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FUEL CELL CATALYSTS BY SPONTANEOUS DEPOSITION

,
CHARACTERIZATION BY EC-NMR
π/2 π Echo

τ τ
H0 V

Andrzej Wieckowski

Department of Chemistry
University of Illinois at Urbana-Champaign
Urbana, IL 61801, USA
ELECTROCHEMICAL NUCLEAR MAGNETIC RESONANCE

•Electrochemical NMR spectroscopy (EC-NMR) can
probe the metal (195Pt) and adsorbate (13CO) side of the
electrochemical interface.

•We measure the Knight shift (K) and spin-lattice
relaxation rate (1/T1) and then use phenomenological
two-band models to extract Ef-LDOS.

•EC-NMR is capable of probing the properties of
electrocatalysts, alloying effects, electrode adsorption,
surface diffusion of adsorbates and poisoning
intermediates, in an electrochemical environment which
closely resembles real world conditions.
Electrochemistry: Enhancement in CO
Tolerance by spontaneously deposited
Ru onto Pt surfaces
CO stripping of CO ex MeOH MeOH Electrooxidation (at 0.3V)

Pt/Ru – 0
-14
-35
-52

Significant potential shift ~20 times current enhancement
13CNMR spectra of CO on Pt/Ru
as a function of Ru coverage

Pt/Ru – 0
-14
-35
-52
13C NMR of CO on Polycrystalline Pt and Pt/Ru Electrodes

A - Pt/Ru-0
B – Pt/Ru-14
C – Pt/Ru-35
D – Pt/Ru-53

Korringa plus diffusion :

T1-1= aT + 2(∆ω)2τ/(1+ω02τ2)
Variation of LDOS at both C and Pt sites with Ru Coverage

15
Metal surface
10
..

5
D(Ef) (atom •Ry )
-1

CO 2 π*
7
-1

6

5

CO 5 σ
1.0

0.5

0.0
0.0 0.2 0.4 0.6
Ru Coverage
Correlation Between the 2π*-LDOS and Methanol
Oxidation Current Density
A Ru Decorated Pt Nanoparticle
(by Spontaneous Deposition)

Ruthenium

Platinum
3.0

2.5

Reactivity E = 0.3 V

of the Ru Decorated 2.0

Pt Catalyst 1.5

1.0

0.5

-2
j/µA cm
Pt/Ru Decorated (UIUC)
30
PtRu Alloy (JM)

25

20
E = 0.4 V
15

10
Oxidation
in 0.5 M Methanol Solution 5
in 0.5 M H2SO4
Supporting Electrolyte 0
0 1 2 3 4

10-4 t/s
Acknowledgments
Collaboration with the Fuel Cell Group at Los Alamos National
Laboratory is acknowledged.

This work is supported by the National Science Foundation
and by the US Department of Energy

Typical recent references:

Analytical Chemistry, 70, 518A, (1998)
Phys. Rev. Lett., 83, 2457 (1999)
J. Am. Chem. Soc., 122, 1123 (2000)
J. Am. Chem. Soc., in press.