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PreprintCC BY-NC-NDChemRxiv

Fourteen-Membered Macrocyclic Copper Complex for Highly Selective Electrochemical Nitrate Reduction to Ammonia

  • Yuantao Yang1
  • Ryotaro Iwata1
  • Shoji Iguchi1,2
  • Ritsu Hibino3
  • Koyata Nishiyama3
  • Makoto Moriya3,4,5
  • Shimpei Naniwa1
  • Kentaro Teramura1,6
6 affiliations
  1. 1Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615−8510, Japan
  2. 2PRESTO, Japan Science and Technology Agency (JST, 4-1-8 Honcho, Kawaguchi, Saitama, Japan, 332-0012
  3. 3Graduate School of Science and Technology, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka, Japan, 422-8529
  4. 4Research Institute of Green Science and Technology, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka, Japan, 422-8529
  5. 5Academic Institute, Shizuoka University, 836, Ohya, Suruga-ku, Shizuoka, Japan, 422-8529
  6. 6Fukui Institute for Fundamental Chemistry, Kyoto University, Takano Nishibiraki-cho 34-4, Sakyo-ku, Kyoto, Japan, 606-8103
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Abstract

The selective electrochemical reduction of nitrate (NO3−) to ammonia (NH3) represents a promising route for sustainable NH3 production. However, achieving high NH3 selectivity remains challenging due to competing reactions. Additionally, many reported catalysts rely on noble metals and often require relatively elevated catalyst loadings to achieve high apparent activity, while most systems operate only at relatively low current densities. Herein, a fourteen-membered macrocyclic copper complex supported on Ketjenblack (Cu-14MR/KB) is reported as a cathode catalyst for the highly selective electrochemical reduction of NO3− to NH3. With a low Cu loading of 1.34 μmol cm−2, Cu-14MR/KB delivered a high Faraday efficiency for NH3 synthesis of up to 94.8% at a current density of −26.3 mA cm−2 and maintained high NH3 selectivity over a wide current density range from −26.3 to −150 mA cm−2. Notably, at −150 mA cm−2, Cu-14MR/KB achieved an NH3 yield rate of 604 μmol cm−2 h−1 with an NH3 Faraday efficiency of 86.4%. Furthermore, a more contracted Cu–N4 coordination environment was revealed in Cu-14MR than in CuPc, with a shorter Cu–N bond distance, suggesting relatively stronger Cu–N interactions. This work provides an efficient strategy for high-performance NO3− electroreduction using a low-loading and non-noblemetal catalyst.

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Cite

BibTeXRIS
BibTeX
@misc{yang2026fourteenmembered,
  title = {{Fourteen-Membered Macrocyclic Copper Complex for Highly Selective Electrochemical Nitrate Reduction to Ammonia}},
  author = {Yuantao Yang and Ryotaro Iwata and Shoji Iguchi and Ritsu Hibino and Koyata Nishiyama and Makoto Moriya and Shimpei Naniwa and Kentaro Teramura},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15009889/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009889/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Fourteen-Membered Macrocyclic Copper Complex for Highly Selective Electrochemical Nitrate Reduction to Ammonia
AU  - Yuantao Yang
AU  - Ryotaro Iwata
AU  - Shoji Iguchi
AU  - Ritsu Hibino
AU  - Koyata Nishiyama
AU  - Makoto Moriya
AU  - Shimpei Naniwa
AU  - Kentaro Teramura
PY  - 2026
DA  - 2026/10/05
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009889/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009889/v1
AB  - The selective electrochemical reduction of nitrate (NO3−) to ammonia (NH3) represents a promising route for sustainable NH3 production. However, achieving high NH3 selectivity remains challenging due to competing reactions. Additionally, many reported catalysts rely on noble metals and often require relatively elevated catalyst loadings to achieve high apparent activity, while most systems operate only at relatively low current densities. Herein, a fourteen-membered macrocyclic copper complex supported on Ketjenblack (Cu-14MR/KB) is reported as a cathode catalyst for the highly selective electrochemical reduction of NO3− to NH3. With a low Cu loading of 1.34 μmol cm−2, Cu-14MR/KB delivered a high Faraday efficiency for NH3 synthesis of up to 94.8% at a current density of −26.3 mA cm−2 and maintained high NH3 selectivity over a wide current density range from −26.3 to −150 mA cm−2. Notably, at −150 mA cm−2, Cu-14MR/KB achieved an NH3 yield rate of 604 μmol cm−2 h−1 with an NH3 Faraday efficiency of 86.4%. Furthermore, a more contracted Cu–N4 coordination environment was revealed in Cu-14MR than in CuPc, with a shorter Cu–N bond distance, suggesting relatively stronger Cu–N interactions. This work provides an efficient strategy for high-performance NO3− electroreduction using a low-loading and non-noblemetal catalyst.
ER  -