The potential of novel carbon nanocages as a carbon support for an enhanced methanol electro-oxidation reaction in a direct methanol fuel cell
Zatil A. C. Ramli
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorCorresponding Author
S. K. Kamarudin
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, University Kebangsaan Malaysia, Bangi, Malaysia
Correspondence
S. K. Kamarudin, Fuel Cell Institute, University Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia.
Email: [email protected]
Search for more papers by this authorSahriah Basri
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorAzran M. Zainoodin
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorZatil A. C. Ramli
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorCorresponding Author
S. K. Kamarudin
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, University Kebangsaan Malaysia, Bangi, Malaysia
Correspondence
S. K. Kamarudin, Fuel Cell Institute, University Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia.
Email: [email protected]
Search for more papers by this authorSahriah Basri
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorAzran M. Zainoodin
Fuel Cell Institute, University Kebangsaan Malaysia, Bangi, Malaysia
Search for more papers by this authorFunding information: Ministry of Higher Education, Malaysia, Grant/Award Number: TRGS/1/2018/UKM/01/6/2; Universiti Kebangsaan Malaysia, Grant/Award Number: DIP-2019-021
Summary
In this study, we introduce the potential for a new catalyst support, namely, carbon nanocages (CNCs) for anodic direct methanol fuel cell (DMFC). The synthesis, characterization and catalytic activities of four electrocatalysts, PtRu/CNC, PtNi/CNC, PtFe/CNC and PtCo/CNC, have been investigated. These electrocatalysts are synthesized using pyrolysis, followed by a microwave-assisted ethylene glycol reduction method. From X-ray diffraction analysis, PtNi/CNC and PtRu/CNC showed the smallest crystallite particle size of Pt-alloy, which corresponded to the (111) plane. The Raman spectra confirmed the presence of the carbon support material in all prepared electrocatalysts. The ratio value of the D band and G band (ID/IG) of all prepared samples was not much different within the electrocatalyst and CNC. The ID/IG values calculated for the CNC, PtNi/CNC, PtRu/CNC, PtCo/CNC and PtFe/CNC electrocatalysts were 0.90, 0.89, 0.83, 0.78 and 0.77, respectively. Therefore, the number of defects of graphitization in increasing order (ID/IG) was PtFe/CNC < PtCo/CNC < PtRu/CNC < PtNi/CNC < CNC. Brunauer-Emmett-Teller analysis revealed that the CNC support has a mesoporous-type structure with a high surface area of 416 m2 g−1, which indicates that this support has a high potential to act as an excellent catalyst support. From the cyclic voltammetry curve, PtRu/CNC showed the highest catalytic activity in methanol electro-oxidation and reached a value of 427 mA mg−1, followed by PtNi/CNC (384.11 mA mg−1), PtCo/CNC (150.53 mA mg−1) and PtFe/CNC (144.11 mA mg−1). PtFe/CNC exhibited a higher ratio value of If/Ib (3.24) compared with PtRu/CNC (2.34), PtNi/CNC (1.43) and PtCo/CNC (1.62). These values show that the combination of Pt and Fe catalysts in PtFe/CNC had better CO tolerance than PtRu/CNC, PtNi/CNC and PtCo/CNC electrocatalysts. The higher performance of PtRu/CNC was attributed to the fact that it had the smallest bimetallic-Pt crystallite; there was a smooth distribution of bimetallic-Pt on its CNC support, as shown by field emission scanning electron microscopy; it had the highest electrochemical surface area value (16.23 m2 g−1); and it had an overall catalytic performance enhanced by the advantages of the unique and large surface area from the CNC as support material. In passive DMFC mode, PtRu/CNC showed a maximum power density of 3.35 mW cm−2, which is 1.72 times higher than that of the PtRu/C commercial electrocatalyst.
REFERENCE
- 1Ince AC, Karaoglan MU, Glüsen A, Colpan CO, Müller M, Stolten D. Semiempirical thermodynamic modeling of a direct methanol fuel cell system. Int J Energy Res. 2019; 43(8): 3601-3615.
- 2Bahari NA, Isahak WNR, Masdar MS, Yaakob Z. Clean hydrogen generation and storage strategies via CO2 utilization into chemicals and fuels: a review. Int J Energy Res. 2019; 43(10): 5128-5150.
- 3Munjewar SS, Thombre SB, Mallick RK. Approaches to overcome the barrier issues of passive direct methanol fuel cell-review. Renew Sustain Energy Rev. 2017; 67: 1087-1104.
- 4Thiam H, Daud WRW, Kamarudin SK, et al. Performance of direct methanol fuel cell with a palladium-silica nanofibre/Nafion composite membrane. Energ Conver Manage. 2013; 75: 718-726.
- 5Ahmed M, Dincer I. A review on methanol crossover in direct methanol fuel cells: challenges and achievements. Int J Energy Res. 2011; 35(14): 1213-1228.
- 6Ahmad MM, Kamarudin SK, Daud WRW, Yaakub Z. High power passive μDMFC with low catalyst loading for small power generation. Energ Conver Manage. 2010; 51: 821-825.
- 7Shaari N. The optimization performance of cross-linked sodium alginate polymer electrolyte bio-membranes in passive direct methanol/ethanol fuel cells. Int J Energy Res. 2019; 43(14): 8275-8285.
- 8Formo E, Peng Z, Lee E, Lu X, Yang H, Xia Y. Direct oxidation of methanol on Pt nanostructures supported on electrospun nanofibers of anatase. J Phys Chem C. 2008; 112(27): 9970-9975.
- 9Johánek V, Ostroverkh A, Fiala R. Vapor-feed low temperature direct methanol fuel cell with Pt and PtRu electrodes: chemistry insight. Renew Energy. 2019; 138: 409-415.
- 10Çögenli MS, Yurtcan AB. Catalytic activity, stability and impedance behavior of PtRu/C, PtPd/C and PtSn/C bimetallic catalysts toward methanol and formic acid oxidation. Int J Hydrogen Energy. 2018; 43(23): 10698-10709.
- 11Xiao Y, Wang Y, Varma A. Low-temperature selective oxidation of methanol over Pt-bi bimetallic catalysts. J Catal. 2018; 363: 144-153.
- 12Ramli ZAC, Kamarudin SK. Platinum based catalysts on various carbon supports and conducting polymers for direct methanol fuel cell applications: a review. Nanoscale Res Lett. 2018; 13(1): 410.
- 13Hall SC, Subramanian V, Teeter G, Rambabu B. Influence of metal-support interaction in Pt/C on CO and methanol oxidation reactions. Solid State Ion. 2004; 175(1-4): 809-813.
- 14Hanaei H, Assadi MK, Saidur R. Highly efficient antireflective and self-cleaning coatings that incorporate carbon nanotubes (CNTs) into solar cells: a review. Renew Sustain Energy Rev. 2016; 59(c): 620-635.
- 15Abdullah M, Kamarudin SK, Shyuan LK. TiO2 nanotube-carbon (TNT-C) as support for Pt-based catalyst for high methanol oxidation reaction in direct methanol fuel. Nanoscale Res Lett. 2016; 11(1): 553.
- 16Kang S, Lim S, Peck D, Kim S, Jung D. Stability and durability of PtRu catalysts supported on carbon nanofibers for direct methanol fuel cells. Int J Hydrogen Energy. 2011; 37(5): 4685-4693.
- 17Tsukagoshi Y, Ishitobi H, Nakagawa N. Improved performance of direct methanol fuel cells with the porous catalyst layer using highly-active nanofiber catalyst. Carbon Resour Convers. 2018; 1(1): 61-72.
10.1016/j.crcon.2018.03.001 Google Scholar
- 18Wang Y, Zou L, Huang Q, Zou Z, Yang H. 3D carbon aerogel-supported PtNi intermetallic nanoparticles with high metal loading as a durable oxygen reduction electrocatalyst. Int J Hydrogen Energy. 2017; 42(43): 26695-26703.
- 19Zhao L, Wang ZB, Li JL, Zhang JJ, Sui XL, Zhang LM. Hybrid of carbon-supported Pt nanoparticles and three dimensional graphene aerogel as high stable electrocatalyst for methanol electrooxidation. Electrochim Acta. 2016; 189: 175-183.
- 20Ma X, Luo L, Zhu L, et al. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: direct synthesis and electrochemical performance for methanol oxidation. J Power Sources. 2013; 241: 274-280.
- 21Sieben JM, Ansón-Casaos A, Martínez MT, Morallón E. Single-walled carbon nanotube buckypapers as electrocatalyst supports for methanol oxidation. J Power Sources. 2013; 242: 7-14.
- 22Wang XX, Tan ZH, Zeng M, Wang JN. Carbon nanocages: a new support material for Pt catalyst with remarkably high durability. Sci Rep. 2014; 4: 1-11.
- 23Huo W, He H, Sun F. Microfluidic direct methanol fuel cell by electrophoretic deposition of platinum/carbon nanotubes on electrode surface. Int J Energy Res. 2015; 39(10): 1430-1436.
- 24Baronia R, Goel J, Tiwari S, Singh P, Singh D, Singh SP. Efficient electro-oxidation of methanol using PtCo nanocatalysts supported reduced graphene oxide matrix as anode for DMFC. Int J Hydrogen Energy. 2017; 42(15): 10238-10247.
- 25Elbaz L, Kreller CR, Henson NJ, Brosha EL. Electrocatalysis of oxygen reduction with platinum supported on molybdenum carbide-carbon composite. J Electroanal Chem. 2014; 720: 34-40.
- 26Nassr ABAA, Sinev I, Grünert W, Bron M. PtNi supported on oxygen functionalized carbon nanotubes: in depth structural characterization and activity for methanol electrooxidation. Appl Catal Environ. 2013; 142-143: 849-860.
- 27Zheng FS, Liu SH, Kuo CW. Ultralow Pt amount of Pt-Fe alloys supported on ordered mesoporous carbons with excellent methanol tolerance during oxygen reduction reaction. Int J Hydrogen Energy. 2016; 41(4): 2487-2497.
- 28Eshghi A, Kheirmand M, Sabzehmeidani MM. Platinum-Iron nanoparticles supported on reduced graphene oxide as an improved catalyst for methanol electro oxidation. Int J Hydrogen Energy. 2018; 43(12): 6107-6116.
- 29Ramli ZAC, Asim N, Isahak WNR, et al. Photocatalytic degradation of methylene blue under UV light irradiation on prepared carbonaceous TiO2. Sci World J. 2014; 13-15: 1-8.
10.1155/2014/964731 Google Scholar
- 30Qin H, Huang Y, Liu S, Fang Y, Kang S. Synthesis and properties of magnetic carbon nanocages particles for dye removal. J Nanomater. 2015; 2015: 1-8.
- 31Jiang X, Wang X, Shen L, et al. High-performance Pt catalysts supported on hierarchical nitrogen-doped carbon nanocages for methanol electrooxidation. Chin J Catal. 2016; 37(7): 1149-1155.
- 32Abdullah N, Kamarudin SK, Shyuan LK. Novel anodic catalyst support for direct methanol fuel cell: characterizations and single-cell performances. Nanoscale Res Lett. 2018; 13: 1-13.
- 33Zainoodin AM, Kamarudin SK, Masdar MS, Daud WRW. High power direct methanol fuel cell with a porous carbon nanofiber anode layer. Appl Energy. 2014; 113: 946-954.
- 34Cordero-Borboa AE, Sterling-Black E, Gómez-Cortés A, Vázquez-Zavala A. X-ray diffraction evidence of the single solid solution character of bi-metallic Pt-Pd catalyst particles on an amorphous SiO2 substrate. Appl Surf Sci. 2003; 220(1-4): 169-174.
- 35Lv Q, Xiao Y, Ge J, Xing W, Liu C. Reconstructed PtFe alloy nanoparticles with bulk-surface differential structure for methanol oxidation. Electrochim Acta. 2014; 139: 61-68.
- 36Wang S, Ping S, Wang X. Microwave-assisted one-pot synthesis of metal/metal oxide nanoparticles on graphene and their electrochemical applications. Electrochim Acta. 2011; 56(9): 3338-3344.
- 37Tan Y, Xu C, Chen G, et al. Synthesis of ultrathin nitrogen-doped graphitic carbon Nanocages as advanced electrode materials for Supercapacitor. ACS Appl Mater Interfaces. 2013; 5: 2241-2248.
- 38Wang Y, Su F, Wood CD, Lee JY, Zhao XS. Preparation and characterization of carbon Nanospheres as anode materials in lithium-ion secondary batteries. Ind Eng Chem Res. 2008; 47(7): 2294-2300.
- 39Li Z, Jaroneic M, Papakonstantinou P, et al. Supercritical fluid growth of porous carbon Nanocages. Chem Mater. 2007; 19(13): 3349-3354.
- 40Azizi MAH, Isahak WNR, Masdar MS, Somalu MR, Yarmo MA. Enhanced hydrogen selectivity from catalystic decomposition of formic acid over FeZnIr nanocatalyst at room temperature. Res Chem Intermed. 2018; 44: 6787-6802.
- 41Kim DW, Oh SG. Agglomeration behavior of chromia nanoparticles prepared by amorphous complex method using chelating effect of citric acid. Mater Lett. 2005; 59(8-9): 976-980.
- 42Nair AAS, Sundara R, Anitha N. Hydrogen storage performance of palladium nanoparticles decorated graphitic carbon nitride. Int J Hydrogen Energy. 2015; 40(8): 3259-3267.
- 43Bagheri S, Julkapli NM, Hamid SBA. Titanium dioxide as a catalyst support in heterogeneous catalysis. Sci World J. 2014; 2014: 1-21.
- 44Lin Y, Cui X, Yen C, Wai CM. Platinum/carbon nanotube nanocomposite synthesized in supercritical fluid as electrocatalysts for low-temperature fuel cells. J Phys Chem B. 2005; 109(30): 14410-14415.
- 45Chen F, Ren J, He Q, Liu J, Song R. Facile and one-pot synthesis of uniform PtRu nanoparticles on polydopamine-modified multiwalled carbon nanotubes for direct methanol fuel cell application. J Colloid Interface Sci. 2017; 497: 276-283.
- 46Rodriguez JR, Félix RM, Reynoso EA, et al. Synthesis of Pt and Pt-Fe nanoparticles supported on MWCNTs used as electrocatalysts in the methanol oxidation reaction. J Energy Chem. 2014; 23(4): 483-490.
- 47Sahin O, Kivrak HA. Comparative study of electrochemical methods on Pt-Ru DMFC anode catalysts: the effect of Ru addition. Int J Hydrogen Energy. 2013; 38(2): 901-909.
- 48Cooper KR. In Situ Pem Fuel cell electrochemical surface area and catalyst utilization measurement, in fuel cell magazine. North Carolina: Scribner Associates; 2009.
- 49Kim HY, Kim DY, Han H, Shu YG. PtRu/C-Au/TiO2 electrocatalyst for a direct methanol fuel cell. J Power Sources. 2006; 159(1): 484-490.
- 50Yan Z, Wang H, Zhang M, Jiang Z, Jiang T, Xie J. Pt supported on Mo2C particles with synergistic effect and strong interaction force for methanol electro-oxidation. Electrochim Acta. 2013; 95: 218-224.
- 51Yung T, Liu TY, Wang KS, et al. Synthesis of PtNi alloy nanoparticles on graphene-based polymer nanohybrids for electrocatalytic oxidation of methanol. Catalysts. 2016; 6: 1-11.
- 52Shi M, Zhang W, Zhao D, Chu Y, Ma C. Reduced graphene oxide-supported tungsten carbide modified with ultralow-platinum and ruthenium-loading for methanol oxidation. Electrochim Acta. 2014; 143: 222-231.
- 53Chen W, Wei X, Zhang Y. A comparative study of tungsten-modified PtRu electrocatalysts for methanol oxidation. Int J Hydrogen Energy. 2014; 39(13): 6995-7003.
- 54Yen CH, Shimizu K, Lin YY, Bailey F, Cheng F, Wai CM. Chemical fluid deposition of Pt-based bimetallic nanoparticles on multiwalled carbon nanotubes for direct methanol fuel cell application. Energy Fuel. 2007; 21(4): 2268-2271.
- 55Kolla P, Smirnova A. Methanol oxidation on hybrid catalysts: PtRu/C nanostructures promoted with cerium and titanium oxides. Int J Hydrogen Energy. 2013; 38(35): 15152-15159.
- 56Kim M, Fang B, Chaudhari NB, Song M, Bae TS, Yu JS. A highly efficient synthesis approach of supported Pt-Ru catalyst for direct methanol fuel cell. Electrochim Acta. 2010; 55(15): 4543-4550.
- 57Jurzinsky T, Cremers C, Jung F, Pinkwart K, Tübke J. Development of materials for anion-exchange membrane direct alcohol fuel cells. Int J Hydrogen Energy. 2015; 40(35): 11569-11576.
- 58Pierozynski B, Mikolajczyk T, Turemko M. On the temperature performance of ethanol oxidation reaction at palladium-activated nickel foam. Electrocatalysis. 2015; 6(2): 173-178.
- 59Hashim N, Kamarudin SK, Daud WRW. Design, fabrication and testing of a PMMA-based passive single-cell and a multi-cell stack micro-DMFC. Int J Hydrogen Energy. 2009; 34(19): 8263-8269.
- 60Shimizu T, Momma T, Mohamedi M, Osaka T, Sarangapani S. Design and fabrication of pumpless small direct methanol fuel cells for portable applications. J Power Sources. 2004; 137(2): 277-283.
- 61Eccarius S, Krause F, Beard K, Agert C. Passively operated vapor-fed direct methanol fuel cells for portable applications. J Power Sources. 2008; 182(2): 565-579.
- 62Chang I, Ha S, Kim J, Lee JY, Cha SW. Performance evaluation of a passive direct methanol fuel cell. J Power Sources. 2008; 184(1): 9-15.
