Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Redox Defect Thermochemistry of FeAl2O4 Hercynite in Water Splitting from First-Principles Methods

Journal Article · · Chemistry of Materials
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
+ Show Author Affiliations

Solar thermochemical hydrogen (STCH) production is a promising route to produce fuels from sunlight via high-temperature water splitting. However, efficient and technologically viable implementations of this process only allow a narrow window of thermodynamic boundary conditions that can be used to cycle the system, thus limiting the design space for suitable metal oxide redox mediators. An oxygen defect redox mechanism can contribute a favorable reduction entropy to expand this window, and computational evaluation of materials with high oxygen defect entropies could play a pivotal role in guiding the discovery and design of suitable oxides. This study employs first-principles calculations to investigate the redox mediating defect mechanism of the STCH candidate material, hercynite (FeAl2O4). We compare the results of total energy calculations from density functional theory (DFT) with beyond-DFT approaches, including hybrid functionals and the random phase approximation, which are among the most advanced methods currently feasible for supercell defect calculations. Using the predicted formation energies, we perform thermodynamic modeling of FeAl2O4 reduction and oxidation via free energy minimization that incorporates ideal gas, configurational, and vibrational entropy contributions evaluated within the quasi-harmonic approximation. Special attention is devoted to understanding interactions among co-existing defects, such as the association of pairs and complexes of O vacancies and cation antisite defects, and the effect of mutually compensating defect charges. Our results corroborate the notion that the details of defect interactions can be decisive for the viability of hydrogen production within the desirable STCH process window.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (EE-3F)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1840916
Report Number(s):
NREL/JA--5K00-79573; MainId:35794; UUID:558f9692-e373-4638-a4f1-72692e288afb; MainAdminID:63622
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 2 Vol. 34; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (58)

A First‐Principles‐Based Sub‐Lattice Formalism for Predicting Off‐Stoichiometry in Materials for Solar Thermochemical Applications: The Example of Ceria journal August 2020
Solar-thermal production of renewable hydrogen journal February 2009
Density functional theory and the band gap problem journal March 1985
A review and perspective of efficient hydrogen generation via solar thermal water splitting: A review and perspective of efficient hydrogen generation
  • Muhich, Christopher L.; Ehrhart, Brian D.; Al-Shankiti, Ibraheam
  • Wiley Interdisciplinary Reviews: Energy and Environment, Vol. 5, Issue 3 https://doi.org/10.1002/wene.174
journal May 2015
Hydrogen production from water utilizing solar heat at high temperatures journal January 1977
Comparative experimental investigations of the water-splitting reaction with iron oxide Fe1−yO and iron manganese oxides (Fe1−xMnx)1−yO journal May 1995
Production of solar hydrogen by a novel, 2-step, water-splitting thermochemical cycle journal April 1995
A spinel ferrite/hercynite water-splitting redox cycle journal April 2010
Thermochemical water-splitting for H2 generation using sol-gel derived Mn-ferrite in a packed bed reactor journal February 2012
Comparison of thermochemical, electrolytic, photoelectrolytic and photochemical solar-to-hydrogen production technologies journal November 2012
Oxygen exchange materials for solar thermochemical splitting of H2O and CO2: a review journal September 2014
First principles phonon calculations in materials science journal November 2015
Decomposition of Zn-ferrite for O2 generation by concentrated solar radiation journal January 2004
Solar thermochemical production of hydrogen––a review journal May 2005
Thermochemical hydrogen production by a redox system of ZrO2-supported Co(II)-ferrite journal May 2005
Kinetics and mechanism of solar-thermochemical H2 and CO production by oxidation of reduced CeO2 journal January 2018
Design Aspects Of Solar Thermochemical Engineering—A Case Study: Two-Step Water-Splitting Cycle Using The Fe3O4/FeO Redox System journal January 1999
Solar hydrogen production via a two-step water-splitting thermochemical cycle based on Zn/ZnO redox reactions journal June 2002
First-Principles Analysis of Cation Diffusion in Mixed Metal Ferrite Spinels journal December 2015
Thermochemistry and Geometries for Transition-Metal Chemistry from the Random Phase Approximation journal October 2016
Two-Step Water Splitting Using Mixed-Metal Ferrites: Thermodynamic Analysis and Characterization of Synthesized Materials journal November 2008
Study of a Magnetically Stabilized Porous Structure for Thermochemical Water Splitting via TGA, High-Temperature-XRD, and SEM Analyses journal March 2013
Characterization of Two-Step Tin-Based Redox System for Thermochemical Fuel Production from Solar-Driven CO 2 and H 2 O Splitting Cycle journal March 2014
Giant onsite electronic entropy enhances the performance of ceria for water splitting journal August 2017
Efficient first-principles prediction of solid stability: Towards chemical accuracy journal March 2018
Screened hybrid density functionals for solid-state chemistry and physics journal January 2009
Oxygen transport and isotopic exchange in iron oxide/YSZ thermochemically-active materials via splitting of C(18O)2 at high temperature studied by thermogravimetric analysis and secondary ion mass spectrometry journal January 2012
Predicting the solar thermochemical water splitting ability and reaction mechanism of metal oxides: a case study of the hercynite family of water splitting cycles 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
Hybrid functionals based on a screened Coulomb potential journal May 2003
Screened hybrid density functionals applied to solids journal April 2006
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal June 2006
H 2 generation from two-step thermochemical water-splitting reaction using sol-gel derived Sn x Fe y O z journal November 2011
Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles journal February 2018
Accurate prediction of defect properties in density functional supercell calculations journal November 2009
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies journal March 2012
Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations journal January 2009
Magnetism without Magnetic Ions: Percolation, Exchange, and Formation Energies of Magnetism-Promoting Intrinsic Defects in CaO journal March 2006
Exchange-correlation energy of a metallic surface: Wave-vector analysis journal March 1977
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
Implementation and performance of the frequency-dependent G W method within the PAW framework journal July 2006
Cohesive energy curves for noble gas solids calculated by adiabatic connection fluctuation-dissipation theory journal January 2008
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs journal December 2008
Semiconductor thermochemistry in density functional calculations journal December 2008
Energetics of quaternary III-V alloys described by incorporation and clustering of impurities journal September 2009
First-principles thermodynamic framework for the evaluation of thermochemical H 2 O - or CO 2 -splitting materials journal December 2009
Band-structure calculations for the 3 d transition metal oxides in G W journal February 2013
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
Green’s-function approach to linear response in solids journal May 1987
Generalized Gradient Approximation Made Simple journal October 1996
First-principles calculations for point defects in solids journal March 2014
Phase Equilibria in the System Fe-Al-O journal November 1980
A Two-Step Thermochemical Water Splitting by Iron-Oxide on Stabilized Zirconia journal January 2006
Tin as a Possible Candidate for Solar Thermochemical Redox Process for Hydrogen Production journal April 2009
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria journal December 2010
Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions journal November 2010

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
first principles calculations
hydrogen
transition metal oxides