首页|"Buckets effect"in the kinetics of electrocatalytic reactions
"Buckets effect"in the kinetics of electrocatalytic reactions
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In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxy-gen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectan-gular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relation-ships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concen-tration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structure-performance relationships.
Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics,University of Science and Technology of China,Hefei 230026,Anhui,China
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