Synergistically Activating N2 and CO2 at Water Microdroplet Interfaces

Zaifa Shi; Jing Nie; Zuo‐Chang Chen; Thomas Ka Yam Lam; Jianing Wang; Lei Guo; Yunkai Li; Cunhao Cui; Haotian Ying; Jianing Zhang; Xu Cai; Qingjie Zeng; Yanyan Chen; Shui‐Chao Lin; Lan‐Sun Zheng; Zongwei Cai

doi:10.1002/anie.202519068

Synergistically Activating N₂ and CO₂ at Water Microdroplet Interfaces

Zaifa Shi (Co-first author)
, Jing Nie (Co-first author)
, Zuo‐Chang Chen (Co-first author)
, Thomas Ka Yam Lam (Co-first author)
, Jianing Wang
, Lei Guo
, Yunkai Li
, Cunhao Cui
, Haotian Ying
, Jianing Zhang
, Xu Cai
, Qingjie Zeng
, Yanyan Chen
, Shui‐Chao Lin
, Lan‐Sun Zheng
, Zongwei Cai^*

^*Corresponding author for this work

Research output: Contribution to journal › Journal article › peer-review

Abstract

Nitrogen (N₂) fixation is essential for sustaining life but is challenging under ambient conditions. Industrial N₂ fixation is energy-intensive and exacerbates carbon dioxide (CO₂) emissions, while high concentration of atmospheric CO₂ urgently requires scalable mitigation strategies. In this study, we report that simultaneous spontaneous activation of N₂ and CO₂ under ambient conditions in microdroplets, producing ammonium (NH₄⁺), nitrite (NO₂⁻), and formate (HCO₂⁻), as confirmed by isotopic labelling experiments and theoretical calculations. This can clarify the doubts about environmental ammonia pollution in microdroplets. The activation of N₂ and CO₂ exhibits a synergistic enhancement effect in microdroplets. Mechanistic investigation reveals novel pathways involving the CO₂-facilitated N₂ fixation and the oxygen radical (^•O)-mediated N₂ fixation. This discovery offers a sustainable pathway for green N₂ fixation and atmospheric CO₂ utilization, and offers insights into the potential formation pathway of HONO in the atmosphere.

Original language	English
Article number	e19068
Number of pages	8
Journal	Angewandte Chemie. International Edition
Volume	65
Issue number	3
DOIs	https://doi.org/10.1002/anie.202519068
Publication status	E-pub ahead of print - 24 Nov 2025

User-Defined Keywords

Ammonium
CO2 activation
N2 ﬁxation
Nitrous acid
Water microdroplet

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10.1002/anie.202519068

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Shi, Z., Nie, J., Chen, ZC., Lam, T. K. Y., Wang, J., Guo, L., Li, Y., Cui, C., Ying, H., Zhang, J., Cai, X., Zeng, Q., Chen, Y., Lin, SC., Zheng, LS., & Cai, Z. (2025). Synergistically Activating N₂ and CO₂ at Water Microdroplet Interfaces. Angewandte Chemie. International Edition, 65(3), Article e19068. Advance online publication. https://doi.org/10.1002/anie.202519068

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title = "Synergistically Activating N2 and CO2 at Water Microdroplet Interfaces",

abstract = "Nitrogen (N2) fixation is essential for sustaining life but is challenging under ambient conditions. Industrial N2 fixation is energy-intensive and exacerbates carbon dioxide (CO2) emissions, while high concentration of atmospheric CO2 urgently requires scalable mitigation strategies. In this study, we report that simultaneous spontaneous activation of N2 and CO2 under ambient conditions in microdroplets, producing ammonium (NH4+), nitrite (NO2−), and formate (HCO2−), as confirmed by isotopic labelling experiments and theoretical calculations. This can clarify the doubts about environmental ammonia pollution in microdroplets. The activation of N2 and CO2 exhibits a synergistic enhancement effect in microdroplets. Mechanistic investigation reveals novel pathways involving the CO2-facilitated N2 fixation and the oxygen radical (•O)-mediated N2 fixation. This discovery offers a sustainable pathway for green N2 fixation and atmospheric CO2 utilization, and offers insights into the potential formation pathway of HONO in the atmosphere.",

keywords = "Ammonium, CO2 activation, N2 ﬁxation, Nitrous acid, Water microdroplet",

author = "Zaifa Shi and Jing Nie and Zuo‐Chang Chen and Lam, \{Thomas Ka Yam\} and Jianing Wang and Lei Guo and Yunkai Li and Cunhao Cui and Haotian Ying and Jianing Zhang and Xu Cai and Qingjie Zeng and Yanyan Chen and Shui‐Chao Lin and Lan‐Sun Zheng and Zongwei Cai",

note = "This work was supported by the National Natural Science Foundation of China (grants 21827801, 22171235, and 22301105) and Natural Science Foundation of Fujian Province (grants 2023J05088). Publisher Copyright: {\textcopyright} 2025 Wiley-VCH GmbH.",

year = "2025",

month = nov,

day = "24",

doi = "10.1002/anie.202519068",

language = "English",

volume = "65",

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TY - JOUR

T1 - Synergistically Activating N2 and CO2 at Water Microdroplet Interfaces

AU - Shi, Zaifa

AU - Nie, Jing

AU - Chen, Zuo‐Chang

AU - Lam, Thomas Ka Yam

AU - Wang, Jianing

AU - Guo, Lei

AU - Li, Yunkai

AU - Cui, Cunhao

AU - Ying, Haotian

AU - Zhang, Jianing

AU - Cai, Xu

AU - Zeng, Qingjie

AU - Chen, Yanyan

AU - Lin, Shui‐Chao

AU - Zheng, Lan‐Sun

AU - Cai, Zongwei

N1 - This work was supported by the National Natural Science Foundation of China (grants 21827801, 22171235, and 22301105) and Natural Science Foundation of Fujian Province (grants 2023J05088). Publisher Copyright: © 2025 Wiley-VCH GmbH.

PY - 2025/11/24

Y1 - 2025/11/24

N2 - Nitrogen (N2) fixation is essential for sustaining life but is challenging under ambient conditions. Industrial N2 fixation is energy-intensive and exacerbates carbon dioxide (CO2) emissions, while high concentration of atmospheric CO2 urgently requires scalable mitigation strategies. In this study, we report that simultaneous spontaneous activation of N2 and CO2 under ambient conditions in microdroplets, producing ammonium (NH4+), nitrite (NO2−), and formate (HCO2−), as confirmed by isotopic labelling experiments and theoretical calculations. This can clarify the doubts about environmental ammonia pollution in microdroplets. The activation of N2 and CO2 exhibits a synergistic enhancement effect in microdroplets. Mechanistic investigation reveals novel pathways involving the CO2-facilitated N2 fixation and the oxygen radical (•O)-mediated N2 fixation. This discovery offers a sustainable pathway for green N2 fixation and atmospheric CO2 utilization, and offers insights into the potential formation pathway of HONO in the atmosphere.

AB - Nitrogen (N2) fixation is essential for sustaining life but is challenging under ambient conditions. Industrial N2 fixation is energy-intensive and exacerbates carbon dioxide (CO2) emissions, while high concentration of atmospheric CO2 urgently requires scalable mitigation strategies. In this study, we report that simultaneous spontaneous activation of N2 and CO2 under ambient conditions in microdroplets, producing ammonium (NH4+), nitrite (NO2−), and formate (HCO2−), as confirmed by isotopic labelling experiments and theoretical calculations. This can clarify the doubts about environmental ammonia pollution in microdroplets. The activation of N2 and CO2 exhibits a synergistic enhancement effect in microdroplets. Mechanistic investigation reveals novel pathways involving the CO2-facilitated N2 fixation and the oxygen radical (•O)-mediated N2 fixation. This discovery offers a sustainable pathway for green N2 fixation and atmospheric CO2 utilization, and offers insights into the potential formation pathway of HONO in the atmosphere.

KW - Ammonium

KW - CO2 activation

KW - N2 ﬁxation

KW - Nitrous acid

KW - Water microdroplet

UR - https://doi.org/10.26434/chemrxiv-2025-rrs8g

UR - https://www.scopus.com/pages/publications/105022801169

U2 - 10.1002/anie.202519068

DO - 10.1002/anie.202519068

M3 - Journal article

SN - 1433-7851

VL - 65

JO - Angewandte Chemie. International Edition

JF - Angewandte Chemie. International Edition

IS - 3

M1 - e19068

ER -

Synergistically Activating N₂ and CO₂ at Water Microdroplet Interfaces

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