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Dual-effect electrocatalyst: activating interfacial water and optimizing adsorption energy on adjacent Fe3C/FeN4
Chenhong Liu1, Xiaoli Yang1, Kai Zhu1
1Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
None:
The oxygen reduction reaction (ORR) is crucial for sustainable power generation, yet its sluggish kinetics, mainly caused by insufficient proton supply and excessive intermediates adsorption, severely limit the overall efficiency. An important ongoing challenge is to regulate both factors to significantly enhance ORR. Herein, a dual-effect catalyst, Fe3C@Fe/NC, was designed and synthesized via a systematic two-step Fe3+ doping strategy to achieve closely adjacent multiple active sites. This catalyst features activated interfacial water to provide sufficient protons and optimized intermediate adsorption energy. Structural characterization revealed uniformly distributed FeN4 sites alongside adjacent Fe3C nanoparticles interwoven by carbon nanotubes. In-situ spectroscopic techniques and theoretical calculations demonstrated that Fe3C nanoparticles can activate interfacial water, enhancing dynamic active hydrogen donation to neighboring FeN4 sites, thereby accelerating the proton-coupled electron transfer (PCET) kinetics. Simultaneously, the regulated electronic structure around FeN4 sites offers appropriate intermediate adsorption energy, further boosting ORR activity and durability. The Fe3C@Fe/NC catalyst exhibits a remarkable half-wave potential of 0.904 V, a higher power density of 221.3 mW cm-2 and excellent durability with 1250 h operation at 5 mA cm-2 in zinc-air battery test. This work establishes a proximal proton-donation strategy to overcome the alkaline ORR bottleneck.
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