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Vol. 16 (2024)

Oxygen-Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

https://doi.org/10.1007/s40820-023-01217-z
Shengbo Zhang
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Yuankang Zha
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Yixing Ye
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Ke Li
Key Laboratory of Agricultural Sensors, Ministry of Agriculture, School of Information and Computer, Anhui Agricultural University, Hefei 230026, People’s Republic of China
Yue Lin
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, People’s Republic of China
Lirong Zheng
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquan Road, Beijing 100049, People’s Republic of China
Guozhong Wang
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Yunxia Zhang
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Huajie Yin
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Tongfei Shi
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China
Haimin Zhang
Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, People’s Republic of China

Corresponding Author: Haimin Zhang

zhanghm@issp.ac.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 9

Abstract

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection. Here, we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen (O) coordination on bacterial cellulose-converted graphitic carbon (Mn–O–C). Evidence of the atomically dispersed Mn–(O–C2)4 moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy. As a result, the as-synthesized Mn–O–C catalyst exhibits superior NitRR activity with an NH3 yield rate (RNH3) of 1476.9 ± 62.6 μg h−1 cm−2 at − 0.7 V (vs. reversible hydrogen electrode, RHE) and a faradaic efficiency (FE) of 89.0 ± 3.8% at − 0.5 V (vs. RHE) under ambient conditions. Further, when evaluated with a practical flow cell, Mn–O–C shows a high RNH3 of 3706.7 ± 552.0 μg h−1 cm−2 at a current density of 100 mA cm−2, 2.5 times of that in the H cell. The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn–(O–C2)4 sites not only effectively inhibit the competitive hydrogen evolution reaction, but also greatly promote the adsorption and activation of nitrate (NO3−), thus boosting both the FE and selectivity of NH3 over Mn–(O–C2)4 sites.


Highlights:
1 Oxygen-coordinated single-atom Mn catalyst was fabricated via introducing oxygen functional groups rich bacterial cellulose as the adsorption regulator through a combined impregnation–pyrolysis–etching synthetic route.
2 Mn–O–C as the electrocatalyst exhibits superior electrocatalytic activity toward ammonia synthesis with a maximum NH3 yield rate of 1476.9 ± 62.6 μg h−1 cm−2 at − 0.7 V (vs. RHE) and a faradaic efficiency of 89.0 ± 3.8% at − 0.5 V (vs. RHE) under ambient conditions.
3 Electrocatalytic mechanism of Mn–(O–C2)4 site for nitrate reduction reaction is unveiled by a combination of in situ spectroscopy characterization and computational study.

Keywords

Atomically dispersed Oxygen coordination Nitrate reduction reaction In situ spectroscopic studies Hydrogen evolution reaction
Zhang, Shengbo, Yuankang Zha, Yixing Ye, Ke Li, Yue Lin, Lirong Zheng, Guozhong Wang, Yunxia Zhang, Huajie Yin, Tongfei Shi, and Haimin Zhang. 2023. “Oxygen-Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia”. Nano-Micro Letters 16 (November):9. https://doi.org/10.1007/s40820-023-01217-z.
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