Citation: Jing Feng, Jing He, Qinling Liu, Qin Chen, Qin Deng, Yunxiang He, Yajing Zhang, Zhenju Jiang, Xinghua Zhu, Junling Guo. Towards reducing the overpotential of C-Fe₃O₄ in electrochemical hydrazine oxidation with Fe-TA coordination complexes as a tunable buffering coating[J]. Chinese Chemical Letters, ;2026, 37(10): 111994. doi: 10.1016/j.cclet.2025.111994 shu

Towards reducing the overpotential of C-Fe₃O₄ in electrochemical hydrazine oxidation with Fe-TA coordination complexes as a tunable buffering coating

Jing Feng ^{a, b, 1} ,
Jing He ^{a, 1} ,
Qinling Liu ^{b, c, 1} ,
Qin Chen ^a ,
Qin Deng ^a ,
Yunxiang He ^b ,
Yajing Zhang ^b ,
Zhenju Jiang ^a ,
Xinghua Zhu ^{a, *,} ,
Junling Guo ^{b, *,}

a.
School of Science, Xihua University, Chengdu 610039, China
b.
BMI Center for Biomass Materials and Nanointerfaces, National Engineering Laboratory for Clean Technology of Leather Manufacture, Ministry of Education Key Laboratory of Leather Chemistry and Engineering, College of Biomass Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China
c.
Tea Resources Utilization and Quality Testing Key Laboratory of Sichuan Province, College of Horticulture, Sichuan Agricultural University, Chengdu 611130, China

13778012637@163.com

junling.guo@scu.edu.cn

Received Date: 31 July 2025
Revised Date: 14 October 2025
Accepted Date: 21 October 2025
Available Online: 22 October 2025

Figures(6)

Hydrazine oxidation reaction (HzOR) is highly thermodynamically favorable, but typically kinetically slow with a significant overpotential at most electrodes. Developing and illustrating a generic methodology for reducing the overpotential is of great significance but challenging. Here we designed a Fe-tannic acid (Fe-TA) buffering coating for carbon-hybridized Fe₃O₄ (C-Fe₃O₄) particles to reduce the overpotential of the multiple-proton-involved HzOR, which was further applied to highly efficient hydrazine-assisted hydrogen production and electrochemical hydrazine detection. A series of comparative experiments confirmed that the Fe-TA coating significantly reduces the isoelectric point, enhances the wettability, increases the electric double-layer capacitance, and decreases the charge transfer resistance, thereby lowering the resistance overpotential. Notably, C-Fe₃O₄@Fe-TA exhibited an excellent buffering effect that effectively decreases the concentration overpotential for electrochemical HzOR, which can be attributed to the reversible transformations among the mono-, bis-, and tris-complexes of Fe(Ⅲ) with tannic acid. Correspondingly, C-Fe₃O₄@Fe-TA achieved current density of 10 mA/cm² at 23 mV (vs. RHE) in the electrolyte containing 1.0 mol/L KOH and 0.3 mol/L hydrazine. Coupled with HzOR, the C-Fe₃O₄@Fe-TA║Pt wire electrolysis system required a low working voltage of only 0.22 V at 10 mA/cm² for synchronous hydrogen production, which was significantly lower than that of a traditional overall water splitting system (1.23 V). Moreover, C-Fe₃O₄@Fe-TA showed good performance in electrochemical hydrazine detection, simultaneously exhibiting high sensitivity (1478 µA L mmol⁻¹ cm⁻²), a low detection limit (0.15 µmol/L), high selectivity, excellent stability, and high reliability for the analysis of real samples. This study reveals that the Fe-TA buffering coating can effectively decrease both the concentration and resistance overpotentials in electrochemical HzOR, demonstrating its potential as a general methodology for reducing the overpotential in this class of multiple-proton-involved reactions.
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Towards reducing the overpotential of C-Fe3O4 in electrochemical hydrazine oxidation with Fe-TA coordination complexes as a tunable buffering coating

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通讯作者: 陈斌, bchen63@163.com

Towards reducing the overpotential of C-Fe₃O₄ in electrochemical hydrazine oxidation with Fe-TA coordination complexes as a tunable buffering coating