Spin polarized Fe1-Ti pairs for highly efficient electroreduction nitrate to ammonia

Jie Dai; Yawen Tong; Long Zhao; Zhiwei Hu; Chien-Te Chen; Chang-Yang Kuo; Guangming Zhan; Jiaxian Wang; Xingyue Zou; Qian Zheng; Wei Hou; Ruizhao Wang; Kaiyuan Wang; Rui Zhao; Xiang-Kui Gu; Yancai Yao; Lizhi Zhang

doi:10.1038/s41467-023-44469-4

Spin polarized Fe₁-Ti pairs for highly efficient electroreduction nitrate to ammonia

Nat Commun. 2024 Jan 2;15(1):88. doi: 10.1038/s41467-023-44469-4.

Authors

Jie Dai^#¹, Yawen Tong^#², Long Zhao^#¹, Zhiwei Hu³, Chien-Te Chen⁴, Chang-Yang Kuo^{4

5}, Guangming Zhan¹, Jiaxian Wang¹, Xingyue Zou¹, Qian Zheng¹, Wei Hou¹, Ruizhao Wang¹, Kaiyuan Wang¹, Rui Zhao¹, Xiang-Kui Gu⁶, Yancai Yao⁷, Lizhi Zhang⁸

Affiliations

¹ School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
² School of Power and Mechanical Engineering, Wuhan University, Wuhan, 430072, China.
³ Max Planck Institute for Chemical Physics of Solids, Nothnitzer Strasse 40, 01187, Dresden, Germany.
⁴ National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu, 300092, Taiwan, China.
⁵ Department of Electrophysics, National Yang Ming Chiao Tung University, Hsinchu, Taiwan, China.
⁶ School of Power and Mechanical Engineering, Wuhan University, Wuhan, 430072, China. xiangkuigu@whu.edu.cn.
⁷ School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China. yyancai@sjtu.edu.cn.
⁸ School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China. zhanglz@ccnu.edu.cn.

^# Contributed equally.

Abstract

Electrochemical nitrate reduction to ammonia offers an attractive solution to environmental sustainability and clean energy production but suffers from the sluggish *NO hydrogenation with the spin-state transitions. Herein, we report that the manipulation of oxygen vacancies can contrive spin-polarized Fe₁-Ti pairs on monolithic titanium electrode that exhibits an attractive NH₃ yield rate of 272,000 μg h^-1 mg_Fe^-1 and a high NH₃ Faradic efficiency of 95.2% at -0.4 V vs. RHE, far superior to the counterpart with spin-depressed Fe₁-Ti pairs (51000 μg h^-1 mg_Fe^-1) and the mostly reported electrocatalysts. The unpaired spin electrons of Fe and Ti atoms can effectively interact with the key intermediates, facilitating the *NO hydrogenation. Coupling a flow-through electrolyzer with a membrane-based NH₃ recovery unit, the simultaneous nitrate reduction and NH₃ recovery was realized. This work offers a pioneering strategy for manipulating spin polarization of electrocatalysts within pair sites for nitrate wastewater treatment.

Abstract

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