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Title: High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis

Abstract

Solar thermochemical ammonia (NH 3) synthesis (STAS) is a potential route to produce NH 3 from air, water, and concentrated sunlight. This process involves the chemical looping of an active redox pair that cycles between a metal nitride and its complementary metal oxide to yield NH 3. To identify promising candidates for STAS cycles, we performed a high-throughput thermodynamic screening of 1,148 metal nitride/metal oxide pairs. This data-driven screening was based on Gibbs energies of crystalline metal oxides and nitrides at elevated temperatures, G(T), calculated using a recently introduced statistically learned descriptor and 0 K DFT formation energies tabulated in the Materials Project database. Using these predicted G(T) values, we assessed the viability of each of the STAS reactions - hydrolysis of the metal nitride, reduction of the metal oxide, and nitrogen fixation to reform the metal nitride - and analyzed a revised cycle that directly converts between metal oxides and nitrides, which alters the thermodynamics of the STAS cycle. For all 1148 redox pairs analyzed and each of the STAS-relevant reactions, we implemented a Gibbs energy minimization scheme to predict the equilibrium composition and yields of the STAS cycle, which reveals new active materials based on B, V, Fe,more » and Ce that warrant further investigation for their potential to mediate the STAS cycle. This work details a high-throughput approach to assessing the relevant temperature-dependent thermodynamics of thermochemical redox processes that leverages the wealth of publicly available temperature-independent thermodynamic data calculated using DFT. This approach is readily adaptable to discovering optimal materials for targeted thermochemical applications and enabling the predictive synthesis of new compounds using thermally controlled solid-state reactions.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1506620
Report Number(s):
NREL/JA-5K00-73634
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; chemical looping; high-throughput screening; reaction engineering; renewable fuels; thermochemical ammonia synthesis

Citation Formats

Bartel, Christopher J., Rumptz, John R., Weimer, Alan W., Holder, Aaron M., and Musgrave, Charles B. High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis. United States: N. p., 2019. Web. doi:10.1021/acsami.9b01242.
Bartel, Christopher J., Rumptz, John R., Weimer, Alan W., Holder, Aaron M., & Musgrave, Charles B. High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis. United States. doi:10.1021/acsami.9b01242.
Bartel, Christopher J., Rumptz, John R., Weimer, Alan W., Holder, Aaron M., and Musgrave, Charles B. Thu . "High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis". United States. doi:10.1021/acsami.9b01242.
@article{osti_1506620,
title = {High-Throughput Equilibrium Analysis of Active Materials for Solar Thermochemical Ammonia Synthesis},
author = {Bartel, Christopher J. and Rumptz, John R. and Weimer, Alan W. and Holder, Aaron M. and Musgrave, Charles B.},
abstractNote = {Solar thermochemical ammonia (NH3) synthesis (STAS) is a potential route to produce NH3 from air, water, and concentrated sunlight. This process involves the chemical looping of an active redox pair that cycles between a metal nitride and its complementary metal oxide to yield NH3. To identify promising candidates for STAS cycles, we performed a high-throughput thermodynamic screening of 1,148 metal nitride/metal oxide pairs. This data-driven screening was based on Gibbs energies of crystalline metal oxides and nitrides at elevated temperatures, G(T), calculated using a recently introduced statistically learned descriptor and 0 K DFT formation energies tabulated in the Materials Project database. Using these predicted G(T) values, we assessed the viability of each of the STAS reactions - hydrolysis of the metal nitride, reduction of the metal oxide, and nitrogen fixation to reform the metal nitride - and analyzed a revised cycle that directly converts between metal oxides and nitrides, which alters the thermodynamics of the STAS cycle. For all 1148 redox pairs analyzed and each of the STAS-relevant reactions, we implemented a Gibbs energy minimization scheme to predict the equilibrium composition and yields of the STAS cycle, which reveals new active materials based on B, V, Fe, and Ce that warrant further investigation for their potential to mediate the STAS cycle. This work details a high-throughput approach to assessing the relevant temperature-dependent thermodynamics of thermochemical redox processes that leverages the wealth of publicly available temperature-independent thermodynamic data calculated using DFT. This approach is readily adaptable to discovering optimal materials for targeted thermochemical applications and enabling the predictive synthesis of new compounds using thermally controlled solid-state reactions.},
doi = {10.1021/acsami.9b01242},
journal = {ACS Applied Materials and Interfaces},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 28, 2020
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