Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study

Hu，Qikun1; Yang，Ke2; Peng，Ouwen1; Li，Minzhang3; Ma，Lu4; Huang，Songpeng5; Du，Yonghua4; Xu，Zong Xiang3; Wang，Qing5; Chen，Zhongxin1,6; Yang，Ming2; Loh，Kian Ping1

2024-01-10

10.1021/jacs.3c10516

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to the traditional Haber-Bosch process. Most research focuses on the low concentration range representative of the nitrate level in wastewater, leaving the high concentration range, which exists in nuclear and fertilizer wastes, unexplored. The use of a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that a cocatalytic system of Ru/CuO catalyst enables NO3RR at 10.0 A in 1 M nitrate electrolyte in a 16 cm flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies by deuterium labeling and operando Fourier transform infrared (FTIR) spectroscopy allow us to probe the hydrogen transfer rate and intermediate species on Ru/CuO. Ab initio molecular dynamics (AIMD) simulations reveal that adsorbed hydroxide on Ru nanoparticles increases the density of the hydrogen-bonded water network near the CuO surface, which promotes the hydrogen transfer rate. Our work highlights the importance of engineering synergistic interactions in cocatalysts for addressing the kinetic bottleneck in electrosynthesis.

SCI ; EI

英语

NI论文

其他

2-s2.0-85181569891

Scopus

1.Department of Chemistry,National University of Singapore,Singapore,3 Science Drive 3,117543,Singapore
2.Department of Applied Physics,The Hong Kong Polytechnic University,Kowloon,999077,Hong Kong
3.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518000,China
4.National Synchrotron Light Source II,Brookhaven National Lab,Upton,11973,United States
5.Department of Materials Science and Engineering,National University of Singapore,Singapore,117576,Singapore
6.School of Science and Engineering,The Chinese University of Hong Kong,Shenzhen,Guangdong,518172,China

Hu，Qikun,Yang，Ke,Peng，Ouwen,et al. Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study[J]. Journal of the American Chemical Society,2024,146(1):668-676.

Hu，Qikun.,Yang，Ke.,Peng，Ouwen.,Li，Minzhang.,Ma，Lu.,...&Loh，Kian Ping.(2024).Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study.Journal of the American Chemical Society,146(1),668-676.

Hu，Qikun,et al."Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study".Journal of the American Chemical Society 146.1(2024):668-676.