Fabrication of Nanoporous PtRuFe by Dealloying Amorphous Fe(Pt, Ru)B Ribbons and Their Methanol Electrocatalytic Properties
XU Xiuyue, LI Yanhui(), ZHANG Wei
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
Cite this article:
XU Xiuyue, LI Yanhui, ZHANG Wei. Fabrication of Nanoporous PtRuFe by Dealloying Amorphous Fe(Pt, Ru)B Ribbons and Their Methanol Electrocatalytic Properties. Acta Metall Sin, 2020, 56(10): 1393-1400.
The growing technological demand for high-efficiency direct methanol fuel cells (DMFCs) drives the exploration of catalysts with improved catalytic performance. Conventional pure Pt with good catalytic activity for methanol oxidation reaction (MOR) have been applied in the DMFCs for several decades, while their CO tolerance still needs to be further enhanced. Formation of nanoporous structure with a high specific surface area is an effective way to increase the catalytic efficiency by providing more active sites. Alloying suitable Fe and Ru into Pt is promising for the improvements of both catalytic activity and anti-CO poisoning. In this work, the nanoporous alloys have been fabricated by dealloying Fe65Pt10-xRuxB25 (x=0, 2, 4, atomic fraction, %) melt-spun alloy ribbons in 0.1 mol/L H2SO4 solution, and the phase structures, morphologies, chemical compositions, and magnetic properties of the melt-spun ribbons and nanoporous alloys were characterized by XRD, TEM, SEM, EDS, XPS and VSM, respectively. The electrocatalytic properties for MOR of the nanoporous alloys were examined by cycle voltammetry in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution. The results reveal that all melt-spun ribbons are fully amorphous, and nanoporous (Pt, Ru)Fe with a single-fcc phase can be obtained after dealloying. The nanoporous (Pt, Ru)Fe dealloyed from x=0 and 2 precursors possess a similar fine bicontinuous ligament/channel structure with average pore diameter and ligament size of 6~7 and 7~8 nm, respectively. Cracks can be found on the surficial nanoporous architecture for the nanoporous PtRuFe obtained from the x=4 alloy. With enriching of Ru, the oxidation peak potential of the nanoporous alloys exhibits a negative shift, and the ratio (jf/jb) of the peak current density in the forward scan (jf) to that in the backward scan (jb) increases gradually. The jf and jf/jb for the nanoporous PtRuFe dealloyed from the x=2 alloy is 0.87 mA/cm2 and 4.6, which are 1.7 and 2.7 times of those for the nanoporous PtFe, respectively, indicating the superior electrocatalytic activity for MOR and CO tolerance in comparison with the binary PtFe alloy. The improvement in electrocatalytic performance after Ru addition can be attribute to the combination of Pt/Ru bifunctional mechanism and weakened Pt-COads adsorption energy. In addition, the nanoporous PtRuFe alloys also exhibit ferromagnetic characteristic with saturation magnetization values of 0.41~0.42 T, which can be easily separated and recycled in the practical applications. This work paves the way for the development of high-performance MOR electrocatalyst.
Fig.1 XRD spectra of melt-spun Fe65Pt10-xRuxB25 (x=0~4) ribbons before (a) and after (b) dealloying
Fig.2 Surface (a~c) and cross-sectional (d, e) SEM images and EDS (f) of Fe65Pt10-xRuxB25 amorphous alloy ribbons after dealloying (Insets in Figs.2d and e show the enlarged views) (a) x=0 (b, d) x=2 (c, e) x=4
x
Phase
d
nm
l
nm
Atomic fraction / %
Pt
Ru
Fe
0
fcc-PtFe
7
8
66.02
-
33.98
2
fcc-PtRuFe
6
7
52.02
13.23
34.75
4
fcc-PtRuFe
3
-
37.86
25.82
36.32
Table 1 The phase constitution, average pore diameter (d), ligament size (l) and atomic fractions of Pt, Ru and Fe concentrations of Fe65Pt10-xRuxB25 (x=0~4) amorphous alloy ribbons after dealloying
Fig.3 Bright-field TEM images and corresponding SAED patterns (insets) of melt-spun Fe65Pt8Ru2B25 ribbons before (a) and after (b) dealloying
Fig.4 CV curves of nanoporous alloys fabricated by dealloying Fe65Pt10-xRuxB25 (x=0~4) amorphous alloy ribbons in 0.5 mol/L H2SO4 (a) and 0.5 mol/L H2SO4+1.0 mol/L CH3OH solutions (b), and peak current density in the forward scan (jf) and ratio of peak current density in the forward scan to that in the backward scan (jf /jb) as a function of Ru content (The data of Pt/C are shown for comparison) (c)
Fig.5 XPS spectra of nanoporous alloys fabricated by dealloying Fe65Pt10-xRuxB25 (x=0~4) amorphous alloy ribbons(a1~a3) x=2: Pt4f, Ru3d and Fe2p, respectively (b) x=0~4: Pt4f
Fig.6 Hysteresis loops of Fe65Pt10-xRuxB25 (x=0~4) melt-spun alloy ribbons before and after dealloying
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