Direct oxidation of methane at low temperature using Pt/C, Pd/C, Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process
-
Abstract: The main objective of this paper was to characterize the voltammetric profiles of the Pt/C, Pt/C-ATO, Pd/C and Pd/C-ATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25℃ and in a direct methane proton exchange membrane fuel cell at 80℃. The electrocatalysts prepared also were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic (fcc) structure, and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic (fcc) structure. For Pt/C-ATO and Pd/C-ATO, characteristic peaks of cassiterite (SnO2) phase are observed, which are associated with Sb-doped SnO2 (ATO) used as supports for electrocatalysts. Cyclic voltammograms (CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However, this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism, where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed, which indicates the production of carbon dioxide. Polarization curves at 80℃ in a direct methane fuel cell (DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.
-
Figure 2 TEM images and histograms of the nanoparticles size distribution to Pt/C (a) and (b) Pt/C-ATO electrocatalysts
Figure 3 TEM images and histograms of the nanoparticles size distribution to Pd/C (a) and (b) Pd/C-ATO electrocatalysts
Figure 4 Comparison of the current-potential curves for (a) Pt/C, (b) Pt/C-ATO, (c) Pd/C and (d) Pd/C-ATO electrodes in the absence of methane and methane (CH4) passing through the 0.5 mol/L H2SO4 electrolyte for 30 min
Figure 5 In situ ATR-FTIR spectra and integrated bands in the range of 3250 to 850 cm-1 of electrochemical oxidation of methane on Pt/C and Pt/C-ATO electrocatalysts at potentials range from 0.05 to 1.2 V with an interval of 0.1 V
Figure 6 In situ ATR-FTIR spectra and integrated bands in the range of 3250 to 850 cm-1 of electrochemical oxidation of methane on Pd/C and Pd/C-ATO electrocatalysts at potentials range from 0.05 to 1.2 V with an interval of 0.1 V
-
[1] JACQUINATA P, MÜLLER B, WEHRLI B, HAUSER P C. Determination of methane and other small hydrocarbons with a platinum-Nafion electrode by stripping voltammetry[J]. Anal Chim Acta, 2001, 432(1):1-10. doi: 10.1016/S0003-2670(00)01359-3 [2] ZHANG Y, ZHANG L, SHUANG S, FENG F, QIAO J, GUO Y, CHOI Y, MARTIN M F, DONG C. Electro-oxidation of methane on roughened palladium electrode in acidic electrolytes at ambient temperatures[J]. Anal Lett, 2010, 43(6):1055-1065. doi: 10.1080/00032710903492508 [3] HAHN F, MELENDRES C A. Anodic oxidation of methane at noble metal electrodes:An 'in situ' surface enhanced infrared spectroelectrochemical study[J]. Electrochim Acta, 2001, 46(23):3525-3534. doi: 10.1016/S0013-4686(01)00649-1 [4] TYAGIA S, GANESH A, AGHALAYAM P. Direct methane proton exchange membrane fuel cell[J]. ECS Trans, 2008, 6(25):371-378. http://d.old.wanfangdata.com.cn/NSTLQK/NSTL_QKJJ0226020563/ [5] HWANG D Y, MEBEL A M. Activation of methane by neutral transition metal oxides (ScO, NiO, and PdO):A Theoretical Study[J]. J Phys Chem A, 2002, 106(50):12072-12083. doi: 10.1021/jp026414r [6] SCHRÖDER D, SCHWARZ H. FeO⊕ activates methane[J]. Angew Chem, Int Ed Eng, 1990, 29(12):1433-1434. doi: 10.1002/(ISSN)1521-3773 [7] SCHRÖDER D, SCHWARZ H. C-H and C-C bond activation by bare transition-metal oxide cations in the gas phase[J]. Angew Chem, Int Ed Eng, 1995, 34(18):1973-1995. doi: 10.1002/(ISSN)1521-3773 [8] CLEMMER D E, CHEN Y M, KAHN F A, ARMENTROUT P B. State-specific reactions of Fe+(a6D, a4F) with D2O and reactions of FeO+ with D2[J]. J Phys Chem, 1994, 98(26):6522-6529. doi: 10.1021/j100077a017 [9] SIEGBAHN P E M. Comparison of the C-H activation of methane by M(C5H5)(CO) for M=cobalt, rhodium, and iridium[J]. J Am Chem Soc, 1996, 118(6):1487-1496. doi: 10.1021/ja952338c [10] WITTBORN A M C, COSTAS M, BLOMBERG M R A, SIEGBAHN P E M. The C-H activation reaction of methane for all transition metal atoms from the three transition rows[J]. J Chem Phys, 1997, 107(11):4318-4328. doi: 10.1063/1.474772 [11] BERTHELOT S, GEHAIN E, HAHN F, LÉGER J M, SRINIVASAN S, LAMY C. Extended Abstracts, Electrochemical Society Meeting, Boston, 98-2, 1998, Abstract 1090. [12] BENSEBAA F, FARAH A A, WANG D, BOCK C, DU X, KUNG J, PAGE Y L. Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell[J]. J Phys Chem B, 2005, 109(32):15339-15344. doi: 10.1021/jp0519870 [13] SAVADOGO O, LEE K, OISHI K, MITSUSHIMA S, KAMIYA N, OTA K I. New palladium alloys catalyst for the oxygen reduction reaction in an acid medium[J]. Electrochem Commun, 2004, 6(2):105-109. doi: 10.1016/j.elecom.2003.10.020 [14] JOGLEKAR M, NGUYEN V, PYLYPENKO S, NGO C, LI Q, O'REILLY M E, GRAY T S, HUBBARD W A, GUNNOE T B, HERRING A M, TREWYN B G. Organometallic complexes anchored to conductive carbon for electrocatalytic oxidation of methane at low temperature[J]. J Am Chem Soc, 2016, 138(1):116-125. doi: 10.1021/jacs.5b06392 [15] NETO A O, BRANDALISE M, DIAS R R, AYOUB J M S, SILVA A C, PENTEADO J C, LINARDI M, SPINACÉ E V. The performance of Pt nanoparticles supported on Sb2O5·SnO2, on carbon and on physical mixtures of Sb2O5·SnO2 and carbon for ethanol electro-oxidation[J]. Int J Hydrogen Energy, 2010, 35(17):9177-9181. doi: 10.1016/j.ijhydene.2010.06.028 [16] LI Z, GAO J, XING X, WU S, SHUANG S, DONG C, PAAU M C, CHOI M M F. Synthesis and characterization of n-alkylamine-stabilized palladium nanoparticles for electrochemical oxidation of methane[J]. J Phys Chem C, 2010, 114(2):723-733. doi: 10.1021/jp907745v [17] AGARWAL N, FREAKLEY S J, MCVICKER R U, ALTHAHBAN S M, DIMITRATOS N, HE Q, MORGAN D J, JENKINS R L, WILLOCK D J, TAYLOR S H, KIELY=C J, HUTCHINGS G J. Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions[J]. Science, 2017, 358(6360):223-227. doi: 10.1126/science.aan6515 [18] DA SILVA S G, FONTES E H, ASSUMP O M H M T, LINARDI M, SPINACÉ E V, SILVA J C M, NETO A O. Fuel cell and electrochemical studies of the ethanol electro-oxidation in alkaline media using PtAuIr/C as anodes[J]. Ionics, 2017, 23(9):2367-2376. doi: 10.1007/s11581-017-2088-8 [19] MAYA-CORNEJO J, CARRERA-CERRITOS R, SEBASTÍAN D, LEDESMA-GARCÍA J, ARRIAGA L G, ARICÒ A S, BAGLIO V. PtCu catalyst for the electro-oxidation of ethanol in an alkaline direct alcohol fuel cell[J]. Int J Hydrogen Energy, 2017, 42(46):27919-27928. doi: 10.1016/j.ijhydene.2017.07.226 [20] GUO J, CHEN R, ZHU F C, SUN S G, VILLULLAS H M. New understandings of ethanol oxidation reaction mechanism on Pd/C and Pd2Ru/C catalysts in alkaline direct ethanol fuel cells[J]. Appl Catal B:Environ, 2018, 224(5):602-611. https://www.sciencedirect.com/science/article/pii/S0926337317310111 [21] OTTONI C A, DE SOUZA R R, DA SILVA S G, SPINACÉ E V, DE SOUZA R F B, NETO A O. Performance of Pd electrocatalyst supported on a physical mixture indium tin oxide-carbon for glycerol electro-oxidation in alkaline media[J]. Electroanalysis, 2017, 29(4):960-964. doi: 10.1002/elan.v29.4 [22] SHIMANOUCHI T. National Bureau of Standards. 1972, 1-160. [23] HAHN F, MELENDRES C A. Anodic oxidation of methane at noble metal electrodes:An 'in situ' surface enhanced infrared spectroelectrochemical study[J]. Electrochimica Acta, 2001, 46(23):3525-3534. doi: 10.1016/S0013-4686(01)00649-1 [24] MILLIGAN D E, JACOX M E. Matrix-isolation study of the infrared and ultraviolet spectra of the free radical HCO. The hydrocarbon flame bands.[J]. J Chem Phys, 1969, 51(1):277-288. doi: 10.1063/1.1671720 [25] COOL T A, SONG X M. Resonance ionization spectroscopy of HCO and DCO. Ⅱ. The B2A' state[J]. J Chem Phys, 96(12): 8675-8683. -
下载:
点击查看大图
图(8)
计量
- 文章访问数: 120
- HTML全文浏览量: 30
- PDF下载量: 15
- 被引次数: 0
