Fabrication of 3D Porous Core-shell PdNi@Au Nanocatalyst for Formic Acid Electro-oxidation†

doi:10.7503/cjcu20180776

Abstract

Abstract:

K₂PdCl₄ and K₂Ni(CN)₄ were employed as precursors to fabricate cyanogel, which was then reduced by NaBH₄ to prepare 3D porous coral-like PdNi alloy. On the basis of the synthesized PdNi alloy, 3D porous PdNi@Au catalysts with PdNi alloy as inner core and Au layers of different thickness on the surface were synthesized by in situ Galvanic replacement between PdNi alloy and HAuCl₄ aqueous solution. X-Ray diffraction(XRD) and transmission electron microscopy(TEM) indicated that the 3D network structure was composed of interconnected nanoparticles with diameter of 7 nm. Energy dispersive X-ray(EDX) line scanning and mapping could declare its typical core-shell structure. Electrochemical measurements demonstrated that the electro-catalytic performance of PdNi@Au catalysts could be affected by the thickness of Au layer. When the content of Au reached a value of 5.6%(molar fraction), PdNi@Au catalyst exhibited the best catalytic performance for formic acid electro-oxidation. In this case, the peak current density of PdNi@Au catalyst was 7.2 times that of commercial Pd black.

Key words: Pd-based catalyst, Galvanic replacement, Formic acid electro-oxidation

CLC Number:

O646

TrendMD:

LI Jiahui,QIN Menghan,ZHANG Jie,DU Yi,SUN Dongmei,TANG Yawen. Fabrication of 3D Porous Core-shell PdNi@Au Nanocatalyst for Formic Acid Electro-oxidation^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 988.

Figures/Tables 11

Scheme 1 Synthetic routes of PdNi@Au catalyst(A) Orange jelly-like PdNi cyanogel and its ball-stick model; (B) photograph of 3D porous PdNi alloy with network structure; (C) schematic diagram of PdNi@Au catalyst.

Fig.1 UV spectroscopy of reaction system at different time

Fig.2 EDX pattern of PdNi@Au-5.6 catalyst(B)

Fig.3 Typical SEM(A), TEM(B) and HRTEM(C) images of PdNi@Au-5.6 catalyst The insets in (B) and (C) are corresponding SAED pattern and the outer Au layer, respectively.

Fig.4 EDX line scanning pattern of PdNi@Au-5.6 catalystInset is corresponding HRTEM image of the EDX line scanning test region.

Fig.5 HAADF-STEM image(A) and EDX mapping patterns of PdNi@Au-5.6 catalyst(B—E) (B) Ni; (C) Pd; (D) Au; (E) overlap.

Fig.6 XRD patterns of different catalysts

Fig.7 XPS spectra of PdNi@Au-5.6(A) Full scan; (B) Pd3d region; (D) Au4f region.

Fig.8 CV curves of different catalysts in N2-saturated 0.5 mol/L H2SO4(A) and in N2-saturated 0.5 mol/L H2SO4+0.1 mol/L HCOOH(B)Inset in (B) is corresponding Tafel plots.

Fig.9 Chronoamperometry curves at 0 V for 3000 s in N2-saturated 0.5 mol/L H2SO4+0.1 mol/L HCOOH(A) and CO-stripping voltammograms in N2-saturated 0.5 mol/L H2SO4(B) of different catalysts

Fig.10 CV curves of different catalysts in N2-saturated 0.5 mol/L H2SO4+ 0.1 mol/L HCOOH solution(A) and histogram of mass-normalized peak current for different catalysts(B)a. PdNi@Au-2.8; b. PdNi@Au-5.6; c. PdNi@Au-11.2; d. PdNi@Au-16.8.

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