Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance

被引：90

作者：

Cai, Xiyang ^{[1
]}

Fu, Cehuang ^{[1
]}

Iriawan, Haldrian ^{[2
,3
]}

Yang, Fan ^{[1
]}

Wu, Aiming ^{[1
]}

Luo, Liuxuan ^{[1
]}

Shen, Shuiyun ^{[1
]}

Wei, Guanghua ^{[4
]}

Shao-Horn, Yang ^{[2
,5
]}

Zhang, Junliang ^{[1
]}

机构：

[1] Shanghai Jiao Tong Univ, Inst Fuel Cells, Sch Mech Engn, Shanghai 200240, Peoples R China

[2] MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA

[3] Imperial Coll London, Dept Mat, London SW7 5RB, England

[4] Shanghai Jiao Tong Univ, SJTU Paris Tech Elite Inst Technol, Shanghai 200240, Peoples R China

[5] MIT, Dept Mech Engn, Cambridge, MA 02139 USA

来源：

ISCIENCE | 2021年 / 24卷 / 10期

基金：

中国国家自然科学基金;

关键词：

INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; AMMONIA; EFFICIENCY; TRANSITION; CATALYSTS; FIXATION; BATTERY;

D O I：

10.1016/j.isci.2021.103105

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Green synthesis of ammonia by electrochemical nitrogen reduction reaction (NRR) shows great potential as an alternative to the Haber-Bosch process but is hampered by sluggish production rate and low Faradaic efficiency. Recently, lithium-mediated electrochemical NRR has received renewed attention due to its reproducibility. However, further improvement of the system is restricted by limited recognition of its mechanism. Herein, we demonstrate that lithium-mediated NRR began with electrochemical deposition of lithium, followed by two chemical processes of dinitrogen splitting and protonation to ammonia. Furthermore, we quantified the extent to which the freshly deposited active lithium lost its activity toward NRR due to a parasitic reaction between lithium and electrolyte. A high ammonia yield of 0.410 +/- 0.038 mg s(-1) cm(-2) geo and Faradaic efficiency of 39.5 +/- 1.7% were achieved at 20 mA cm(-2) geo and 10 mA cm(-2) geo, respectively, which can be attributed to fresher lithium obtained at high current density.

引用

页数：17

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