The Thermal Kinetics of Methanol Oxidation on Pt/MWCNT Electrocatalysts in Alkaline Media
Haitao zheng （ Energy Centre, Council for Scientific and Industrial Research (CSIR), POBOX 395, Pretoria 0001, South Africa. ）
Mmalewane Modibedi （ Energy Centre, Council for Scientific and Industrial Research (CSIR), POBOX 395, Pretoria 0001, South Africa. ）
https://doi.org/10.37155/2717-526X-0501-7Abstract
In this study, the thermal electrooxidation of methanol on a Pt/MWCNT catalyst was examined in alkaline media across the temperature range of 298-363 K. The investigation utilized cyclic voltammetry (CV), quasi-state polarization, and electrochemical impedance spectroscopy (EIS) methods to explore the kinetics of the methanol electrooxidation reaction (MEOR). At elevated temperatures, the kinetics of methanol electro-oxidation on the Pt/MWCNT catalyst within an alkaline solution (1.0 mol/L KOH) were notably accelerated compared to room temperature. This acceleration can be attributed to the reduced methanol dehydrogenation reaction at relatively low temperatures. The Tafel slopes experienced changes as the temperature increased. These variations in Tafel slopes are likely linked to alterations in the rate-determining step of the MEOR as a function of temperature. The EIS outcomes revealed a decrease in charge-transfer resistance as temperature increased. This phenomenon is associated with the interplay between interfacial and diffusion impedances, as well as the surface roughness of the highly dispersed electrode surface.
Keywords
Electro-oxidation of methanol; Pd/MWCNT; Catalyst; Alkaline media; TemperatureFull Text
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[2] Gong L, Yang Z, Li K, et al. Recent development of methanol electrooxidation catalysts for direct methanol fuel cell. Journal of Energy Chemistry, 2018;27(6):1618-1628. https://doi.org/10.1016/j.jechem.2018.01.029
[3] Wang Y, Zou S and Cai WB. Recent advances on electro-oxidation of ethanol on Pt-and Pd-based catalysts: from reaction mechanisms to catalytic materials. Catalysts, 2015;5(3):1507-1534. https://doi.org/10.3390/catal5031507
[4] Zhao X, Liu Q, Li Q, et al. Two-dimensional electrocatalysts for alcohol oxidation: a critical review. Chemical Engineering Journal, 2020;400:125744. https://doi.org/10.1016/j.cej.2020.125744
[5] Chen W, Xue J, Bao Y, et al. Surface engineering of nano-ceria facet dependent coupling effect on Pt nanocrystals for electro-catalysis of methanol oxidation reaction. Chemical Engineering Journal, 2020;381:122752. https://doi.org/10.1016/j.cej.2019.122752
[6] Zhang K, Wang H, Qiu J, et al. Multi-dimensional Pt/Ni(OH)2/nitrogen-doped graphene nanocomposites with low platinum content for methanol oxidation reaction with highly catalytic performance. Chemical Engineering Journal, 2021;421:127786. https://doi.org/10.1016/j.cej.2020.127786
[7] Silva JCM, de Freitas IC, Neto AO, et al. Palladium nanoparticles supported on phosphorus-doped carbon for ethanol electro-oxidation in alkaline media. Ionics, 2018;24:1111-1119. https://doi.org/10.1007/s11581-017-2257-9
[8] Ning L, Liu X, Deng M, et al. Palladium-based nanocatalysts anchored on CNT with high activity and durability for ethanol electro-oxidation. Electrochimica Acta, 2019;297:206-214. https://doi.org/10.1016/j.electacta.2018.11.188
[9] Wang J, Sun H, Shah SA, et al. Palladium nanoparticles supported by three-dimensional freestanding electrodes for high-performance methanol electro-oxidation. International Journal of Hydrogen Energy, 2020;45(19):11089-11096. https://doi.org/10.1016/j.ijhydene.2020.02.046
[10] Tripković AV, Popović K D, Grgur BN, et al. Methanol electrooxidation on supported Pt and PtRu catalysts in acid and alkaline solutions. Electrochimica Acta, 2002;47(22-23):3707-3714. https://doi.org/10.1016/S0013-4686(02)00340-7
[11] Jayabal S, Saranya G, Geng D, et al. Insight into the correlation of Pt-support interactions with electrocatalytic activity and durability in fuel cells. Journal of Materials Chemistry A, 2020;8(19):9420-9446. https://doi.org/10.1039/D0TA01530J
[12] Zagoraiou E, Daletou MK, Sygellou L, et al. Highly dispersed platinum supported catalysts-effect of properties on the electrocatalytic activity. Applied Catalysis B: Environmental, 2019;259:118050. https://doi.org/10.1016/j.apcatb.2019.118050
[13] Yaqoob AA, Umar K and Ibrahim MNM. Silver nanoparticles: various methods of synthesis, size affecting factors and their potential applications-a review. Applied Nanoscience, 2020;10:1369-1378. https://doi.org/10.1007/s13204-020-01318-w
[14] Ortiz-Herrera JC, Cruz-Martínez H, Solorza-Feria O, et al. Recent progress in carbon nanotubes support materials for Pt-based cathode catalysts in PEM fuel cells. International Journal of Hydrogen Energy, 2022;47(70):30213-30224. https://doi.org/10.1016/j.ijhydene.2022.03.218
[15] Saha MS and Kundu A. Functionalizing carbon nanotubes for proton exchange membrane fuel cells electrode. Journal of Power Sources, 2010;195(19):6255-6261. https://doi.org/10.1016/j.jpowsour.2010.04.015
[16] Devrim Y and Arıca ED. Investigation of the effect of graphitized carbon nanotube catalyst support for high temperature PEM fuel cells. International Journal of Hydrogen Energy, 2020;45(5):3609-3617. https://doi.org/10.1016/j.ijhydene.2019.01.111
[17] Luo C, Xie H, Wang Q, et al. A review of the application and performance of carbon nanotubes in fuel cells. Journal of Nanomaterials, 2015;2015:4-4. https://doi.org/10.1155/2015/560392
[18] Hsieh CT, Gu J L, Tzou DY, et al. Microwave deposition of Pt catalysts on carbon nanotubes with different oxidation levels for formic acid oxidation. International Journal of Hydrogen Energy, 2013;38(25):10345-10353. https://doi.org/10.1016/j.ijhydene.2013.05.146
[19] Zhang W, Chen J, Swiegers GF, et al. Microwave-assisted synthesis of Pt/CNT nanocomposite electrocatalysts for PEM fuel cells. Nanoscale, 2010;2(2):282-286. https://doi.org/10.1039/B9NR00140A
[20] Xin Y, Liu J, Jie X, et al. Preparation and electrochemical characterization of nitrogen doped graphene by microwave as supporting materials for fuel cell catalysts. Electrochimica Acta, 2012;60:354-358. https://doi.org/10.1016/j.electacta.2011.11.062
[21] Bharti A, Cheruvally G and Muliankeezhu S. Microwave assisted, facile synthesis of Pt/CNT catalyst for proton exchange membrane fuel cell application. International Journal of Hydrogen Energy, 2017;42(16):11622-11631. https://doi.org/10.1016/j.ijhydene.2017.02.109
[22] Matseke MS, Munonde TS, Mallick K, et al. Pd/PANI/C nanocomposites as electrocatalysts for oxygen reduction reaction in alkaline media. Electrocatalysis, 2019;10:436-444. https://doi.org/10.1007/s12678-019-00536-3
[23] Gasteiger HA, Markovic N, Ross Jr PN, et al. Methanol electrooxidation on well-characterized platinum-ruthenium bulk alloys. The Journal of Physical Chemistry, 1993;97(46):12020-12029. https://doi.org/10.1021/j100148a030
[24] Li M, Wang Y, Cai J, et al. Surface sites assembled-strategy on Pt-Ru nanowires for accelerated methanol oxidation. Dalton Transactions, 2020;49(40):13999-14008. https://doi.org/10.1039/D0DT02567D
[25] Mekazni DS, Arán-Ais RM, Ferre-Vilaplana A, et al. Why methanol electro-oxidation on platinum in water takes place only in the presence of adsorbed OH. ACS Catalysis, 2022;12(3):1965-1970. https://doi.org/10.1021/acscatal.1c05122
[26] Díaz V, Ohanian M and Zinola CF. Kinetics of methanol electrooxidation on Pt/C and PtRu/C catalysts. International Journal of Hydrogen Energy, 2010;35(19):10539-10546. https://doi.org/10.1016/j.ijhydene.2010.07.135
[27] Zhang Y, Liu Y, Liu W, et al. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media. Applied Surface Science, 2017;407:64-71. https://doi.org/10.1016/j.apsusc.2017.02.158
[28] Jovanović VM, Terzić S, Tripković AV, et al. The effect of electrochemically treated glassy carbon on the activity of supported Pt catalyst in methanol oxidation. Electrochemistry Communications, 2004;6(12):1254-1258. https://doi.org/10.1016/j.elecom.2004.10.001
[29] Chen J, Wang M, Liu B, et al. Platinum catalysts prepared with functional carbon nanotube defects and its improved catalytic performance for methanol oxidation. The Journal of Physical Chemistry B, 2006;110(24):11775-11779. https://doi.org/10.1021/jp061045a
[30] Tripković AV, Popović KD, Lović JD, et al. Methanol oxidation at platinum electrodes in alkaline solution: comparison between supported catalysts and model systems. Journal of Electroanalytical Chemistry, 2004;572(1):119-128. https://doi.org/10.1016/j.jelechem.2004.06.007
[31] Kauranen PS, Skou E and Munk J. Kinetics of methanol oxidation on carbon-supported Pt and Pt+ Ru catalysts. Journal of Electroanalytical Chemistry, 1996;404(1):1-13. https://doi.org/10.1016/0022-0728(95)04298-9
[32] Iwasita T. Electrocatalysis of methanol oxidation. Electrochimica Acta, 2002;47(22-23):3663-3674. https://doi.org/10.1016/S0013-4686(02)00336-5
[33] Melnick RE and Palmore GTR. Impedance spectroscopy of the electro-oxidation of methanol on polished polycrystalline platinum. The Journal of Physical Chemistry B, 2001;105(5):1012-1025. https://doi.org/10.1021/jp0030847
[34] Cai GX, Guo JW, Wang J, et al. Negative resistance for methanol electro-oxidation on platinum/carbon (Pt/C) catalyst investigated by an electrochemical impedance spectroscopy. Journal of Power Sources, 2015;276:279-290. https://doi.org/10.1016/j.jpowsour.2014.11.131
[35] Jeon MK, Won JY, Oh KS, et al. Performance degradation study of a direct methanol fuel cell by electrochemical impedance spectroscopy. Electrochimica Acta, 2007;53(2):447-452. https://doi.org/10.1016/j.electacta.2007.06.063
[36] Wu G and Xu BQ. Carbon nanotube supported Pt electrodes for methanol oxidation: a comparison between multi-and single-walled carbon nanotubes. Journal of Power Sources, 2007;174(1):148-158. https://doi.org/10.1016/j.jpowsour.2007.08.024
[37] Mahapatra SS, Dutta A and Datta J. Temperature dependence on methanol oxidation and product formation on Pt and Pd modified Pt electrodes in alkaline medium. International Journal of Hydrogen Energy, 2011;36(22):14873-14883. https://doi.org/10.1016/j.ijhydene.2010.11.085
Copyright © 2023 Haitao zheng, Mmalewane Modibedi
Publishing time:2023-03-10
This work is licensed under a Creative Commons Attribution 4.0 International License
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