Ru-Loaded C12A7:e– Electride as a Catalyst for Ammonia Synthesis

The artificial mass production of ammonia has supported the increase in human population and modern civilization for over 100 years. However, more efficient ammonia production is now a significant concern for society. Here we show that Ru-loaded C12A7:e– electride derived from 12CaO·7Al2O3 (C12A7:O2–) acts as an efficient and stable catalyst for ammonia synthesis. Ammonia synthesis over Ru nanoparticles-loaded C12A7:e– (Ru/C12A7:e–) is distinct from other conventional catalysts in both mechanism and properties. The dissociative adsorption of N2 molecules, which is the largest energy barrier in ammonia synthesis for conventional catalysts, is no longer the rate-limiting step for the Ru/C12A7:e– catalyst. In addition, Ru on the electride prevents the inhibition of ammonia synthesis by hydrogen adatoms, known as hydrogen poisoning, which is a common and serious drawback of Ru catalysts. This characteristic results in the highly efficient formation of ammonia over the Ru/C12A7:e– catalyst.

[1]  J. L. Dye,et al.  Electrons as Anions , 2003, Science.

[2]  Hideo Hosono,et al.  High-Density Electron Anions in a Nanoporous Single Crystal: [Ca24Al28O64]4+(4e-) , 2003, Science.

[3]  S. Dahl,et al.  Atomic-Resolution in Situ Transmission Electron Microscopy of a Promoter of a Heterogeneous Catalyst , 2001, Science.

[4]  G. Ertl,et al.  The role of potassium in the catalytic synthesis of ammonia , 1979 .

[5]  H. Hosono,et al.  Ammonia decomposition by ruthenium nanoparticles loaded on inorganic electride C12A7:e− , 2013 .

[6]  H. Hosono,et al.  Superconductivity in an inorganic electride 12CaO x 7Al2O3:e-. , 2007, Journal of the American Chemical Society.

[7]  P. Chirik,et al.  Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex , 2004, Nature.

[8]  C. Jacobsen,et al.  Ammonia synthesis with barium-promoted iron–cobalt alloys supported on carbon , 2003 .

[9]  T. Bécue,et al.  Effect of Cationic Promoters on the Kinetics of Ammonia Synthesis Catalyzed by Ruthenium Supported on Zeolite X , 1998 .

[10]  O. Kato,et al.  Support and promoter effect of ruthenium catalyst. III. Kinetics of ammonia synthesis over various Ru catalysts , 1986 .

[11]  F. Haber,et al.  Über die Bildung von Ammoniak den Elementen , 1905 .

[12]  J. L. Dye Electrides: early examples of quantum confinement. , 2009, Accounts of chemical research.

[13]  H. Hosono,et al.  Electron localization and a confined electron gas in nanoporous inorganic electrides. , 2003, Physical review letters.

[14]  M. Muhler,et al.  The Ammonia-Synthesis Catalyst of the Next Generation: Barium-Promoted Oxide-Supported Ruthenium. , 2001, Angewandte Chemie.

[15]  T. Kamiya,et al.  Thin film and bulk fabrication of room-temperature-stable electride C12A7:e− utilizing reduced amorphous 12CaO · 7Al2O3(C12A7) , 2008 .

[16]  T. Kamiya,et al.  Localized and Delocalized Electrons in Room-Temperature Stable Electride [Ca24Al28O64]4+(O2-)2-x(e-)2x : Analysis of Optical Reflectance Spectra , 2008 .

[17]  G. Ertl,et al.  The Kinetics of Ammonia Synthesis over Ru-Based Catalysts: 1. The Dissociative Chemisorption and Associative Desorption of N2 , 1997 .

[18]  H. Hosono,et al.  From insulator to electride: a theoretical model of nanoporous oxide 12CaO.7Al2O3. , 2007, Journal of the American Chemical Society.

[19]  G. Ertl,et al.  A vibrational spectroscopy study on the interaction of N2 with clean and K-promoted Fe(111) surfaces: π-bonded dinitrogen as precursor for dissociation , 1985 .

[20]  Zhaobin Wei,et al.  Ammonia synthesis over Ru/C catalysts with different carbon supports promoted by barium and potassium compounds , 2001 .

[21]  H. Hosono,et al.  Synthesis and properties of 12CaO · 7Al2O3 electride: review of single crystal and thin film growth , 2012 .

[22]  AikaKen-ichi,et al.  AMMONIA SYNTHESIS OVER RHODIUM, IRIDIUM AND PLATINUM PROMOTED BY POTASSIUM , 1973 .

[23]  W. Frankenburg,et al.  Early Studies of Multicomponent Catalysts , 1950 .

[24]  H. Hosono,et al.  Kinetic evidence: the rate-determining step for ammonia synthesis over electride-supported Ru catalysts is no longer the nitrogen dissociation step , 2017 .

[25]  S. Gambarotta,et al.  Multimetallic cooperative activation of N2. , 2004, Angewandte Chemie.

[26]  C. Rao,et al.  Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques , 1991 .

[27]  H. Hosono,et al.  Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts , 2016, Chemical science.

[28]  T. Kamiya,et al.  Metallic state in a lime-alumina compound with nanoporous structure. , 2007, Nano letters.

[29]  H. Hosono,et al.  Superconductivity in room-temperature stable electride and high-pressure phases of alkali metals , 2015, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[30]  K. Aika,et al.  A New Catalyst System for Ammonia Synthesis , 1971 .

[31]  H. Hosono,et al.  Direct Synthesis of Powdery Inorganic Electride [Ca24Al28O64]4+(e−)4 and Determination of Oxygen Stoichiometry , 2009 .

[32]  G. Somorjai,et al.  Structure sensitivity in the iron single-crystal catalysed synthesis of ammonia , 1981, Nature.

[33]  Hideo Hosono,et al.  Work Function of a Room-Temperature, Stable Electride [Ca24Al28O64] 4+(e-)4. , 2008 .

[34]  Patrick B. Smith,et al.  Cesium 18-crown-6 compounds. A crystalline ceside and a crystalline electride , 1983 .

[35]  G. Ertl,et al.  Ruthenium catalysts for ammonia synthesis at high pressures: Preparation, characterization, and power-law kinetics , 1997 .

[36]  H. Hosono,et al.  Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. , 2012, Nature chemistry.

[37]  H. Hosono,et al.  Iodometric Determination of Electrons Incorporated into Cages in 12CaO·7Al2O3 Crystals , 2010 .

[38]  H. Hosono,et al.  Efficient and Stable Ammonia Synthesis by Self-Organized Flat Ru Nanoparticles on Calcium Amide , 2016 .

[39]  H. Hosono,et al.  Active anion manipulation for emergence of active functions in the nanoporous crystal 12CaO·7Al2O3: a case study of abundant element strategy , 2007 .

[40]  Robert J. Davis,et al.  Use of kinetic models to explore the role of base promoters on Ru/MgO ammonia synthesis catalysts , 2004 .

[41]  K. Hayashi Heavy doping of H− ion in 12CaO·7Al2O3 , 2011 .

[42]  H. Hosono,et al.  Enhanced N2 dissociation on Ru-loaded inorganic electride. , 2014, Journal of the American Chemical Society.

[43]  H. Hosono,et al.  Hydride ions in oxide hosts hidden by hydroxide ions , 2014, Nature Communications.

[44]  K. Aika,et al.  Activation of nitrogen by alkali metal promoted transition metal I. Ammonia synthesis over ruthenium promoted by alkali metal , 1972 .

[45]  H. Michaelson The work function of the elements and its periodicity , 1977 .

[46]  H. Hosono,et al.  Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis , 2015, Nature Communications.

[47]  H. Hosono,et al.  Mechanism Switching of Ammonia Synthesis Over Ru-Loaded Electride Catalyst at Metal-Insulator Transition. , 2015, Journal of the American Chemical Society.