Methanol oxidation in acidic and alkaline electrolytes using PtRuIn/C electrocatalysts prepared by borohydride reduction process
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Abstract: PtRuIn/C electrocatalysts (20% metal loading by weight) were prepared by sodium borohydride reduction process using H2PtCl6·6H2O, RuCl3·xH2O and InCl3·xH2O as metal sources, borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis (EDX), transmission electron microscopy(TEM), cyclic voltammetry (CV), chronoamperommetry (CA) and polarization curves in alkaline and acidic electrolytes (single cell experiments). The XRD patterns show Pt peaks are attributed to the face-centered cubic (fcc) structure, and a shift of Pt (fcc) peaks indicates that Ru or In is incorporated into Pt lattice. TEM micrographs show metal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature, by CV and CA. PtRu/C (50:50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80℃ show PtRuIn/C (50:25:25) with superior performance for methanol oxidation, when compared to Pt/C, PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C (50:25:25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Pt alloy.
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Key words:
- borohydride reduction process /
- PtRuIn/C electrocatalysts /
- methanol oxidation /
- acidic and alkaline electrolytes /
- polarization curves
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Figure 1 Typical SEM images of the PtRuIn/C electrocatalysts prepared by borohydride reduction process and their typical EDX spectra
Figure 2 X-ray diffractograms of the Pt/C, PtIn/C, PtRu/C and PtRuIn/C electrocatalysts prepared by borohydride reduction process
Figure 3 TEM images and histograms of the particle size distribution to Pt/C, PtRu/C (50:50), PtIn/C (50:50) and PtRuIn/C (50:40:10) electrocatalysts
Figure 4 TEM images and histograms of the particle size distribution of PtRuIn/C (50:10:40), PtRuIn/C (50:25:25), PtRuIn/C (70:20:10) and PtRuIn/C (90:5:5) electrocatalysts
Figure 5 Cyclic voltammograms of Pt/C, PtRu/C (50:50), PtIn/C (50:50) and PtRuIn/C electrocatalysts in (a) 0.5 mol/L H2SO4 and (b)1 mol/L KOH solution with a scan rate of 10 mV/s at 25 ℃
Figure 6 Cyclic voltammograms of Pt/C, PtRu/C (50:50), PtIn/C (50:50) and PtRuIn/C with different atomic ratios electrocatalysts in the presence of (a)0.5 mol/L H2SO4 + 1 mol/L methanol solution or (b)1 mol/L KOH + 1 mol/L methanol with a scan rate of 10 mV/s at 25 ℃
Figure 7 Chronoamperometry curves in the presence of 0.5 mol/L H2SO4 + 1.0 mol/L methanol at 0.5 V in 30 min (a) or 1 mol/L KOH + 1 mol/L methanol at -0.35 V in 30 min(b)for Pt/C, PtRu/C (50:50), PtIn/C (50:50) and PtRuIn/C electrocatalysts at 25 ℃
Figure 8 Polarization curves (a) and power density curves (b) in a 5 cm2 DMFC at 80 ℃ using Pt/C, PtRu/C, PtIn/C and PtRuIn/C electrocatalysts as anode catalysts (1 mg (Pt) /cm2) and Pt/C BASF as the cathode catalyst (1 mg (Pt) /cm2), Nafion 117 was used as the membrane. Methanol 2 mol/L with 1.0 mL/min flux and oxygen pressure (0.2 MPa). (c)I-V polarization curves and the (d) power density curves at 80 ℃ of a 5 cm2 DAMFC using Pt/C, PtRu/C, PtIn/C and PRuIn/C electrocatalysts anodes (1 mg (Pt) /cm2 catalyst loading) and Pt/C BASF electrocatalyst cathode (1 mg (Pt) /cm2 catalyst loading with 20% Pt loading on carbon), Nafion 117 membrane treated with KOH, 1.0 mol/L KOH + 1.0 mol/L methanol was used as fuel
■：Pt/C; ●：PtRu/C(50:50); ▲：PtIn/C(50:50); ▼：PtRuIn/C(50:10:40); ◀：PtRuIn/C(50:25:25); ▶：PtRuIn/C(50:40:10); ◆：PtRuIn/C(70:20:10); PtRuIn/C(90:5:5)
Table 1 Pt:Ru, Pt:In and Pt:Ru:In atomic ratios of the prepared electrocatalysts
Eletrocatalyst EDX results (molar ratio) Pt/C PtRu/C (50:50) 62:38 PtIn/C (50:50) 58:42 PtRuIn/C (50:40:10) 63:31:06 PtRuIn/C (50:10:40) 71:13:16 PtRuIn/C (50:25:25) 61:23:16 PtRuIn/C (70:20:10) 80:16:04 PtRuIn/C (90:5:5) 93:5:2 
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Table 2 The average crystallite size and lattice parameter values for Pt/C, PtRu/C, PtIn/C and PtRuIn/C prepared with different atomic ratios
Material Average crystallite size d/nm Lattice parameter values /nm Pt/C 5 0.392 PtRu/C (50:50) 6 0.388 PtIn/C (50:50) 3 0.398 PtRuIn/C (50:10:40) 3 0.396 PtRuIn/C (50:25:25) 2 0.397 PtRuIn/C (50:40:10) 3 0.390 PtRuIn/C (70:20:10) 4 0.392 PtRuIn/C (90:5:5) 5 0.393
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