11.210
6. Daş, E., Kaplan, B. Y., Gürsel, S. A., ve Yurtcan, A. B. (2019) Graphene nanoplatelets-carbon black hybrids as an efficient catalyst support for Pt nanoparticles for polymer electrolyte membrane fuel cells, Renewable Energy, 139, 1099-1110. doi:10.1016/j.renene.2019.02.137
7. Figueiredo, J.L. ve Pereira, M.F.R. (2013) Synthesis and functionalization of carbon xerogels to be used as supports for fuel cell catalysts, Journal of Energy Chemistry, 22, 195‐201. doi: 10.1016/S2095-4956(13)60025-X
8. Gasteiger, H. A., Kocha, S. S., Sompalli, B., ve Wagner, F. T. (2005) Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs, Applied Catalysis B: Environmental, 56(1-2), 9-35. doi: 10.1016/j.apcatb.2004.06.021

9. Gasteiger, H. A., ve Yan, S. G. (2004) Dependence of PEM fuel cell performance on catalyst loading, Journal of Power Sources, 127(1-2), 162-171. doi: 10.1016/j.jpowsour.2003.09.013
10. Hong, T.Z., Xue, Q., Yang, Z.-Y., Dong, Y.-P. (2016) Great-enhanced performance of Pt nanoparticles by the unique carbon quantum dot/reduced graphene oxide hybrid supports towards methanol electrochemical oxidation, Journal of Power Sources, 303,109–117. doi: 10.1016/j.jpowsour.2015.10.092
11. Hsueh, Y.J., Yu, C.C., Lee, K.R., ve diğ. (2013) Ordered porous carbon as the catalyst support for proton‐exchange membrane fuel cells, International Journal of Hydrogen Energy. 38,10998‐11003. doi:10.1016/j.ijhydene.2013.01.007
12. Jung, J.H., Park, H.J., Kim, J., Hur, S.H., (2014) Highly durable Pt/graphene oxide and Pt/C hybrid catalyst for polymer electrolyte membrane fuel cell, Journal of Power Sources, 248, 1156-1162. doi:10.1016/j.jpowsour.2013.10.055
13. Kaplan, B. Y., Haghmoradi, N., Biçer, E., Merino, C., ve Gürsel, S. A. (2018) High performance electrocatalysts supported on graphene based hybrids for polymer electrolyte membrane fuel cells, International Journal of Hydrogen Energy, 43(52), 23221-23230. doi: 10.1016/j.ijhydene.2018.10.222
14. Karteri, İ., Karataş, Ş., Al-Ghamdi, A., Yakuphanoğlu, F., (2015) The electrical characteristics of thin film transistors with graphene oxide and organic insulators, Synthetic Metals, 199, 241– 245. doi: 10.1016/j.synthmet.2014.11.036
15. Kundu, P., Nethravathi, C., Deshpande, P.A., Rajamathi, M., Madras, G., Ravishankar, N. (2011) Ultrafast microwave‐assisted route to surfactant‐free ultrafine Pt nanoparticles on graphene: synergistic co‐reduction mechanism and high catalytic activity, Chemistry of Materials, 23, 2772‐2780. doi: 10.1021/cm200329a
16. Liao, K.H., Mittal, A., Bose, S., Leighton, C., Mkhoyan, K.A., Macosko, C.W., (2011) Aqueous only route toward graphene from graphite oxide, ACS Nano, 5(2), 1253-1258. doi:10.1021/nn1028967
17. Lim, B., Jiang, M., Camargo, P.H.C., Cho, E.C., Tao, J., Lu, X., Zhu, Y., Xia, Y. (2009) Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction, Science, 324, 1302-1305. doi: 10.1126/science.1170377
18. Lori, O., ve Elbaz, L. (2020) Recent advances in synthesis and utilization of ultra‐low loading of precious metal‐based catalysts for fuel cells, ChemCatChem, 12(13), 3434-3446 doi:10.1002/cctc.202000001
19. Marinkas, A., Arena, F., Mitzel, J., Prinz, G. M., Heinzel, A., Peinecke, V. ve Natter, H. (2013) Graphene as catalyst support: The influences of carbon additives and catalyst preparation methods on the performance of PEM fuel cells, Carbon, 58, 139-150. doi: 10.1016/j.carbon.2013.02.043
20. Mondal, A. ve Jana, N. R., (2014) Surfactant-free, stable noble metal–graphene nanocomposite as high performance electrocatalyst, ACS Catalysis, 4(2), 593-599. doi: 0.1021/cs401032p
21. Park, S., Shao, Y., Wan, H., Rieke, P. C., Viswanathan, V. V., Towne, S. A., ... ve Wang, Y. (2011), Design of graphene sheets-supported Pt catalyst layer in PEM fuel cells. Electrochemistry communications, 13(3), 258-261. doi: 10.1016/j.elecom.2010.12.028
22. Shahgaldi, S. ve Hamelin, J. (2015) Improved carbon nanostructures as a novel catalyst support in the cathode side of PEMFC: a critical review, Carbon, 94, 705‐728. doi: 10.1016/j.carbon.2015.07.055
23. Sharma, S., Ganguly, A., Papakonstantinou, P., ve diğ. (2010) Rapid microwave synthesis of CO tolerant reduced graphene oxide‐supported platinum electrocatalysts for oxidation of methanol, Journal of Physical Chemistry C, 114,19459‐19466. doi: 10.1021/jp107872z
24. Song, J., Li, G., Qiao, J. (2015) Ultrafine porous carbon fiber and its supported platinum catalyst for enhancing performance of proton exchange membrane fuel cells, Electrochimica Acta, 177, 174‐180. doi: 10.1016/j.electacta.2015.03.142
25. Sopian, K., Daud, W.R.W., (2006) Challenges and future developments in proton exchange membrane fuel cells, Renewable Energy, 31(5), 719-727. doi: 10.1016/j.renene.2005.09.003
26. Şanlı, L.I., Bayram, V., Yarar, B., Ghobadi, S., Gürsel, S.A. (2016) Development of graphene supported platinum nanoparticles for polymer electrolyte membrane fuel cells: effect of support type and impregnation–reduction methods, International Journal of Hydrogen Energy, 41, 3414‐3427. doi: 10.1016/j.ijhydene.2015.12.166
27. Wang, Y., Jin, J., Yang, S., Li, G., Qiao, J. (2015) Highly active and stable platinum catalyst supported on porous carbon nanofibers for improved performance of PEMFC, Electrochimica Acta, 177, 181‐189. doi: 10.1016/j.electacta.2015.01.134
28. Yarar Kaplan, B., Haghmoradi, N., Jamil, E., Merino, C., Alkan Gürsel, S. (2020) Platinum nanoparticles decorated carbon nanofiber hybrids as highly active electrocatalysts for polymer electrolyte membrane fuel cells, International Journal of Energy Research, 44(13), 10251-10261. doi: 10.1002/er.5646
29. Yılmaz, M. S., Kaplan, B. Y., Metin, Ö., ve Gürsel, S. A. (2018) A facile synthesis and assembly of ultrasmall Pt nanoparticles on reduced graphene oxide‑carbon black hybrid for enhanced performance in PEMFC, Materials & Design, 151, 29-36. doi: 10.1016/j.matdes.2018.04.041
30. Zecevic, S.K., Wainright, J.S., Litt, M.H., Gojkovic, S.L., Savinell, R.F. (1997) Kinetics of O 2 Reduction on a Pt Electrode Covered with a Thin Film of Solid Polymer Electrolyte, Journal of Electrochemical Society, 144, 2973–2982.