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Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
Published on: December 4, 2017
Calcium-Mediated Fe─N Bond Reinforcement for Ultra-Stable Oxygen Reduction Reaction
Xuan Xie1, Quanyu Wen1, Zhuang Wu2
1Key Laboratory of Polymer Materials of Gansu Province, Analytical Testing Center, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, College of Engineering, Northwest Normal University, Lanzhou, P. R. China.
Abstract:
The practical deployment of atomically dispersed Fe-N-C catalysts for the oxygen reduction reaction (ORR) is severely hampered by the electrochemical leaching of Fe active sites. Inspired by the stabilizing role of Ca2+ in metalloenzyme active sites, a novel Fe-Ca dual-atom sites catalyst (Ca/Fe-N-C) is constructed on amorphous porous carbon nanosheets. The introduced Ca atom acts as an "electronic modulator" and "structural stabilizer," which effectively lowers the oxidation state of Fe and reinforces Fe-N coordination bond. This ingenious design results in an exceptional ORR catalyst with the half-wave potential of 0.912 V in alkaline media and unprecedented durability, exhibiting negligible decay after 80000 cycles. When integrated into Zn-air batteries (ZABs), the Ca/Fe-N-C-based cathode delivers a peak power density of 215 mW cm-2 and sustains operation for exceeding 1110 h, markedly superior to benchmark Pt/C. This work not only unveils the pivotal role of alkaline-earth metals in stabilizing transition-metal sites but also establishes a general paradigm for designing durable atomically dispersed catalysts for advanced energy conversion devices.
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