Electro-synthesis of ammonia from nitrogen at ambient temperature and pressure in ionic liquids

Ammonia as the source of most fertilizers has become one of the most important chemicals globally. It also is being increasingly considered as an easily transported carrier of hydrogen energy that can be generated from “stranded” renewable-energy resources. However, the traditional Haber–Bosch process for the production of ammonia from atmospheric nitrogen and fossil fuels is a high temperature and pressure process that is energy intensive, currently producing more than 1.6% of global CO2 emissions. An ambient temperature, electrochemical synthesis of ammonia is an attractive alternative approach, but has, to date, not been achieved at high efficiency. We report in this work the use of ionic liquids that have high N2 solubility as electrolytes to achieve high conversion efficiency of 60% for N2 electro-reduction to ammonia on a nanostructured iron catalyst under ambient conditions.

[1]  M. Gomes,et al.  Solubility of carbon dioxide, nitrous oxide, ethane, and nitrogen in 1-butyl-1-methylpyrrolidinium and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate (eFAP) ionic liquids , 2013 .

[2]  Jong-In Han,et al.  Communication—Electrochemical Reduction of Nitrogen to Ammonia in 2-Propanol under Ambient Temperature and Pressure , 2016 .

[3]  Anthony Manerbino,et al.  Electrochemical enhancement of ammonia synthesis in a BaZr0.7Ce0.2Y0.1O2.9 solid electrolyte cell , 2016 .

[4]  Claudio Ampelli,et al.  Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst. , 2017, Angewandte Chemie.

[5]  R. Lan,et al.  Synthesis of ammonia directly from wet air at intermediate temperature , 2014 .

[6]  Michael Stoukides,et al.  Progress in the Electrochemical Synthesis of Ammonia , 2017 .

[7]  G. Kyriacou,et al.  Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell , 2000 .

[8]  P. Kenis,et al.  Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials , 2011, Science.

[9]  Shaozheng Hu,et al.  Photofixation of atmospheric nitrogen to ammonia with a novel ternary metal sulfide catalyst under visible light , 2016 .

[10]  L. Bourgeois,et al.  Nanostructured photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced black silicon , 2016, Nature Communications.

[11]  A. Katsaounis,et al.  High-Pressure Electrochemical Promotion of Ammonia Synthesis over an Industrial Iron Catalyst , 2000 .

[12]  H. Misawa,et al.  Selective Dinitrogen Conversion to Ammonia Using Water and Visible Light through Plasmon-induced Charge Separation. , 2016, Angewandte Chemie.

[13]  J. Peters,et al.  Catalytic conversion of nitrogen to ammonia by a molecular Fe model complex , 2013, Nature.

[14]  Joseph H. Montoya,et al.  The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations. , 2015, ChemSusChem.

[15]  Zhipeng Sun,et al.  Preparation of La1.9Ca0.1Zr2O6.95 with pyrochlore structure and its application in synthesis of ammonia at atmospheric pressure , 2004 .

[16]  C. Yoo,et al.  Electrochemical ammonia synthesis from steam and nitrogen using proton conducting yttrium doped barium zirconate electrolyte with silver, platinum, and lanthanum strontium cobalt ferrite electrocatalyst , 2015 .

[17]  R. Lan,et al.  Electrochemical Synthesis of Ammonia Based on Co3Mo3N Catalyst and LiAlO2–(Li,Na,K)2CO3 Composite Electrolyte , 2015, Electrocatalysis.

[18]  S. Back,et al.  On the mechanism of electrochemical ammonia synthesis on the Ru catalyst. , 2016, Physical chemistry chemical physics : PCCP.

[19]  J. Gregoire,et al.  Electrocatalytic Reduction of Nitrogen and Carbon Dioxide to Chemical Fuels: Challenges and Opportunities for a Solar Fuel Device. , 2015, Journal of photochemistry and photobiology. B, Biology.

[20]  Tejs Vegge,et al.  Electroreduction of N2 to ammonia at ambient conditions on mononitrides of Zr, Nb, Cr, and V – A DFT guide for experiments , 2016 .

[21]  Matthias Wessling,et al.  Galvanic deposition of Rh and Ru on randomly structured Ti felts for the electrochemical NH3 synthesis. , 2015, Physical chemistry chemical physics : PCCP.

[22]  R. Hamers,et al.  Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. , 2013, Nature materials.

[23]  P. Simon,et al.  Energy applications of ionic liquids , 2014 .

[24]  J. Otomo,et al.  In situ formation of Ru nanoparticles on La1−xSrxTiO3-based mixed conducting electrodes and their application in electrochemical synthesis of ammonia using a proton-conducting solid electrolyte , 2017, Journal of Materials Science.

[25]  H. Jónsson,et al.  A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. , 2012, Physical chemistry chemical physics : PCCP.

[26]  S. Bobroff,et al.  Nuclear magnetic resonance measurement of ammonia diffusion in dense solid-liquid slurries , 1997 .

[27]  J. Davies,et al.  An investigation of the putative photosynthesis of ammonia on iron-doped titania and other metal oxides , 1995 .

[28]  J. Shang,et al.  Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets. , 2015, Journal of the American Chemical Society.

[29]  Shiguo Zhang,et al.  Ionic liquids and their solid-state analogues as materials for energy generation and storage , 2016, Nature Reviews Materials.

[30]  Joan F Brennecke,et al.  Solubility of CO2, CH4, C2H6, C2H4, O2, and N2 in 1-hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide: comparison to other ionic liquids. , 2007, Accounts of chemical research.

[31]  Didem Balun Kayan,et al.  Low overpotential reduction of dinitrogen to ammonia in aqueous media , 2010 .

[32]  Shanwen Tao,et al.  Solid-state electrochemical synthesis of ammonia: a review , 2011 .

[33]  W. Marsden.  I and J , 2012 .

[34]  John T. S. Irvine,et al.  Synthesis of ammonia directly from air and water at ambient temperature and pressure , 2013, Scientific Reports.

[35]  Younes Abghoui,et al.  Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design. , 2015, Physical chemistry chemical physics : PCCP.

[36]  S. Badwal,et al.  Review of Electrochemical Ammonia Production Technologies and Materials , 2013 .

[37]  Chenghua Sun,et al.  Promising prospects for 2D d2–d4 M3C2 transition metal carbides (MXenes) in N2 capture and conversion into ammonia , 2016 .

[38]  M. Koper,et al.  Challenges in reduction of dinitrogen by proton and electron transfer. , 2014, Chemical Society reviews.

[39]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[40]  J. Nørskov,et al.  Sustainable Ammonia Synthesis – Exploring the scientific challenges associated with discovering alternative, sustainable processes for ammonia production , 2016 .

[41]  J. Renner,et al.  Electrochemical Synthesis of Ammonia: A Low Pressure, Low Temperature Approach , 2015 .

[42]  M. Wasielewski,et al.  Photochemical nitrogen conversion to ammonia in ambient conditions with FeMoS-chalcogels. , 2015, Journal of the American Chemical Society.

[43]  Lirong Zheng,et al.  Layered‐Double‐Hydroxide Nanosheets as Efficient Visible‐Light‐Driven Photocatalysts for Dinitrogen Fixation , 2017, Advanced materials.

[44]  Stuart Licht,et al.  Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3 , 2014, Science.

[45]  R. Gebauer,et al.  Nitrogen electrochemically reduced to ammonia with hematite: density-functional insights. , 2015, Physical chemistry chemical physics : PCCP.

[46]  Macarena Munoz,et al.  Accelerating Oxygen-Reduction Catalysts through Preventing Poisoning with Non-Reactive Species by Using Hydrophobic Ionic Liquids. , 2016, Angewandte Chemie.