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Title: A physical catalyst for the electrolysis of nitrogen to ammonia

Ammonia synthesis consumes 3 to 5% of the world’s natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N 2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at –1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 μg hour –1 cm –2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N 2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N 2 concentration within the Stern layer. In conclusion, the energy efficiency of the reactionmore » is estimated to be 5.25% at the current FE of 11.56%.« less
Authors:
ORCiD logo [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [2] ;  [2] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [3] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1468286

Song, Yang, Johnson, Daniel A., Peng, Rui, Hensley, Dale K., Bonnesen, Peter V., Liang, Liangbo, Huang, Jingsong, Yang, Fengchang, Zhang, Fei, Qiao, Rui, Baddorf, Arthur P., Tschaplinski, Timothy J., Engle, Nancy L., Hatzell, Marta C., Wu, Zili, Cullen, David A., Meyer, III, Harry M., Sumpter, Bobby G., and Rondinone, Adam Justin. A physical catalyst for the electrolysis of nitrogen to ammonia. United States: N. p., Web. doi:10.1126/sciadv.1700336.
Song, Yang, Johnson, Daniel A., Peng, Rui, Hensley, Dale K., Bonnesen, Peter V., Liang, Liangbo, Huang, Jingsong, Yang, Fengchang, Zhang, Fei, Qiao, Rui, Baddorf, Arthur P., Tschaplinski, Timothy J., Engle, Nancy L., Hatzell, Marta C., Wu, Zili, Cullen, David A., Meyer, III, Harry M., Sumpter, Bobby G., & Rondinone, Adam Justin. A physical catalyst for the electrolysis of nitrogen to ammonia. United States. doi:10.1126/sciadv.1700336.
Song, Yang, Johnson, Daniel A., Peng, Rui, Hensley, Dale K., Bonnesen, Peter V., Liang, Liangbo, Huang, Jingsong, Yang, Fengchang, Zhang, Fei, Qiao, Rui, Baddorf, Arthur P., Tschaplinski, Timothy J., Engle, Nancy L., Hatzell, Marta C., Wu, Zili, Cullen, David A., Meyer, III, Harry M., Sumpter, Bobby G., and Rondinone, Adam Justin. 2018. "A physical catalyst for the electrolysis of nitrogen to ammonia". United States. doi:10.1126/sciadv.1700336. https://www.osti.gov/servlets/purl/1468286.
@article{osti_1468286,
title = {A physical catalyst for the electrolysis of nitrogen to ammonia},
author = {Song, Yang and Johnson, Daniel A. and Peng, Rui and Hensley, Dale K. and Bonnesen, Peter V. and Liang, Liangbo and Huang, Jingsong and Yang, Fengchang and Zhang, Fei and Qiao, Rui and Baddorf, Arthur P. and Tschaplinski, Timothy J. and Engle, Nancy L. and Hatzell, Marta C. and Wu, Zili and Cullen, David A. and Meyer, III, Harry M. and Sumpter, Bobby G. and Rondinone, Adam Justin},
abstractNote = {Ammonia synthesis consumes 3 to 5% of the world’s natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at –1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 μg hour–1 cm–2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N2 concentration within the Stern layer. In conclusion, the energy efficiency of the reaction is estimated to be 5.25% at the current FE of 11.56%.},
doi = {10.1126/sciadv.1700336},
journal = {Science Advances},
number = 4,
volume = 4,
place = {United States},
year = {2018},
month = {4}
}

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