The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,t...The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,the mechanistic origin of this stabilisation remained obscure.It is established herein with rotating ring disc experiments that the side product,H_(2)O_(2),which is known to damage FeNC catalysts,is suppressed by the presence of Pt.The formation of reactive oxygen species is additionally inhibited,independent of intrinsic H_(2)O_(2) formation,as determined by electron paramagnetic resonance.Transmission electron microscopy identifies an oxidised Fe-rich layer covering the Pt particles,thus explaining the inactivity of the latter towards the ORR.These insights develop understanding of Fe NC degradation mechanisms during ORR catalysis,and crucially establish the required properties of a precious metal free protective catalyst to improve Fe NC stability in acidic media.展开更多
Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon...Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon have to be activated by extrinsic factors. Pure carbon has no catalytic activity when used as electrode for electrocatalytic water oxidation. The evolution of oxygen functional groups on the carbon surface with increasing potential and the subsequent formation of real active sites with iron impurities from the electrolyte have been confirmed. These in-situ formed active sites protect the carbon from deep oxidation. This unprecedented finding not only provides insight into the dynamic evolution of carbon electrode surface chemistry and raises awareness of the need for detailed surface analysis under operando conditions, but also suggests a direction for the development of scalable and high-performance carbonbased electrode systems for various electrochemical applications.展开更多
基金a fellowship from the Alexander von Humboldt foundation。
文摘The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,the mechanistic origin of this stabilisation remained obscure.It is established herein with rotating ring disc experiments that the side product,H_(2)O_(2),which is known to damage FeNC catalysts,is suppressed by the presence of Pt.The formation of reactive oxygen species is additionally inhibited,independent of intrinsic H_(2)O_(2) formation,as determined by electron paramagnetic resonance.Transmission electron microscopy identifies an oxidised Fe-rich layer covering the Pt particles,thus explaining the inactivity of the latter towards the ORR.These insights develop understanding of Fe NC degradation mechanisms during ORR catalysis,and crucially establish the required properties of a precious metal free protective catalyst to improve Fe NC stability in acidic media.
文摘Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon have to be activated by extrinsic factors. Pure carbon has no catalytic activity when used as electrode for electrocatalytic water oxidation. The evolution of oxygen functional groups on the carbon surface with increasing potential and the subsequent formation of real active sites with iron impurities from the electrolyte have been confirmed. These in-situ formed active sites protect the carbon from deep oxidation. This unprecedented finding not only provides insight into the dynamic evolution of carbon electrode surface chemistry and raises awareness of the need for detailed surface analysis under operando conditions, but also suggests a direction for the development of scalable and high-performance carbonbased electrode systems for various electrochemical applications.
