Selectivity of Nitrate Reduction and Hydrogen Evolution Reaction Modulated by Aggregation of Carbon-Supported Fe Species.
- 1Department of Chemistry, National Tsing Hua University, Hsinchu30013, Taiwan.
- 2National Synchrotron Radiation Research Center , Hsinchu300092, Taiwan.
Abstract
Fe-species distribution plays an important role in electrochemical nitrate reduction, yet its influence on the competing hydrogen evolution reaction (HER) remains insufficiently understood. Herein, carbon-supported Fe catalysts with distinct Fe-species distributions were prepared by controlling the Fe precursor concentration. FeAC consists of highly dispersed atomic-scale Fe species and FeOx nanoclusters, whereas Fe2O3/FeAC additionally contains crystalline α-Fe2O3 nanoparticles. X-ray absorption spectroscopy, X-ray diffraction, and electron microscopy confirm the distinct Fe dispersion states in the two catalysts. Electrochemical measurements reveal that FeAC achieves significantly higher NH3 Faradaic efficiency (79.6 ± 2.2%) than Fe2O3/FeAC (37.8 ± 3.1%) at -0.8 V versus RHE, whereas Fe2O3/FeAC exhibits a higher NH3 production rate accompanied by enhanced HER. Comparable electrochemically accessible surface areas and interfacial charge-transfer characteristics indicate that the observed catalytic differences are not primarily governed by electrochemical surface area or charge-transfer properties. Operando Raman spectroscopy reveals distinct surface reaction environments, while operando ATR-SEIRAS together with EPR measurements indicates enhanced formation of hydrogen-related Fe-H intermediates and hydrogen radicals on Fe2O3/FeAC, consistent with its stronger HER activity. In contrast, the absence of detectable Fe-H species on FeAC is associated with suppressed hydrogen adsorption and improved nitrate reduction selectivity. These results demonstrate that controlling Fe-species distribution provides an effective strategy for balancing activity and selectivity in carbon-supported Fe electrocatalysts for electrochemical nitrate reduction.
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BibTeX
@article{wu2026selectivity,
title = {{Selectivity of Nitrate Reduction and Hydrogen Evolution Reaction Modulated by Aggregation of Carbon-Supported Fe Species.}},
author = {Wun-Yan Wu and Cheng-Jhe Tsai and Chih-Ying Lin and Serhii Makovetskyi and Ting-Shan Chan and Yao-Chang Lee and Ying-Rui Lu and Wen-Feng Liaw},
journal = {Langmuir : the ACS journal of surfaces and colloids},
year = {2026},
month = sep,
doi = {10.1021/acs.langmuir.6c03729},
url = {https://europepmc.org/article/MED/42915222},
note = {CC BY},
}
RIS
TY - JOUR
TI - Selectivity of Nitrate Reduction and Hydrogen Evolution Reaction Modulated by Aggregation of Carbon-Supported Fe Species.
AU - Wun-Yan Wu
AU - Cheng-Jhe Tsai
AU - Chih-Ying Lin
AU - Serhii Makovetskyi
AU - Ting-Shan Chan
AU - Yao-Chang Lee
AU - Ying-Rui Lu
AU - Wen-Feng Liaw
PY - 2026
DA - 2026/09/01
JO - Langmuir : the ACS journal of surfaces and colloids
DO - 10.1021/acs.langmuir.6c03729
UR - https://europepmc.org/article/MED/42915222
AB - Fe-species distribution plays an important role in electrochemical nitrate reduction, yet its influence on the competing hydrogen evolution reaction (HER) remains insufficiently understood. Herein, carbon-supported Fe catalysts with distinct Fe-species distributions were prepared by controlling the Fe precursor concentration. FeAC consists of highly dispersed atomic-scale Fe species and FeOx nanoclusters, whereas Fe2O3/FeAC additionally contains crystalline α-Fe2O3 nanoparticles. X-ray absorption spectroscopy, X-ray diffraction, and electron microscopy confirm the distinct Fe dispersion states in the two catalysts. Electrochemical measurements reveal that FeAC achieves significantly higher NH3 Faradaic efficiency (79.6 ± 2.2%) than Fe2O3/FeAC (37.8 ± 3.1%) at -0.8 V versus RHE, whereas Fe2O3/FeAC exhibits a higher NH3 production rate accompanied by enhanced HER. Comparable electrochemically accessible surface areas and interfacial charge-transfer characteristics indicate that the observed catalytic differences are not primarily governed by electrochemical surface area or charge-transfer properties. Operando Raman spectroscopy reveals distinct surface reaction environments, while operando ATR-SEIRAS together with EPR measurements indicates enhanced formation of hydrogen-related Fe-H intermediates and hydrogen radicals on Fe2O3/FeAC, consistent with its stronger HER activity. In contrast, the absence of detectable Fe-H species on FeAC is associated with suppressed hydrogen adsorption and improved nitrate reduction selectivity. These results demonstrate that controlling Fe-species distribution provides an effective strategy for balancing activity and selectivity in carbon-supported Fe electrocatalysts for electrochemical nitrate reduction.
SN - 0743-7463
SN - 1520-5827
ER -