Enhanced Methanol Fuel Cell Performance Using Copper-doped Carbon-supported Platinum Catalysts

Abstract

Platinum is a crucial anode catalyst in methanol oxidation reactions (MOR) due to its exceptional electrochemical performance, which has led to its widespread application. However, to enhance its catalytic activity and stability, platinum is typically supported on carrier materials, such as carbon-based substrates. Current commercial platinum-carbon catalysts exhibit limited activity, low utilization efficiency of metallic platinum, and a tendency to bind with intermediate species, leading to a decline in catalytic performance. To address these challenges, this study proposes the utilization of copper-doped carbon for the development of a composite support (Cu₂C₇). Compared with the pure carbon supported platinum catalyst (Pt@Cu₀C₇), the electrochemical activity of Cu₂C₇ supported platinum catalyst (Pt@Cu₂C₇) was significantly enhanced, as evidenced by a current density of 412 mA/cm² and an onset potential of −0.8 V. In chronoamperometry experiments, after 2 h of electrochemical testing, the activity of Pt@Cu₂C₇ decreased by only 4.24%, whereas Pt@Cu₀C₇ experienced a significant reduction of 55% in activity. The incorporation of copper is hypothesized to provide additional active sites for the deposition of metallic platinum on the carrier, thereby enhancing the platinum loading capacity. According to inductively coupled plasma (ICP) analysis, when the copper-to-carbon ratio is 2:7, the platinum loading amount increases by 25.78%. Furthermore, some platinum forms an alloy with the copper embedded in the carbon, a phenomenon corroborated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The literature suggests that the formation of such alloys can significantly improve the catalyst’s resistance to poisoning. The incorporation of copper not only enhances the platinum loading capacity but may also induce a synergistic effect among the active platinum components, thereby further improving catalytic performance. In summary, the findings of this study offer critical theoretical insights and practical guidelines for the design of high-performance MOR electrocatalysts, laying a robust foundation for future advancements in catalyst development.

Keywords

Fuel cell / Carbon material / Doped metal / Pt-Cu alloy / Methanol oxidation / Engineering / Materials Engineering / Chemical Sciences / Physical Chemistry (incl. Structural)

References

[1] de SáM H, MoreiraC S, PintoA M F R, OliveiraV BEnergies, 2022, 15: 17

[2] MansorM, TimmiatiS N, LimK L, WongW Y, KamarudinS K, KamarudinN H NInternational Journal of Hydrogen Energy, 2019, 44: 14744.

[3] ChenF, SunY X, LiH Y, LiC JEnergy Technology, 2022, 10: 6

[4] ZhuH, LuoM C, WangF H, WangZ M, HanK FAbstracts of Papers of the American Chemical Society, 2014, 247: 146

[5] DuanS B, DuZ, FanH S, WangR MNanomaterials, 2018, 8: 11.

[6] WuZ P, HopkinzE, ParkK, YanS, WangJ, WenJ G, LuoJ, WangL C, ZhongC JAbstracts of Papers of the American Chemical Society, 2018256

[7] JoglekarM, GrayT S, GunnoeT B, TrewynB GAbstracts of Papers of the American Chemical Society, 2014, 247: 909

[8] ShiX Y, ChenS SChempluschem, 2023, 88: 5.

[9] HanF, LuA H, LiW CProgress in Chemistry, 2012, 24: 2443

[10] ZhuY Y, WangY H, WangY T, XuT J, ChangPCarbon Energy, 2022, 4: 1182.

[11] TolbinA Y, SpitsynB V, SerdanA A, AverinA A, MalakhoA P, KepmanA V, SorokinaN E, AvdeevV VInorganic Materials, 201349

[12] FanQ Y, ZhaoY B, YuX H, SongY X, ZhangW, YunS NDiamond and Related Materials, 2020106

[13] WangH L, GaoQ MChem. J. Chinese Universities, 2011, 32: 462

[14] BorchardtL, OschatzM, KaskelSMaterials Horizons, 2014, 1: 157.

[15] LiD G, GongY L, LiG, LyuX, DaiZ Q, WangQNew Journal of Chemistry, 2021, 45: 13088.

[16] ShihK Y, WeiJ J, TsaiM CNanomaterials, 2021, 11: 9.

[17] ChenY J, JiS F, ChenC, PengQ, WangD S, LiY DJoule, 2018, 2: 1242.

[18] ChangY N, YangJ Y, ZhangM, YueM, WangW, LiJ W, WangJ D, SongK F, LiuY, ZuoY X, XingRJournal of Alloys and Compounds, 20241005

[19] LiangC X, WangM, LiuW, LiuH Y, HuangD W, ZhangY Z, ZhangK H, JiangL S, JiaY Y, NiuC GChemical Engineering Journal, 2023466

[20] ChenW M, LuoM, YangK, ZhangD T, ZhouX YJournal of Cleaner Production, 2021282

[21] GuyF, RunttiH, DuclauxL, OndartsM, ReinertL, OutinJ, GonzeE, BonnamyS, SonedaYMicroporous and Mesoporous Materials, 2021322

[22] JosephS R, SebastianL, MythiliUBiomass Conversion and Biorefinery, 2023, 10: 1007

[23] Palomero-GallagherN, BidmonH J, CremerM, SchleicherA, KircheisG, ReifenbergerG, KostopoulosG, HäussingerD, ZillesKCellular Physiology and Biochemistry, 2009, 24: 291.

[24] PavletsA S, AlekseenkoA A, NikolskiyA V, KozakovA T, SafronenkoO I, PankovI V, GutermanV EInternational Journal of Hydrogen Energy, 2022, 47: 30460.

[25] LinR H, FangL, LiX P, ZhangS FPolymer-Plastics Technology and Engineering, 2006, 45: 1243.

[26] RenQ G, XueY H, CuiZ J, LuY H, LiW M, ZhangW J, YeTDiamond and Related Materials, 2022, 125: 25.

[27] WeiJ J, GeL, WangW L, HongP D, LiY L, LiY H, XieC, WuZ J, HeJ Y, KongL TJournal of Environmental Chemical Engineering, 2024, 12: 2

[28] ShimboriYY, ShiroishiH, OnoR, KosakaS, SaitoM, YoshidaT, KatagiriH, MiyazawaK, TanakaYMaterials Science and Engineering B: Advanced Functional Solid-State Materials, 2018, 228: 190.

[29] ZhouP, ErningJ W, OgleKElectrochimica Acta, 2019, 293: 290.

[30] WeiZ, ZhaoH X, NiuY B, ZhangS Y, WuY B, YanH J, XinS, YinY X, GuoY GMaterials Chemistry Frontiers, 2021, 5: 3911.

[31] YiL H, LiuL, LiuX, WangX Y, YiW, HeP Y, WangX YInternational Journal of Hydrogen Energy, 2012, 37: 12650.

[32] BelenovS V, GutermanV E, TabachkovaN Y, MoguchikhE A, AlekseenkoA ARussian Journal of Electrochemistry, 2018, 54: 1209.

[33] LiuD, CuiW, YaoM G, LiQ J, CuiT, LiuB B, LiuD P, SundqvistBOptical Materials, 2013, 36: 449.

[34] YoshioM, NakamuraH, WangH YElectrochemical and Solid State Letters, 2006, 9: 12.

[35] SankarS, AhmedA T A, InamdarA I, ImH, ImY, Bin, LeeY, KimD Y, LeeSMaterials & Design, 2019, 169: 107688.

[36] WuMM X, WuX, ZhangL, AbdelhafizA, ChangI, QuC, JiangY C, ZengJ H, AlamgirFElectrochimica Acta, 2019, 306: 167.

[37] TateG L, MehrabadiB A T, XiongW, KenvinA, MonnierJ RNanomaterials, 2021, 11: 793.

[38] MintsouliI, GeorgievaJ, ArmyanovS, ValovaE, AvdeevG, HubinA, SteenhautO, DilleJ, TsiplakidesD, BalomenouS, SotiropoulosSApplied Catalysis B: Environmental, 2013, 136: 160.

[39] BiesingerM CSurface and Interface Analysis, 2017, 49: 1325.

[40] WangC, KuaiL, CaoW, SinghH, ZakharovA, NiuY R, SunH X, GengB YChemical Engineering Journal, 2021426

[41] DoukA S, SaravaniHAmerican Chemical Society, 2023, 8: 45245

[42] OezaslanM, HascheF, StrasserPJournal of The Electrochemical Society, 2012, 159: 4

[43] ShenS, XuS, ZhaoSACS Sustainable Chemistry and Engineering, 2022, 10: 2

[44] YouH, ZhangF, LiuZACS Catalysis, 2014, 4: 9.

[45] MoulijnJ A, Van DiepenA E, KapteijnFApplied Catalysis A: General, 2001, 212: 1.

[46] NassrA B A A, SinevI, GrünertWApplied Catalysis B: Environmental, 2013, 142: 849.

RIGHTS & PERMISSIONS

Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH