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Nitrogen Reduction Reaction: History
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Contributor: Jack Zhong

Nitrogen reduction reaction is the conversion of dinitrogen (N2) into ammonia or related nitrogen-containing products, most often studied as a six-proton, six-electron process driven electrochemically or photocatalytically at ambient temperature and pressure [1]. Because the N2 triple bond is among the strongest in small molecules, and because the adsorbed N2H, NH2 and NH3 intermediates bind either too weakly or too strongly on most metal surfaces, the attainable rate is constrained by the scaling relations that link their adsorption energies [2]. Rates and Faradaic efficiencies are therefore usually low, and in aqueous electrolytes most of the applied current is consumed by hydrogen evolution rather than by ammonia formation [1]. Reported ammonia yields for metal, carbon-based and single-atom catalysts span several orders of magnitude, and the electrolyte, cell geometry and applied potential shift the measured value substantially; alkali-metal and nitrate or nitrite impurities can also contribute to the detected ammonia, so quantitative control experiments are required [3]. Catalysts examined to date range from transition metals and their nitrides to metal-free carbon materials, and no single material has yet combined high selectivity, high current density and long-term stability [4]. Standardised procedures for ammonia quantification have accordingly become part of how the field reports performance, including isotope labelling with 15N2 and rigorous blank measurements [5].

  • ammonia synthesis
  • electrocatalysis
  • photocatalytic nitrogen fixation
  • dinitrogen activation
  • faradaic efficiency
  • hydrogen evolution reaction
  • single-atom catalyst

Ammonia Synthesis and Nitrogen Reduction·Catalysis·Chemical Engineering·Physical Sciences

 

References

  1. van der Ham, C.J.M.; Koper, M.T.M.; Hetterscheid, D.G.H.; Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev. 2014, 43, 5183-5191, 10.1039/c4cs00085d.
  2. Skúlason, E.; Bligaard, T.; Gudmundsdóttir, S.; Studt, F.; Rossmeisl, J.; Abild-Pedersen, F.; Vegge, T.; Jónsson, H.; Nørskov, J.K.; A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. Phys. Chem. Chem. Phys. 2012, 14, 1235-1245, 10.1039/c1cp22271f.
  3. Zhao, S.; Lu, X.; Wang, L.; Gale, J.; Amal, R.; Carbon-Based Metal-Free Catalysts for Electrocatalytic Reduction of Nitrogen for Synthesis of Ammonia at Ambient Conditions. Advanced Materials 2019, 31, 1805367, 10.1002/adma.201805367.
  4. Moon, Y.H.; Kim, N.Y.; Kim, S.M.; Jang, Y.J.; Recent Advances in Electrochemical Nitrogen Reduction Reaction to Ammonia from the Catalyst to the System. Catalysts 2022, 12, 1015, 10.3390/catal12091015.
  5. Utomo, W.P.; Wu, H.; Ng, Y.H.; Quantification Methodology of Ammonia Produced from Electrocatalytic and Photocatalytic Nitrogen/Nitrate Reduction. Energies 2022, 16, 27, 10.3390/en16010027.
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