open access

https://hdl.handle.net/2115/97868

High Turnover Frequency in the Electrocatalytic Reduction of Nitrous Oxide to Dinitrogen at a Binuclear Copper Complex of 3,5‐Diamino‐1,2,4‐Triazole

英語

2025-06-24

Wiley-VCH

Angewandte Chemie International Edition

64(34)

e202506067

Nitrous oxide (N2O) is a potent greenhouse gas and an ozone-depleting substance. Electrocatalytic N2O reduction (e-N2ORR) is a promising approach to remove N2O from the air under ambient conditions. However, developing noble-metal-free e-N2ORR electrocatalysts with high Faradaic efficiency (FE) and turnover frequency (TOF) remains a challenge because of the weak binding of N2O and the high kinetic barrier for deoxygenation reaction. In this work, inspired by the multinuclear copper active site of nitrous oxide reductases, a binuclear copper complex of 3,5-diamino-1,2,4-triazole supported on carbon black of Ketjenblack (CuHdatrz/KB) was utilized for the e-N2ORR at pH 13 and 298 K. CuHdatrz/KB achieves a high FE of ≈100% at -0.3 V vs. RHE for the e-N2ORR to N2 and TOF up to ≈700 h-1, which is one–two orders of magnitude higher than those of the previously reported molecular-based catalysts. In situ X-ray absorption spectroscopy confirmed that Cu(II) ions of CuHdatrz/KB are reduced to Cu(I) keeping the binuclear core, suggesting that the multinuclear copper active sites is crucial to efficiently catalyze the e-N2ORR like the nitrous oxide reductase.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: : Zhengwei Ma, Masaru Kato, Jenny Pirillo, Yuh Hijikata, Takeshi Watanabe, Yohei Uemura, Bang Lu, Satoru Takakusagi, Ken'ichi Kimijima, Hideo Notsu, Ichizo Yagi, Angew. Chem. Int. Ed. 2025, 64, e202506067, which has been published in final form at https://doi.org/10.1002/anie.202506067. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

1433-7851

1521-3773