Cobalt/copper-decorated carbon nanofibers as novel non-precious electrocatalyst for methanol electrooxidation
© Barakat et al.; licensee Springer. 2014
Received: 7 November 2013
Accepted: 16 December 2013
Published: 3 January 2014
In this study, Co/Cu-decorated carbon nanofibers are introduced as novel electrocatalyst for methanol oxidation. The introduced nanofibers have been prepared based on graphitization of poly(vinyl alcohol) which has high carbon content compared to many polymer precursors for carbon nanofiber synthesis. Typically, calcination in argon atmosphere of electrospun nanofibers composed of cobalt acetate tetrahydrate, copper acetate monohydrate, and poly(vinyl alcohol) leads to form carbon nanofibers decorated by CoCu nanoparticles. The graphitization of the poly(vinyl alcohol) has been enhanced due to presence of cobalt which acts as effective catalyst. The physicochemical characterization affirmed that the metallic nanoparticles are sheathed by thin crystalline graphite layer. Investigation of the electrocatalytic activity of the introduced nanofibers toward methanol oxidation indicates good performance, as the corresponding onset potential was small compared to many reported materials; 310 mV (vs. Ag/AgCl electrode) and a current density of 12 mA/cm2 was obtained. Moreover, due to the graphite shield, good stability was observed. Overall, the introduced study opens new avenue for cheap and stable transition metals-based nanostructures as non-precious catalysts for fuel cell applications.
KeywordsNon-precious catalyst Electrospinning Fuel cells Decorated carbon nanofibers Methanol electrooxidation
The extensive use of fossil fuels is causing environment pollution and global warming problems. Fuel cell is a good technological option for solving energy and pollution problems. Polymer electrolyte membrane fuel cells (PEMFCs) have been investigated as high-density power sources in automobiles and in microelectronics. The efficiency of fuel cells depends on the catalytic activity of the catalysts. The use of methanol as a fuel is getting popular because it is a liquid which can be easily stored and handled. Methanol is also easier to supply to the public using our current infrastructure. In the DMFCs, methanol is directly oxidized to carbon dioxide and water, providing a new way to store and convey the energy [1–3]. The successful commercialization is quite dependent on the cost, activity, and durability of the electrocatalysts [3, 4]. At present, almost all pre-commercial low-temperature fuel cells use Pt-based electrocatalysts [5–8]. Accordingly, the manufacturing cost is relatively high which constrains their wide applications. Moreover, the catalyst poisoning by CO or CHO species is another real problem facing most of the Pt-based electrocatalysts [3, 9, 10]. Compared to the precious metals, transition metals are abundant and very cheap. Among the transition metals, cobalt has a well-known catalytic activity in many chemical reactions. It is also used as a cocatalyst to annihilate the Pt poisoning . Beside cobalt, copper-based materials also show good performance as electrocatalysts [12, 13].
In the DMFCs, methanol is oxidized to carbon dioxide at the anode according to the reaction: CH3OH + H2O = CO2 + 6H+ + 6e. The reaction is considered to be a combination of adsorption and electrochemical reaction on the anode surface [14, 15]. Accordingly, because of the adsorption capacity of carbon, it was exploited to enhance the electrocatalytic activities for many electrodes [16–20]. Addition of alloying elements to Cu has been demonstrated to provide increased electrocatalytic activity in comparison to the pure Cu electrode. For example, MnCu alloy shows a much improved electrochemical activity for the oxidation of glucose in alkaline media in comparison to that of the pure Cu electrode .
Nanofibers have gained much prominence in the recent years due to the heightened awareness of their potential applications in many fields including textiles, chemical synthesis, medicine, engineering, and defense. Among several methods for nanofiber production, electrospinning is the most widely used technique due to simplicity, high yield, effectiveness and low-cost aspects [22–24]. It is noteworthy mentioning that as compared to nanoparticles, the large axial ratio provides the nanofibrous catalysts a distinct advantage especially when utilizing in the electron transfer-based processes [25, 26]. Carbon nanofibers (CNFs) prepared by the electrospinning process gradually attracted the attention of most researchers because of the associated advantages of the synthesizing technique and the obtained product. Moreover, it is easy to control the morphology and pore structure of the obtained nanofibers . Currently, CNFs are widely used in many fields such as hydrogen energy [28, 29], electrochemical capacitors (EDLCs) , lithium-ion rechargeable batteries (LIBs) , and fuel cells .
Poly(vinyl alcohol) (PVA) is a semi-crystalline compound with comparatively high carbon content (ca. 54.5%), and easily splits into hydroxyl groups in the polymer chain which makes it favorable for use as a precursor for the production of the carbonaceous materials; however, low yield is the main constrain. The low decomposition temperature of PVA is the main reason for the low carbonization yield . Therefore, the researchers are focusing on enhancing the thermal stability of PVA. Some strategies were introduced such as dehydration of PVA from 100°C to 290°C under tension in a mixed gas atmosphere , preoxidation or subsequent dehydration , and using iodine as a stabilizer for PVA to promote dehydrogenative polymerization during the carbonization process . Recently, it was reported that cobalt strongly enhances the graphitization of PVA [22, 37].
Therefore, the main goal of this study is to introduce a new non-precious catalyst with good electrocatalytic activity. Enhancement of the activity will be based on exploiting the influence of synergetic effect of cobalt and copper bimetallic nanoparticles as well as the advantage of the nanofibrous morphology. In this study, Co/Cu-decorated carbon nanofibers are introduced as novel non-precious catalyst for methanol electrooxidation. The introduced nanofibers have been synthesized by calcination of electrospun nanofibers composed of cobalt acetate, copper acetate, and PVA in argon atmosphere at 750°C. The obtained nanofibers revealed good performance as electrocatalyst for methanol oxidation.
Solution containing copper acetate monohydrate (CuAc, 99.9 Sigma-Aldrich Corporation, St. Louis, MO, USA), cobalt acetate tetrahydrate (CoAc, 98% assay Junsei Chemical Co., Ltd, Japan), and poly(vinyl alcohol) (PVA) (10 wt.% concentration in water, molecular weight (MW) = 65,000 g/mol; DC Chemical Co, Ltd, Seoul, South Korea) was electrospun at a voltage of 20 kV using a high-voltage DC power supply. Typically, CuAc (25 wt.%) and CoAc (25 wt.% ) aqueous solutions were mixed with PVA solution to form a mixture containing 80 wt.% polymer and Cu/Co mass ratio of 1:4. The final solution was stirred at 50°C for 5 h and then subjected to the electrospinning process at 20 kV. The formed nanofiber mats were initially dried for 24 h at 80°C under vacuum and then calcined at 750°C for 5 h in argon atmosphere with a heating rate of 2.3°C/min.
The surface morphology was studied by scanning electron microscope (SEM) (JEOL JSM-5900; JEOL Ltd, Tokyo, Japan) and field-emission scanning electron microscope equipped with energy-dispersive X-ray (EDX) analysis tool (field emission scanning electron microscopy, FESEM; Hitachi S-7400, Japan). Information about the phase and crystallinity was obtained by using Rigaku x-ray diffractometer (XRD; Rigaku Corporation, Tokyo, Japan) with Cu Kα (λ = 1.540 Å) radiation over Bragg angle ranging from 10° to 90°. High-resolution image and selected area electron diffraction patterns were obtained with transmission electron microscope (TEM) (JEOL JEM-2010, JEOL Ltd, Tokyo, Japan) operated at 200 kV equipped with EDX analysis. The Raman spectra were measured using Nanofinder 30 spectrometer (Tokyo Inst. Co., Machida-shi, Tokyo, Japan) equipped with a He/Ne (λ = 633 nm laser) and the scattering peaks were calibrated with a reference peak from a Si wafer (520 cm-1). Raman spectra were recorded under a microscope with a × 40 objective in range of 0–1,600 cm-1 and 3 mW of power at the sample. The electrochemical measurements were performed in a 1 M KOH solution at room temperature. The measurements were performed on a VersaSTAT 4 (USA) electrochemical analyzer and a conventional three-electrode electrochemical cell. A Pt wire and an Ag/AgCl electrode were used as the auxiliary and reference electrodes, respectively. Glassy carbon electrode was used as working electrode. Preparation of the working electrode was carried out by mixing 2 mg of the functional material, 20 μL of Nafion solution (5 wt.%) and 400 μL of isopropanol. The slurry was sonicated for 30 min at room temperature. An amount of 15 μL from the prepared slurry was poured on the active area of the glassy carbon electrode which was then subjected to drying process at 80°C for 20 min. All potentials were quoted with regard to the Ag/AgCl electrode. High-purity nitrogen gas was used before and during measurements to deaerate the electrolyte in all measurements. Normalization of the current density was achieved based on the surface area of the utilized glassy carbon electrode (0.07 cm2).
Results and discussion
Additionally, a broad peak at 2θ of 26.3° corresponding to an experimental d spacing of 3.37 Å which indicates the presence of graphite-like carbon (d (002), JCPDS card no 41–1487) can be observed in the figure.
Increasing the number of potential sweeps results in a progressive increase of the current density values of the cathodic peak because of the entry of OH– into the Cu(OH)2 surface layer, which leads to the progressive formation of a thicker CuOOH layer corresponding to the Cu(OH)2/CuOOH transition . On the other hand, it can be concluded from Figure 6 that Co has no surface activation which explains the known low electrocatalytic activity of this metal. It is noteworthy mentioning that high cobalt percentage was utilized in preparation of the introduced nanofibers to exploit the activity of Co in PVA graphitization to produce CNFs. Recently, supporting of the electrocatalysts on carbonaceous materials is carrying on to take the advantage of the adsorption capacity of the carbon and increase the active catalyst surface area [10, 47]. The bottom panel in Figure 6 displays the obtained results in case of utilizing the introduced nanofibers. As shown in the figure, the presence of carbon and the nanofibrous morphology strongly enhance the current density compared to the pristine cobalt and copper nanoparticles.
- 1.Adsorption of the methanol on the introduced catalyst (M) and partial release of the protons(10)
- 2.Further release of the protons(11)(12)
- 4.Later on, CO is oxidized by the OH group ; however, as aforementioned, CO oxidation on the surface of the introduced catalyst is not detected, so it is believed that reaction 13 does not occur. Instead, this reaction is taking place(14)
The electrospinning process can be efficiently utilized to produce carbon nanofibers decorated by metallic nanoparticles. Cobalt/copper-decorated carbon nanofibers can be produced by electrospinning of a sol–gel composed of cobalt acetate tetrahydrate, copper acetate monohydrate and poly(vinyl alcohol). Calcination of the electrospun mats in argon atmosphere produces Co/Cu-decorated CNFs. The produced decorated nanofibers can be utilized as electrocatalyst for methanol oxidation; the corresponding onset potential and current density are satisfactory. Moreover, good stability is expected because the metallic nanoparticles are sheathed inside the thin graphite layer. Overall, this study introduces new methodology to produce metal-decorated CNFs based on PVA. The proposed decorated nanofibers can be further modified to be more efficient non-precious electrocatalysts for fuel cell applications.
This research was supported by NPST program by King Saud University project number 11-ENE1721-02. We thank Mr. T. S. Bae and Mr. J. C. Lim from KBSI, Jeonju Branch and Mr. Jong-Gyun Kang from Centre for University Research Facility, for taking high-quality FESEM and TEM images, respectively.
- Guo YG, Hu JS, Wan LJ: Nanostructured materials for electrochemical energy conversion and storage devices. Adv Mater 2008, 20(15):2878–2887. 10.1002/adma.200800627View ArticleGoogle Scholar
- Tian ZQ, Jiang SP, Liang YM, Shen PK: Synthesis and characterization of platinum catalysts on multiwalled carbon nanotubes by intermittent microwave irradiation for fuel cell applications. J Phys Chem B 2006, 110(11):5343–5350. 10.1021/jp056401oView ArticleGoogle Scholar
- Shen J, Hu Y, Li C, Qin C, Ye M: Pt–Co supported on single-walled carbon nanotubes as an anode catalyst for direct methanol fuel cells. Electrochim Acta 2008, 53(24):7276–7280. 10.1016/j.electacta.2008.04.019View ArticleGoogle Scholar
- Shao Y, Sui J, Yin G, Gao Y: Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell. Appl Catal B 2008, 79(1):89–99. 10.1016/j.apcatb.2007.09.047View ArticleGoogle Scholar
- Ren X, Zelenay P, Thomas S, Davey J, Gottesfeld S: Recent advances in direct methanol fuel cells at Los Alamos National Laboratory. J Power Sources 2000, 86(1):111–116.View ArticleGoogle Scholar
- Liu Z, Ling XY, Su X, Lee JY: Carbon-supported Pt and PtRu nanoparticles as catalysts for a direct methanol fuel cell. J Phys Chem B 2004, 108(24):8234–8240. 10.1021/jp049422bView ArticleGoogle Scholar
- Mu Y, Liang H, Hu J, Jiang L, Wan L: Controllable Pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells. J Phys Chem B 2005, 109(47):22212–22216. 10.1021/jp0555448View ArticleGoogle Scholar
- Li W, Zhou W, Li H, Zhou Z, Zhou B, Sun G, Xin Q: Nano-stuctured Pt–Fe/C as cathode catalyst in direct methanol fuel cell. Electrochim Acta 2004, 49(7):1045–1055. 10.1016/j.electacta.2003.10.015View ArticleGoogle Scholar
- Yen CH, Shimizu K, Lin YY, Bailey F, Cheng IF, Wai CM: Chemical fluid deposition of Pt-based bimetallic nanoparticles on multiwalled carbon nanotubes for direct methanol fuel cell application. Energy & fuels 2007, 21(4):2268–2271. 10.1021/ef0606409View ArticleGoogle Scholar
- Frackowiak E, Lota G, Cacciaguerra T, Béguin F: Carbon nanotubes with Pt–Ru catalyst for methanol fuel cell. Electrochem Commun 2006, 8(1):129–132. 10.1016/j.elecom.2005.10.015View ArticleGoogle Scholar
- Paulus U, Wokaun A, Scherer G, Schmidt T, Stamenkovic V, Radmilovic V, Markovic N, Ross P: Oxygen reduction on carbon-supported Pt-Ni and Pt-Co alloy catalysts. J Phys Chem B 2002, 106(16):4181–4191.View ArticleGoogle Scholar
- Papavasiliou J, Avgouropoulos G, Ioannides T: CuMnOx catalysts for internal reforming methanol fuel cells: application aspects. Int J Hydrogen Energy 2012, 37(21):16739–16747. 10.1016/j.ijhydene.2012.02.124View ArticleGoogle Scholar
- Gorte RJ, Park S, Vohs JM, Wang C: Anodes for direct oxidation of dry hydrocarbons in a solid‒oxide fuel cell. Adv Mater 2000, 12(19):1465–1469. 10.1002/1521-4095(200010)12:19<1465::AID-ADMA1465>3.0.CO;2-9View ArticleGoogle Scholar
- Hampson N, Willars M, McNicol B: The methanol-air fuel cell: a selective review of methanol oxidation mechanisms at platinum electrodes in acid electrolytes. J Power Sources 1979, 4(3):191–201. 10.1016/0378-7753(79)85010-7View ArticleGoogle Scholar
- Gasteiger HA, Markovic N, Ross PN Jr, Cairns EJ: Methanol electrooxidation on well-characterized platinum-ruthenium bulk alloys. J Phys Chem 1993, 97(46):12020–12029. 10.1021/j100148a030View ArticleGoogle Scholar
- Wang C, Waje M, Wang X, Tang JM, Haddon RC, Yan Y: Proton exchange membrane fuel cells with carbon nanotube based electrodes. Nano Lett 2004, 4(2):345–348. 10.1021/nl034952pView ArticleGoogle Scholar
- Li W, Liang C, Qiu J, Zhou W, Han H, Wei Z, Sun G, Xin Q: Carbon nanotubes as support for cathode catalyst of a direct methanol fuel cell. Carbon 2002, 40(5):787–790. 10.1016/S0008-6223(01)00136-1View ArticleGoogle Scholar
- Li W, Liang C, Zhou W, Qiu J, Zhou Z, Sun G, Xin Q: Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells. J Phys Chem B 2003, 107(26):6292–6299. 10.1021/jp022505cView ArticleGoogle Scholar
- Steigerwalt ES, Deluga GA, Cliffel DE, Lukehart C: A Pt-Ru/graphitic carbon nanofiber nanocomposite exhibiting high relative performance as a direct-methanol fuel cell anode catalyst. J Phys Chem B 2001, 105(34):8097–8101. 10.1021/jp011633iView ArticleGoogle Scholar
- Lu Y, Reddy RG: Electrocatalytic properties of carbon supported cobalt phthalocyanine–platinum for methanol electro-oxidation. Int J Hydrogen Energy 2008, 33(14):3930–3937. 10.1016/j.ijhydene.2007.12.031View ArticleGoogle Scholar
- S-i M, Johnson DC: Electrocatalytic response of carbohydrates at copper-alloy electrodes. J Electroanal Chem 2001, 500(1):524–532.Google Scholar
- Barakat NA, Khalil KA, Kim HY: Toward facile synthesizing of diamond nanostructures via nanotechnological approach: Lonsdaleite carbon nanofibers by electrospinning. Mater Res Bull 2012, 47(9):2140–2147. 10.1016/j.materresbull.2012.06.012View ArticleGoogle Scholar
- Barakat NAM, Abadir MF, Shaheer Akhtar M, El-Newehy M, Y-s S, Yong Kim H: Synthesis and characterization of Pd-doped Co nanofibers as a multifunctional nanostructure. Mater Lett 2012, 85: 120–123. doi:10.1016/j.matlet.2012.06.099 doi:10.1016/j.matlet.2012.06.099View ArticleGoogle Scholar
- Sheikh FA, Macossay J, Kanjwal MA, Abdal-hay A, Tantry MA, Kim H: Titanium dioxide nanofibers and microparticles containing nickel nanoparticles. ISRN Nanomaterials 2012, 2012(1):1–8.View ArticleGoogle Scholar
- Barakat NA, Kanjawal MA, Chronakis IS, Kim HY: Influence of temperature on the photodegrdation process using Ag-doped TiO2 nanostructures: negative impact with the nanofibers. J Mol Catal A Chem 2012, 336(1):333–340.Google Scholar
- Barakat NA, Abdelkareem MA, El-Newehy M, Kim HY: Influence of the nanofibrous morphology on the catalytic activity of NiO nanostructures: an effective impact toward methanol electrooxidation. Nanoscale Res Lett 2013, 8(1):1–6. 10.1186/1556-276X-8-1View ArticleGoogle Scholar
- Inagaki M, Yang Y, Kang F: Carbon nanofibers prepared via electrospinning. Adv Mater 2012, 24(19):2547–2566. doi:10.1002/adma.201104940 doi:10.1002/adma.201104940 10.1002/adma.201104940View ArticleGoogle Scholar
- Yousef A, Barakat NM, Amna T, Abdelkareem M, Unnithan A, Al-Deyab S, Kim H: Activated carbon/silver-doped polyurethane electrospun nanofibers: single mat for different pollutants treatment. Macromol Res 2012, 20(12):1243–1248. 10.1007/s13233-012-0183-2View ArticleGoogle Scholar
- Barakat NAM, Shaheer Akhtar M, Yousef A, El-Newehy M, Kim HY: Pd-Co-doped carbon nanofibers with photoactivity as effective counter electrodes for DSSCs. Chem Eng J 2012, 211–212(1):9–15. doi:10.1016/j.cej.2012.09.040 doi:10.1016/j.cej.2012.09.040View ArticleGoogle Scholar
- Tao X, Zhang X, Zhang L, Cheng J, Liu F, Luo J, Luo Z, Geise HJ: Synthesis of multi-branched porous carbon nanofibers and their application in electrochemical double-layer capacitors. Carbon 2006, 44(8):1425–1428. 10.1016/j.carbon.2005.11.024View ArticleGoogle Scholar
- Liu T, Gu S, Zhang Y, Ren J: Fabrication and characterization of carbon nanofibers with a multiple tubular porous structure via electrospinning. J Polym Res 2012, 19(6):1–6.View ArticleGoogle Scholar
- Tsuji M, Kubokawa M, Yano R, Miyamae N, Tsuji T, Jun MS, Hong S, Lim S, Yoon SH, Mochida I: Fast preparation of PtRu catalysts supported on carbon nanofibers by the microwave-polyol method and their application to fuel cells. Langmuir 2007, 23(2):387–390. 10.1021/la062223uView ArticleGoogle Scholar
- Fatema UK, Jalal Uddin A, Uemura K, Gotoh Y: Fabrication of carbon fibers from electrospun poly(vinyl alcohol) nanofibers. Text Res J 2011, 81: 13.Google Scholar
- Bin Y, Chen Q, Nakamura Y, Tsuda K, Matsuo M: Preparation and characterization of carbon films prepared from poly (vinyl alcohol) containing metal oxide and nano fibers with iodine pretreatment. Carbon 2007, 45(6):1330–1339. 10.1016/j.carbon.2007.01.007View ArticleGoogle Scholar
- Zhang S-J, Yu H-Q, Feng H-M: PVA-based activated carbon fibers with lotus root-like axially porous structure. Carbon 2006, 44(10):2059–2068. 10.1016/j.carbon.2005.12.047View ArticleGoogle Scholar
- Fatema UK, Uddin AJ, Uemura K, Gotoh Y: Fabrication of carbon fibers from electrospun poly (vinyl alcohol) nanofibers. Text Res J 2011, 81(7):659–672. 10.1177/0040517510385175View ArticleGoogle Scholar
- Barakat NAM, Kim B, Park SJ, Jo Y, Jung M-H, Kim HY: Cobalt nanofibers encapsulated in a graphite shell by an electrospinning process. J Mater Chem 2009, 19(39):7371–7378. 10.1039/b904669kView ArticleGoogle Scholar
- Barakat NAM, Hamza A, Al-Deyab SS, Qurashi A, Kim HY: Titanium-based polymeric electrospun nanofiber mats as a novel organic semiconductor. Mater Sci Eng B 2011, 177(1):34–42.View ArticleGoogle Scholar
- Yousef A, Barakat NAM, Amna T, Unnithan AR, Al-Deyab SS, Yong Kim H: Influence of CdO-doping on the photoluminescence properties of ZnO nanofibers: effective visible light photocatalyst for waste water treatment. J Lumin 2012, 132(7):1668–1677. doi:10.1016/j.jlumin.2012.02.031 doi:10.1016/j.jlumin.2012.02.031 10.1016/j.jlumin.2012.02.031View ArticleGoogle Scholar
- Gubin SP, Spichkin YI, Koksharov YA, Yurkov GY, Kozinkin AV, Nedoseikina TI, Korobov MS, Tishin AM: Magnetic and structural properties of Co nanoparticles in a polymeric matrix. J Magn Magn Mater 2003, 265(2):234–242. doi: http://dx.doi.org/10.1016/S0304–8853(03)00271–3 doi: 10.1016/S0304-8853(03)00271-3View ArticleGoogle Scholar
- Barakat NAM, Abadir MF, Nam KT, Hamza AM, Al-Deyab SS, W-i B, Kim HY: Synthesis and film formation of iron-cobalt nanofibers encapsulated in graphite shell: magnetic, electric and optical properties study. J Mater Chem 2011, 21(29):10957–10964. 10.1039/c1jm00052gView ArticleGoogle Scholar
- Wanjun T, Donghua C: Mechanism of thermal decomposition of cobalt acetate tetrahydrate. Chem Pap 2007, 61(4):329–332. doi:10.2478/s11696–007–0042–3 doi:10.2478/s11696-007-0042-3 10.2478/s11696-007-0042-3View ArticleGoogle Scholar
- Afzal M, Butt P, Ahmad H: Kinetics of thermal decomposition of metal acetates. J Therm Anal Calorim 1991, 37(5):1015–1023. 10.1007/BF01932799View ArticleGoogle Scholar
- Flahaut E, Agnoli F, Sloan J, O’Connor C, Green M: CCVD synthesis and characterization of cobalt-encapsulated nanoparticles. Chem Mater 2002, 14(6):2553–2558. 10.1021/cm011287hView ArticleGoogle Scholar
- Fantini C, Jorio A, Souza M, Strano M, Dresselhaus M, Pimenta M: Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects. Phys Rev Lett 2004, 93(14):147406.View ArticleGoogle Scholar
- Rahim A, Abdel Hameed R, Khalil M: Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium. J Power Sources 2004, 134(2):160–169. 10.1016/j.jpowsour.2004.02.034View ArticleGoogle Scholar
- Guo J, Sun G, Wang Q, Wang G, Zhou Z, Tang S, Jiang L, Zhou B, Xin Q: Carbon nanofibers supported Pt–Ru electrocatalysts for direct methanol fuel cells. Carbon 2006, 44(1):152–157. 10.1016/j.carbon.2005.06.047View ArticleGoogle Scholar
- Danaee I, Jafarian M, Mirzapoor A, Gobal F, Mahjani M: Electrooxidation of methanol on NiMn alloy modified graphite electrode. Electrochim Acta 2010, 55(6):2093–2100. 10.1016/j.electacta.2009.11.039View ArticleGoogle Scholar
- Barakat NA, Abdelkareem MA, Yousef A, Al-Deyab SS, El-Newehy M, Kim HY: Cadmium-doped cobalt/carbon nanoparticles as novel nonprecious electrocatalyst for methanol oxidation. Int J Hydrogen Energy 2013, 38(1):183–195.Google Scholar
- Hamnett A: Mechanism and electrocatalysis in the direct methanol fuel cell. Catal Today 1997, 38(4):445–457. 10.1016/S0920-5861(97)00054-0View ArticleGoogle Scholar
- Campbell C, Ertl G, Kuipers H, Segner J: A molecular beam study of the adsorption and desorption of oxygen from a Pt (111) surface. Surf Sci 1981, 107(1):220–236. 10.1016/0039-6028(81)90622-1View ArticleGoogle Scholar
- Khan A, Ahmed R, Mirza ML: Evaluation of catalytic activity of Pt and Pt-Ru catalysts for electro-oxidation of methanol in acid medium by cyclic voltammetry. Port Electrochim Acta 2009, 27(4):429–441. 10.4152/pea.200904429View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.