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Oxygen reduction on silver low-index single-crystal surfaces in alkaline solution: rotating ring disk(Ag(hkl))
B B Blizanac1, P N Ross, N M Marković
1Materials Sciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA. bbblizanac@lbl.gov
The Journal of Physical Chemistry. B
|March 11, 2006
Summary
The oxygen reduction reaction on silver single crystals is structure-sensitive, favoring the (110) surface. This study reveals key factors influencing the reaction kinetics and pathway in alkaline solutions.
Area of Science:
- Electrochemistry
- Surface Science
- Materials Science
Background:
- The oxygen reduction reaction (ORR) is crucial for energy conversion technologies.
- Understanding ORR kinetics on different metal surfaces is essential for catalyst design.
- Silver (Ag) is a promising catalyst for ORR, but its surface structure effects are not fully understood.
Purpose of the Study:
- To investigate the ORR kinetics and mechanism on Ag single-crystal surfaces.
- To determine the influence of crystallographic orientation on ORR performance.
- To elucidate the factors contributing to the observed structure sensitivity.
Main Methods:
- Rotating ring-disk electrode (RRDE) voltammetry was employed.
- Experiments were conducted on Ag(100), Ag(111), and Ag(110) single-crystal electrodes.
- Measurements were performed in alkaline solution across a temperature range of 293-333 K.
Main Results:
- The ORR proceeds via a dominant 4-electron pathway with minimal peroxide formation (<2%) on all tested Ag surfaces.
- The reaction kinetics exhibit significant structure sensitivity, increasing in the order (100) < or = (111) < (110).
- The observed structure sensitivity is attributed to potential-dependent hydroxyl adsorption and variations in O2 adsorption energies.
Conclusions:
- Silver single-crystal surfaces demonstrate structure-dependent ORR activity in alkaline media.
- The (110) surface offers superior kinetics for the ORR compared to (100) and (111) surfaces.
- Potential-dependent adsorption of hydroxyl ions and O2 adsorption energy are critical factors governing ORR on Ag surfaces.
