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
 

Formation of 6H-Ba3Ce0.75Mn2.25O9 during Thermochemical Reduction of 12R-Ba4CeMn3O12: Identification of a Polytype in the Ba(Ce,Mn)O3 Family

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [3];  [4];  [4];  [1];  [2];  [3];  [3];  [3]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
+ Show Author Affiliations
The resurgence of interest in a hydrogen economy and the development of hydrogen-related technologies has initiated numerous research and development efforts aimed at making the generation, storage, and transportation of hydrogen more efficient and affordable. Solar thermochemical hydrogen production (STCH) is a process that potentially exhibits numerous benefits such as high reaction efficiencies, tunable thermodynamics, and continued performance over extended cycling. Although CeO2 has been the de facto standard STCH material for many years, more recently 12R-Ba4CeMn3O12 (BCM) has demonstrated enhanced hydrogen production at intermediate H2/H2O conditions compared to CeO2, making it a contender for large-scale hydrogen production. However, the thermo-reduction stability of 12R-BCM dictates the oxygen partial pressure (pO2) and temperature conditions optimal for cycling. In this study, we identify the formation of a 6H-BCM polytype at high temperature and reducing conditions, experimentally and computationally, as a mechanism and pathway for 12R-BCM decomposition. 12R-BCM was synthesized with high purity and then controllably reduced using thermogravimetric analysis (TGA). Synchrotron X-ray diffraction (XRD) data is used to identify the formation of a 6H-Ba3Ce0.75Mn2.25O9 (6H-BCM) polytype that is formed at 1350 degrees C under strongly reducing pO2. Density functional theory (DFT) total energy and defect calculations show a window of thermodynamic stability for the 6H-polytype consistent with the XRD results. These data provide the first evidence of the 6H-BCM polytype and could provide a mechanistic explanation for the superior water-splitting behaviors of 12R-BCM.
Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC02-76SF00515; NA0003525
OSTI ID:
1865122
Alternate ID(s):
OSTI ID: 1870493
OSTI ID: 1875913
Report Number(s):
NREL/JA-5K00-81381; SAND2022-4800J; MainId:82154; UUID:4466cc95-b2a3-4a8b-b184-cafbed279b79; MainAdminID:64383
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 61; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (31)

Perovskites book March 2016
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Solar fuels production: Two-step thermochemical cycles with cerium-based oxides journal November 2019
An overview of hydrogen production technologies journal January 2009
A computational framework for automation of point defect calculations journal April 2017
Novel rare-earth-containing manganites Ba4REMn3O12 (RE=Ce, Pr) with 12R structure journal March 2004
Structure and magnetism of 4H-BaMnO3−x () and 4H-Ba0.5Sr0.5MnO3−x () journal January 2006
Structure and magnetic properties of Ba5Ce1.25Mn3.75O15, a new 10H-polytype in the Ba–Ce–Mn–O system journal February 2013
A new high pressure form of Ba3NiSb2O9 journal May 2016
Redox Defect Thermochemistry of FeAl 2 O 4 Hercynite in Water Splitting from First-Principles Methods journal January 2022
Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H 2 O and CO 2 journal March 2013
Influence of the synthesis route on the formation of 12R/10H-polytypes and their magnetic properties within the Ba(Ce,Mn)O 3 family journal January 2015
BaCe 0.25 Mn 0.75 O 3−δ —a promising perovskite-type oxide for solar thermochemical hydrogen production journal January 2018
Sr- and Mn-doped LaAlO3−δ for solar thermochemical H2 and CO production journal January 2013
Non-equilibrium origin of high electrical conductivity in gallium zinc oxide thin films journal December 2013
Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles journal February 2018
Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units [J. Phys. Chem. Ref. Data 11, Suppl. 2 (1982)] journal October 1989
Computational discovery of stable and metastable ternary oxynitrides journal June 2021
Solar thermochemical splitting of water to generate hydrogen journal May 2017
Projector augmented-wave method journal December 1994
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Energetics of quaternary III-V alloys described by incorporation and clustering of impurities journal September 2009
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies journal March 2012
Polymorphic energy ordering of MgO, ZnO, GaN, and MnO within the random phase approximation journal May 2013
Convergence of density and hybrid functional defect calculations for compound semiconductors journal September 2013
Generalized Gradient Approximation Made Simple journal October 1996
GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal March 2013
EXPO2013 : a kit of tools for phasing crystal structures from powder data journal July 2013
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria journal December 2010
Zur Kenntnis eines Barium-Lanthanoid-Oxomanganats(IV, V): Ba 3 ErMn 2 O 9 / On a Barium Rare-Earth Oxomanganate(IV, V): Ba 3 ErMn 2 O 9 journal September 1994

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
STCH
layered perovskite
oxide
polytype
thermochemistry