Boosting Electrochemical Oxygen Reduction Performance of Iron Phthalocyanine through Axial Coordination Sphere Interaction

Abstract

Precise regulation of the electronic states of catalytic sites through molecular engineering is highly desired to boost catalytic performance. Herein, a facile strategy was developed to synthesize efficient oxygen reduction reaction (ORR) catalysts, based on mononuclear iron phthalocyanine supported on commercially available multi-walled carbon nanotubes that contain electron-donating functional groups (FePc/CNT-R, with "R" being -NH₂ , -OH, or -COOH). These functional groups acted as axial ligands that coordinated to the Fe site, confirmed by X-ray photoelectron spectroscopy and synchrotron-radiation-based X-ray absorption fine structure. Experimental results showed that FePc/CNT-NH₂ , with the most electron-donating -NH₂ axial ligand, exhibited the highest ORR activity with a positive onset potential (E_onset =1.0 V vs. reversible hydrogen electrode) and half-wave potential (E_1/2 =0.92 V). This was better than the state-of-the-art Pt/C catalyst (E_onset =1.00 V and E_1/2 =0.85 V) under the same conditions. Overall, the functionalized FePc/CNT-R assemblies showed enhanced ORR performance in comparison to the non-functionalized FePc/CNT assembly. The origin of this behavior was investigated using density functional theory calculations, which demonstrated that the coordination of electron-donating groups to FePc facilitated the adsorption and activation of oxygen. This study not only demonstrates a series of advanced ORR electrocatalysts, but also introduces a feasible strategy for the rational design of highly active electrocatalysts for other proton-coupled electron transfer reactions.