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Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters

Journal Article


Abstract


  • © 2020 American Chemical Society. The limitations of the Haber-Bosch reaction, particularly high-temperature operation, have ignited new interests in low-temperature ammonia-synthesis scenarios. Ambient N2 electroreduction is a compelling alternative but is impeded by a low ammonia production rate (mostly <10 mmol gcat-1 h-1), a small partial current density (<1 mA cm-2), and a high-selectivity hydrogen-evolving side reaction. Herein, we report that room-temperature nitrate electroreduction catalyzed by strained ruthenium nanoclusters generates ammonia at a higher rate (5.56 mol gcat-1 h-1) than the Haber-Bosch process. The primary contributor to such performance is hydrogen radicals, which are generated by suppressing hydrogen-hydrogen dimerization during water splitting enabled by the tensile lattice strains. The radicals expedite nitrate-to-ammonia conversion by hydrogenating intermediates of the rate-limiting steps at lower kinetic barriers. The strained nanostructures can maintain nearly 100% ammonia-evolving selectivity at >120 mA cm-2 current densities for 100 h due to the robust subsurface Ru-O coordination. These findings highlight the potential of nitrate electroreduction in real-world, low-temperature ammonia synthesis.

Authors


  •   Li, Jie (external author)
  •   Zhan, Guangming (external author)
  •   Yang, Jianhua (external author)
  •   Quan, Fengjiao (external author)
  •   Mao, Chengliang (external author)
  •   Liu, Yang (external author)
  •   Wang, Bo (external author)
  •   Lei, Fengcai (external author)
  •   Li, Lejing (external author)
  •   Chan, Alice (external author)
  •   Xu, Liangpang (external author)
  •   Shi, Yanbiao (external author)
  •   Du, Yi
  •   Hao, Weichang (external author)
  •   Wong, Po (external author)
  •   Wang, Jianfang (external author)
  •   Dou, Shi Xue
  •   Zhang, Lizhi (external author)
  •   Yu, Jimmy (external author)

Publication Date


  • 2020

Citation


  • Li, J., Zhan, G., Yang, J., Quan, F., Mao, C., Liu, Y., Wang, B., Lei, F., Li, L., Chan, A., Xu, L., Shi, Y., Du, Y., Hao, W., Wong, P., Wang, J., Dou, S., Zhang, L. & Yu, J. (2020). Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters. Journal of the American Chemical Society, 142 (15), 7036-7046.

Scopus Eid


  • 2-s2.0-85084399561

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/4150

Number Of Pages


  • 10

Start Page


  • 7036

End Page


  • 7046

Volume


  • 142

Issue


  • 15

Place Of Publication


  • United States

Abstract


  • © 2020 American Chemical Society. The limitations of the Haber-Bosch reaction, particularly high-temperature operation, have ignited new interests in low-temperature ammonia-synthesis scenarios. Ambient N2 electroreduction is a compelling alternative but is impeded by a low ammonia production rate (mostly <10 mmol gcat-1 h-1), a small partial current density (<1 mA cm-2), and a high-selectivity hydrogen-evolving side reaction. Herein, we report that room-temperature nitrate electroreduction catalyzed by strained ruthenium nanoclusters generates ammonia at a higher rate (5.56 mol gcat-1 h-1) than the Haber-Bosch process. The primary contributor to such performance is hydrogen radicals, which are generated by suppressing hydrogen-hydrogen dimerization during water splitting enabled by the tensile lattice strains. The radicals expedite nitrate-to-ammonia conversion by hydrogenating intermediates of the rate-limiting steps at lower kinetic barriers. The strained nanostructures can maintain nearly 100% ammonia-evolving selectivity at >120 mA cm-2 current densities for 100 h due to the robust subsurface Ru-O coordination. These findings highlight the potential of nitrate electroreduction in real-world, low-temperature ammonia synthesis.

Authors


  •   Li, Jie (external author)
  •   Zhan, Guangming (external author)
  •   Yang, Jianhua (external author)
  •   Quan, Fengjiao (external author)
  •   Mao, Chengliang (external author)
  •   Liu, Yang (external author)
  •   Wang, Bo (external author)
  •   Lei, Fengcai (external author)
  •   Li, Lejing (external author)
  •   Chan, Alice (external author)
  •   Xu, Liangpang (external author)
  •   Shi, Yanbiao (external author)
  •   Du, Yi
  •   Hao, Weichang (external author)
  •   Wong, Po (external author)
  •   Wang, Jianfang (external author)
  •   Dou, Shi Xue
  •   Zhang, Lizhi (external author)
  •   Yu, Jimmy (external author)

Publication Date


  • 2020

Citation


  • Li, J., Zhan, G., Yang, J., Quan, F., Mao, C., Liu, Y., Wang, B., Lei, F., Li, L., Chan, A., Xu, L., Shi, Y., Du, Y., Hao, W., Wong, P., Wang, J., Dou, S., Zhang, L. & Yu, J. (2020). Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters. Journal of the American Chemical Society, 142 (15), 7036-7046.

Scopus Eid


  • 2-s2.0-85084399561

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/4150

Number Of Pages


  • 10

Start Page


  • 7036

End Page


  • 7046

Volume


  • 142

Issue


  • 15

Place Of Publication


  • United States