Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Air-Stable Calcium Cyanamide-Supported Ruthenium Catalyst for Ammonia Synthesis and Decomposition

Journal Article · · ACS Applied Energy Materials
 [1];  [2];  [1];  [3];  [4];  [5];  [1];  [1];  [1]
  1. Tokyo Inst. of Technology, Yokohama (Japan). Materials Research Center for Element Strategy
  2. Tokyo Inst. of Technology, Yokohama (Japan). Materials Research Center for Element Strategy; Japan Science and Technology Agency (JST), Saitama (Japan). PRESTO
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  4. High Energy Accelerator Research Organization (KEK), Tsukuba (Japan). Inst. of Materials Structure Science; SOKENDAI (The Graduate Univ. for Advanced Studies), Tsukuba (Japan). Dept. of Materials Structure Science; Ibaraki Univ. (Japan). Graduate School of Science and Technology
  5. High Energy Accelerator Research Organization (KEK), Tsukuba (Japan). Inst. of Materials Structure Science
+ Show Author Affiliations
Efficient ammonia synthesis and decomposition processes under mild conditions are important to meet the expanding demand in major applications of ammonia as the energy carrier and to provide feedstock for chemical industry. In this study, we report that air-stable calcium cyanamide-supported ruthenium (Ru/CaCN2) works as an efficient and stable catalyst for ammonia synthesis and decomposition. Ru/CaCN2 exhibits greater catalytic performances for both reactions than Ru/Ca2N electride and Ru–Cs/MgO. The kinetic analysis for ammonia synthesis suggests that Ru/CaCN2 exhibits low apparent activation energy and high resistance to hydrogen poisoning, which has characteristics similar to the kinetic parameters of Ru-supported electride catalyst. H2-temperature programmed reaction and temperature programmed desorption revealed that Ru promoted the formation of CN2 vacancies on the CaCN2 surface which in turn capture hydrogen as H– ions during the reaction. Density functional theory calculations provide insights into how the formation of CN2 vacancies is promoted by Ru, which leads to the decrease in the work function of the CaCN2 surface and the hydrogen capture at the Ru-support interface. These results suggest that the high catalytic performance of Ru/CaCN2 can be attributed to the formation of a quasi-electride structure at the Ru–CaCN2 interface.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
Japan Science and Technology Agency (JST); Japan Society for the Promotion of Science (JSPS); USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1673585
Report Number(s):
PNNL-SA--154003
Journal Information:
ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 7 Vol. 3; ISSN 2574-0962
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (50)

The Ammonia-Synthesis Catalyst of the Next Generation: Barium-Promoted Oxide-Supported Ruthenium journal March 2001
Tiered Electron Anions in Multiple Voids of LaScSi and Their Applications to Ammonia Synthesis journal July 2017
Multimetallic Cooperative Activation of N2 journal October 2004
Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture) journal April 2008
Self-organized Ruthenium-Barium Core-Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis journal February 2018
Intermetallic Electride Catalyst as a Platform for Ammonia Synthesis journal January 2019
Large Oblate Hemispheroidal Ruthenium Particles Supported on Calcium Amide as Efficient Catalysts for Ammonia Decomposition journal May 2018
Activation of nitrogen by alkali metal promoted transition metal I. Ammonia synthesis over ruthenium promoted by alkali metal journal December 1972
Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesis 3. A magnesia-supported ruthenium catalyst journal July 1992
Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques journal January 1991
A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications journal December 2004
Nanosized Ru on high-surface-area superbasic ZrO2-KOH for efficient generation of hydrogen via ammonia decomposition journal February 2006
Multi-functional Mo-doping in MnO2 nanoflowers toward efficient and robust electrocatalytic nitrogen fixation journal May 2020
Filling the nitrogen vacancies with sulphur dopants in graphitic C3N4 for efficient and robust electrocatalytic nitrogen reduction journal June 2020
Why the optimal ammonia synthesis catalyst is not the optimal ammonia decomposition catalyst journal March 2005
Ammonia decomposition over the carbon-based ruthenium catalyst promoted with barium or cesium journal September 2003
Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis journal September 2001
Ruthenium catalysts for ammonia synthesis at high pressures: Preparation, characterization, and power-law kinetics journal April 1997
Structure sensitivity of supported ruthenium catalysts for ammonia synthesis journal December 2000
Hydride-Based Electride Material, LnH 2 (Ln = La, Ce, or Y) journal August 2016
Two-dimensional (2D)/2D Interface Engineering of a MoS 2 /C 3 N 4 Heterostructure for Promoted Electrocatalytic Nitrogen Fixation journal January 2020
Efficient and Stable Ammonia Synthesis by Self-Organized Flat Ru Nanoparticles on Calcium Amide journal October 2016
Ammonia Synthesis on Wool-Like Au, Pt, Pd, Ag, or Cu Electrode Catalysts in Nonthermal Atmospheric-Pressure Plasma of N 2 and H 2 journal September 2017
Surface Dynamics for Creating Highly Active Ru Sites for Ammonia Synthesis: Accumulation of a Low-Crystalline, Oxygen-Deficient Nanofraction journal January 2020
Development of alkali-promoted ruthenium as a novel catalyst for ammonia synthesis journal January 1981
Steady-state decomposition of ammonia on the ruthenium(001) surface journal September 1987
Water Durable Electride Y 5 Si 3 : Electronic Structure and Catalytic Activity for Ammonia Synthesis journal March 2016
Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes journal June 2017
Zeolitic Intermetallics: LnNiSi (Ln = La–Nd) journal February 2019
Experimental and Computational Studies of Dinitrogen Activation and Hydrogenation at a Tetranuclear Titanium Imide/Hydride Framework journal January 2019
Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts journal November 2019
Dicalcium nitride as a two-dimensional electride with an anionic electron layer journal January 2013
Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store journal October 2012
Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction journal April 2010
Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis journal March 2015
Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water journal April 2019
Ammonia for hydrogen storage: challenges and opportunities journal January 2008
Ammonia decomposition by ruthenium nanoparticles loaded on inorganic electride C12A7:e− journal January 2013
Challenges in reduction of dinitrogen by proton and electron transfer journal January 2014
Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts journal January 2016
Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis journal January 2017
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal May 1994
Projector augmented-wave method journal December 1994
Multiple-scattering calculations of x-ray-absorption spectra journal July 1995
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal October 2011
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
High-Density Electron Anions in a Nanoporous Single Crystal: [Ca24Al28O64]4+(4e-) journal August 2003
Highly Active Cs 2 O/Ru/Pr 6 O 11 as a Catalyst for Ammonia Decomposition journal September 2010

Similar Records

Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst
Journal Article · Fri Apr 03 20:00:00 EDT 2020 · Journal of the American Chemical Society · OSTI ID:1649278
Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis
Journal Article · Sun Mar 29 20:00:00 EDT 2015 · Nature Communications · OSTI ID:1260712
Promoter action of alkali nitrate in Raney Ruthenium catalyst for activation of dinitrogen
Journal Article · Wed Nov 13 23:00:00 EST 1991 · Journal of Physical Chemistry; (United States) · OSTI ID:7163718

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia decomposition
ammonia synthesis
calcium cyanamide
electride
ruthenuim