Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N2 and H2O
Abstract
Ammonia (NH3) electrosynthesis gains significant attention as NH3 is essentially important for fertilizer production and fuel utilization. However, electrochemical nitrogen reduction reaction (NRR) remains a great challenge because of low activity and poor selectivity. Herein, a new class of atomically dispersed Ni site electrocatalyst is reported, which exhibits the optimal NH3 yield of 115 µg cm-2 h-1 at –0.8 V versus reversible hydrogen electrode (RHE) under neutral conditions. High faradic efficiency of 21 ± 1.9% is achieved at -0.2 V versus RHE under alkaline conditions, although the ammonia yield is lower. The Ni sites are stabilized with nitrogen, which is verified by advanced X-ray absorption spectroscopy and electron microscopy. Density functional theory calculations provide insightful understanding on the possible structure of active sites, relevant reaction pathways, and confirm that the Ni-N3 sites are responsible for the experimentally observed activity and selectivity. Extensive controls strongly suggest that the atomically dispersed NiN3 site-rich catalyst provides more intrinsically active sites than those in N-doped carbon, instead of possible environmental contamination. Overall, this work further indicates that single-metal site catalysts with optimal nitrogen coordination is very promising for NRR and indeed improves the scaling relationship of transition metals.
- Authors:
-
[5];
[5];
[1]
- State Univ. of New York (SUNY), Buffalo, NY (United States)
- Univ. of Pittsburgh, PA (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Univ. of South Carolina, Columbia, SC (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1712715
- Alternate Identifier(s):
- OSTI ID: 1597537
- Grant/Contract Number:
- AC05-00OR22725; 1804534; 1804326; ACI-1053575; AC02‐06CH11357; DE‐AC02‐06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Small Methods
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 6; Journal ID: ISSN 2366-9608
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; electrocatalytic NH3 synthesis; first-principle calculations; metal organic frameworks; single-atom catalysts
Citation Formats
Mukherjee, Shreya, Yang, Xiaoxuan, Shan, Weitao, Samarakoon, Widitha, Karakalos, Stavros, Cullen, David A., More, Karren, Wang, Maoyu, Feng, Zhenxing, Wang, Guofeng, and Wu, Gang. Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N2 and H2O. United States: N. p., 2020.
Web. doi:10.1002/smtd.201900821.
Mukherjee, Shreya, Yang, Xiaoxuan, Shan, Weitao, Samarakoon, Widitha, Karakalos, Stavros, Cullen, David A., More, Karren, Wang, Maoyu, Feng, Zhenxing, Wang, Guofeng, & Wu, Gang. Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N2 and H2O. United States. https://doi.org/10.1002/smtd.201900821
Mukherjee, Shreya, Yang, Xiaoxuan, Shan, Weitao, Samarakoon, Widitha, Karakalos, Stavros, Cullen, David A., More, Karren, Wang, Maoyu, Feng, Zhenxing, Wang, Guofeng, and Wu, Gang. Wed .
"Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N2 and H2O". United States. https://doi.org/10.1002/smtd.201900821. https://www.osti.gov/servlets/purl/1712715.
@article{osti_1712715,
title = {Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N2 and H2O},
author = {Mukherjee, Shreya and Yang, Xiaoxuan and Shan, Weitao and Samarakoon, Widitha and Karakalos, Stavros and Cullen, David A. and More, Karren and Wang, Maoyu and Feng, Zhenxing and Wang, Guofeng and Wu, Gang},
abstractNote = {Ammonia (NH3) electrosynthesis gains significant attention as NH3 is essentially important for fertilizer production and fuel utilization. However, electrochemical nitrogen reduction reaction (NRR) remains a great challenge because of low activity and poor selectivity. Herein, a new class of atomically dispersed Ni site electrocatalyst is reported, which exhibits the optimal NH3 yield of 115 µg cm-2 h-1 at –0.8 V versus reversible hydrogen electrode (RHE) under neutral conditions. High faradic efficiency of 21 ± 1.9% is achieved at -0.2 V versus RHE under alkaline conditions, although the ammonia yield is lower. The Ni sites are stabilized with nitrogen, which is verified by advanced X-ray absorption spectroscopy and electron microscopy. Density functional theory calculations provide insightful understanding on the possible structure of active sites, relevant reaction pathways, and confirm that the Ni-N3 sites are responsible for the experimentally observed activity and selectivity. Extensive controls strongly suggest that the atomically dispersed NiN3 site-rich catalyst provides more intrinsically active sites than those in N-doped carbon, instead of possible environmental contamination. Overall, this work further indicates that single-metal site catalysts with optimal nitrogen coordination is very promising for NRR and indeed improves the scaling relationship of transition metals.},
doi = {10.1002/smtd.201900821},
journal = {Small Methods},
number = 6,
volume = 4,
place = {United States},
year = {Wed Feb 05 00:00:00 EST 2020},
month = {Wed Feb 05 00:00:00 EST 2020}
}
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