A Spectroscopic Study on the Nitrogen Electrochemical Reduction Reaction on Gold and Platinum Surfaces

Yao Yao; Shangqian Zhu; Haijiang Wang; Hui Li; Minhua Shao

doi:10.1021/jacs.7b12101

A Spectroscopic Study on the Nitrogen Electrochemical Reduction Reaction on Gold and Platinum Surfaces

J Am Chem Soc. 2018 Jan 31;140(4):1496-1501. doi: 10.1021/jacs.7b12101. Epub 2018 Jan 18.

Authors

Yao Yao^{1

2}, Shangqian Zhu^{1

2}, Haijiang Wang^{1

2}, Hui Li^{1

2}, Minhua Shao^{1

2}

Affiliations

¹ Department of Chemical and Biological Engineering, and ‡Energy Institute, The Hong Kong University of Science and Technology , Clear Water Bay, Kowloon, Hong Kong.
² Department of Materials Science and Engineering, and ∥Department of Mechanical and Energy Engineering, South University of Science and Technology of China , 1088 Xueyuan Boulevard, Nanshan District, Shenzhen, Guangdong 518055, China.

PMID: 29320173
DOI: 10.1021/jacs.7b12101

Abstract

The electrochemical reduction of nitrogen to ammonia on Au-based catalysts showed a reasonably high Coulombic efficiency. The pathway of this promising reaction, however, is not clear partially due to the lack of information on reaction intermediates. Herein, surface-enhanced infrared absorption spectroscopy (SEIRAS) was employed to study the reaction mechanisms of nitrogen reduction on an Au thin film for the first time. During the nitrogen reduction, the N₂H_y species was detected with bands at 1453 (H-N-H bending), 1298 (-NH₂ wagging), and 1109 cm^-1 (N-N stretching) at potentials below 0 V against reversible hydrogen electrode. This result indicates that the nitrogen reduction reaction on Au surfaces follows an associative mechanism, and the N≡N bond in N₂ tends to break simultaneously with the hydrogen addition. By comparison, no absorption band associated with N was observed on Pt surfaces under the same reaction condition. This result is consistent with the low efficiency of nitrogen reduction on Pt due to the much faster kinetics of hydrogen evolution reaction.

Publication types

Research Support, Non-U.S. Gov't