TY - JOUR
T1 - Influence of phosphate anion adsorption on the kinetics of oxygen electroreduction on low index Pt(hkl) single crystals
AU - He, Qinggang
AU - Yang, Xiaofang
AU - Chen, Wei
AU - Mukerjee, Sanjeev
AU - Koel, Bruce E.
AU - Chen, Shaowei
PY - 2010/10/21
Y1 - 2010/10/21
N2 - The detrimental effects of phosphate anion adsorption on the oxygen reduction reactions (ORR) on low index Pt single crystal electrodes were studied in 0.1 M perchloric acid by using a hanging meniscus rotating disk electrode in the presence of varied concentrations of H3PO4. The kinetic current for ORR decreased dramatically on Pt(100), Pt(110), Pt(111), and PtSn(111) even with the addition of a small amount (1 mM) of H 3PO4 into the perchloric acid solution, most probably due to the adsorption of phosphate anions onto the Pt active sites that impeded the electroreduction of O2. Remarkably, the extent of decline was found to vary with the specific single crystal surface, following the order of Pt(111) > PtSn(111) > Pt(110) ∼ Pt(100). Consistent behaviors were also observed in Tafel analysis and in electrochemical impedance spectroscopic measurements. Within the present experimental context, Pt(110) was found to be the optimal crystal surface for ORR in phosphoric acid fuel cells with the smallest charge transfer resistance, whereas the poisoning effects of phosphate anion adsorption were the most pronounced on Pt(111), most likely because the phosphate anions primarily adsorbed on the 3-fold sites on the Pt(111) faces, as manifested in in situ X-ray absorption spectroscopic measurements.
AB - The detrimental effects of phosphate anion adsorption on the oxygen reduction reactions (ORR) on low index Pt single crystal electrodes were studied in 0.1 M perchloric acid by using a hanging meniscus rotating disk electrode in the presence of varied concentrations of H3PO4. The kinetic current for ORR decreased dramatically on Pt(100), Pt(110), Pt(111), and PtSn(111) even with the addition of a small amount (1 mM) of H 3PO4 into the perchloric acid solution, most probably due to the adsorption of phosphate anions onto the Pt active sites that impeded the electroreduction of O2. Remarkably, the extent of decline was found to vary with the specific single crystal surface, following the order of Pt(111) > PtSn(111) > Pt(110) ∼ Pt(100). Consistent behaviors were also observed in Tafel analysis and in electrochemical impedance spectroscopic measurements. Within the present experimental context, Pt(110) was found to be the optimal crystal surface for ORR in phosphoric acid fuel cells with the smallest charge transfer resistance, whereas the poisoning effects of phosphate anion adsorption were the most pronounced on Pt(111), most likely because the phosphate anions primarily adsorbed on the 3-fold sites on the Pt(111) faces, as manifested in in situ X-ray absorption spectroscopic measurements.
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U2 - 10.1039/c0cp00433b
DO - 10.1039/c0cp00433b
M3 - Article
C2 - 20725683
AN - SCOPUS:77957901596
SN - 1463-9076
VL - 12
SP - 12544
EP - 12555
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 39
ER -