Results for “Splitting” — Page 96

DOE OSTI2013

Computational Fluid Dynamics Analysis of Flexible Duct Junction Box Design

IBACOS explored the relationships between pressure and physical configurations of flexible duct junction boxes by using computational fluid dynamics (CFD) simulations to predict individual box parameters and total system pressure, thereby ensuring improved HVAC performance. Current Air Conditioning Contractors of America (ACCA) guidance (Group 11, Appendix 3, ACCA Manual D, Rutkowski 2009) allows for unconstrained variation in the number of takeoffs, box sizes, and takeoff locations. The only variables currently used in selecting an equivalent length (EL) are velocity of air in the duct and friction rate, given the first takeoff is located at least twice its diameter away from the inlet. This condition does not account for other factors impacting pressure loss across these types of fittings. For each simulation, the IBACOS team converted pressure loss within a box to an EL to compare variation in ACCA Manual D guidance to the simulated variation. IBACOS chose cases to represent flows reasonably correlating to flows typically encountered in the field and analyzed differences in total pressure due to increases in number and location of takeoffs, box dimensions, and velocity of air, and whether an entrance fitting is included. The team also calculated additional balancing losses for all cases due to discrepancies between intended outlet flows and natural flow splits created by the fitting. In certain asymmetrical cases, the balancing losses were significantly higher than symmetrical cases where the natural splits were close to the targets. Thus, IBACOS has shown additional design constraints that can ensure better system performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2014

New Insights for Improving the Designs of Flexible Duct Junction Boxes (Fact Sheet)

IBACOS explored the relationships between pressure and physical configurations of flexible duct junction boxes by using computational fluid dynamics (CFD) simulations to predict individual box parameters and total system pressure, thereby ensuring improved HVAC performance. Current Air Conditioning Contractors of America (ACCA) guidance (Group 11, Appendix 3, ACCA Manual D, Rutkowski 2009) allows for unconstrained variation in the number of takeoffs, box sizes, and takeoff locations. The only variables currently used in selecting an equivalent length (EL) are velocity of air in the duct and friction rate, given the first takeoff is located at least twice its diameter away from the inlet. This condition does not account for other factors impacting pressure loss across these types of fittings. For each simulation, the IBACOS team converted pressure loss within a box to an EL to compare variation in ACCA Manual D guidance to the simulated variation. IBACOS chose cases to represent flows reasonably correlating to flows typically encountered in the field and analyzed differences in total pressure due to increases in number and location of takeoffs, box dimensions, and velocity of air, and whether an entrance fitting is included. The team also calculated additional balancing losses for all cases due to discrepancies between intended outlet flows and natural flow splits created by the fitting. In certain asymmetrical cases, the balancing losses were significantly higher than symmetrical cases where the natural splits were close to the targets. Thus, IBACOS has shown additional design constraints that can ensure better system performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2014

Hood River Passive House, Hood River, Oregon (Fact Sheet)

The Hood River Passive Project was developed by Root Design Build of Hood River Oregon using the Passive House Planning Package (PHPP) to meet all of the requirements for certification under the European Passive House standards. The Passive House design approach has been gaining momentum among residential designers for custom homes and BEopt modeling indicates that these designs may actually exceed the goal of the U.S. Department of Energy's (DOE) Building America program to "reduce home energy use by 30%-50%" (compared to 2009 energy codes for new homes). This report documents the short term test results of the Shift House and compares the results of PHPP and BEopt modeling of the project. The design includes high R-Value assemblies, extremely tight construction, high performance doors and windows, solar thermal DHW, heat recovery ventilation, moveable external shutters and a high performance ductless mini-split heat pump. Cost analysis indicates that many of the measures implemented in this project did not meet the BA standard for cost neutrality. The ductless mini-split heat pump, lighting and advanced air leakage control were the most cost effective measures. The future challenge will be to value engineer the performance levels indicated here in modeling using production based practices at a significantly lower cost.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2014

Hood River Passive House

The Hood River Passive Project was developed by Root Design Build of Hood River Oregon using the Passive House Planning Package (PHPP) to meet all of the requirements for certification under the European Passive House standards. The Passive House design approach has been gaining momentum among residential designers for custom homes and BEopt modeling indicates that these designs may actually exceed the goal of the U.S. Department of Energy's (DOE) Building America program to reduce home energy use by 30%-50% (compared to 2009 energy codes for new homes). This report documents the short term test results of the Shift House and compares the results of PHPP and BEopt modeling of the project. The design includes high R-Value assemblies, extremely tight construction, high performance doors and windows, solar thermal DHW, heat recovery ventilation, moveable external shutters and a high performance ductless mini-split heat pump. Cost analysis indicates that many of the measures implemented in this project did not meet the BA standard for cost neutrality. The ductless mini-split heat pump, lighting and advanced air leakage control were the most cost effective measures. The future challenge will be to value engineer the performance levels indicated here in modeling using production based practices at a significantly lower cost.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2013

Transformations, Inc.: Partnering To Build Net-Zero Energy Houses in Massachusetts

Transformations, Inc. is a residential development and building company that has partnered with Building Science Corporation to build new construction net-zero energy houses in Massachusetts under the Building America program. There are three communities that will be constructed through this partnership: Devens Sustainable Housing ("Devens"), The Homes at Easthampton Meadow ("Easthampton") and Phase II of the Coppersmith Way Development ("Townsend"). This report intends to cover all of the single-family new construction homes that have been completed to date. The houses built in these developments are net zero energy homes built in a cold climate. They will contribute to finding answers to specific research questions for homes with high R double stud walls and high efficiency ductless air source heat pump systems ("mini-splits"); allow to explore topics related to the financing of photovoltaic systems and basements vs. slab-on-grade construction; and provide feedback related to the performance of ductless mini-split air source heat pumps.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2013

Computational Fluid Dynamics Analysis of Flexible Duct Junction Box Design

IBACOS explored the relationships between pressure and physical configurations of flexible duct junction boxes by using computational fluid dynamics (CFD) simulations to predict individual box parameters and total system pressure, thereby ensuring improved HVAC performance. Current Air Conditioning Contractors of America (ACCA) guidance (Group 11, Appendix 3, ACCA Manual D, Rutkowski 2009) allows for unconstrained variation in the number of takeoffs, box sizes, and takeoff locations. The only variables currently used in selecting an equivalent length (EL) are velocity of air in the duct and friction rate, given the first takeoff is located at least twice its diameter away from the inlet. This condition does not account for other factors impacting pressure loss across these types of fittings. For each simulation, the IBACOS team converted pressure loss within a box to an EL to compare variation in ACCA Manual D guidance to the simulated variation. IBACOS chose cases to represent flows reasonably correlating to flows typically encountered in the field and analyzed differences in total pressure due to increases in number and location of takeoffs, box dimensions, and velocity of air, and whether an entrance fitting is included. The team also calculated additional balancing losses for all cases due to discrepancies between intended outlet flows and natural flow splits created by the fitting. In certain asymmetrical cases, the balancing losses were significantly higher than symmetrical cases where the natural splits were close to the targets. Thus, IBACOS has shown additional design constraints that can ensure better system performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2014

Hood River Passive House

The Hood River Passive Project was developed by Root Design Build of Hood River Oregon using the Passive House Planning Package (PHPP) to meet all of the requirements for certification under the European Passive House standards. The Passive House design approach has been gaining momentum among residential designers for custom homes and BEopt modeling indicates that these designs may actually exceed the goal of the U.S. Department of Energy's (DOE) Building America program to "reduce home energy use by 30%-50% (compared to 2009 energy codes for new homes). This report documents the short term test results of the Shift House and compares the results of PHPP and BEopt modeling of the project. The design includes high R-Value assemblies, extremely tight construction, high performance doors and windows, solar thermal DHW, heat recovery ventilation, moveable external shutters and a high performance ductless mini-split heat pump. Cost analysis indicates that many of the measures implemented in this project did not meet the BA standard for cost neutrality. The ductless mini-split heat pump, lighting and advanced air leakage control were the most cost effective measures. The future challenge will be to value engineer the performance levels indicated here in modeling using production based practices at a significantly lower cost.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2013

Transformations, Inc.: Partnering to Build Net-Zero Energy Houses in Massachusetts

Transformations, Inc. is a residential development and building company that has partnered with Building Science Corporation to build new construction net-zero energy houses in Massachusetts under the Building America program. There are three communities that will be constructed through this partnership: Devens Sustainable Housing ('Devens'), The Homes at Easthampton Meadow ('Easthampton') andPhase II of the Coppersmith Way Development ('Townsend'). This report intends to cover all of the single-family new construction homes that have been completed to date. The houses built in these developments are net zero energy homes built in a cold climate. They will contribute to finding answers to specific research questions for homes with high R double stud walls and high efficiency ductlessair source heat pump systems ('mini-splits'); allow to explore topics related to the financing of photovoltaic systems and basements vs. slab-on-grade construction; and provide feedback related to the performance of ductless mini-split air source heat pumps.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2016

Increasing EDV Range through Intelligent Cabin Air Handling Strategies: Annual Progress Report

Computational fluid dynamics (CFD) simulations of a Ford Focus Electric demonstrated that a split flow heating, ventilating and air conditioning (HVAC) system with rear recirculation ducts can reduce cabin heating loads by up to 57.4% relative to full fresh air usage under some conditions (steady state, four passengers, ambient temperature of -5 deg C). Simulations also showed that implementing a continuous recirculation fraction control system into the original equipment manufacturer (OEM) HVAC system can reduce cabin heating loads by up to 50.0% relative to full fresh air usage under some conditions (steady state, four passengers, ambient temperature of -5 deg C). Identified that continuous fractional recirculation control of the OEM system can provide significant energy savings for EVs at minimal additional cost, while a split flow HVAC system with rear recirculation ducts only provides minimal additional improvement at significant additional cost.

33 ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2013

Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation

The weakest link for the large-scale deployment of solar energy and for that matter, any renewable energy source, is its storage. The energy needs of future society demands are so large that storage must be in the form of fuels owing to their high energy density. Indeed, society has intuitively understood this disparity in energy density as it has developed over the last century as all large-scale energy storage in our society is in the form of fuels. But these fuels are carbon-based. The imperative for the discipline of chemistry, and more generally science, is to develop fuel storage methods that are easily scalable, carbon-neutral and sustainable. These methods demand the creation of catalysts to manage the multi-electron, multi-proton transformations of the conversion of small molecules into fuels. The splitting of water using solar light is a fuel-forming reaction that meets the imperative of large scale energy storage. As light does not directly act on water to engender its splitting into its elemental components, we have designed “hangman” catalysts to effect the energy conversion processes needed for the fuel forming reactions. The hangman construct utilizes a pendant acid/base functionality within the secondary coordination sphere that is “hung” above the redox platform onto which substrate binds. In this way, we can precisely control the delivery of a proton to the substrate, thus ensuring efficient coupling between the proton and electron. An emphasis was on the coupling of electron and proton in the hydrogen evolution reaction (HER) on Ni, Co and Fe porphyrin platforms. Electrokinetic rate laws were developed to define the proton-coupled electron transfer (PCET) mechanism. The HER of Co and Fe porphyrins was metal-centered. Surprisingly, HER this was not the case for Ni porphyrins. In this system, the PCET occurred at the porphyrin platform to give rise to a phlorin. This is one of the first examples of an HER occurring via ligand non-innocence. The program was expanded to include other macrocycles with a focus on corroles. The photophyscial and electrochemical properties of a number of new metal- and free-base corroles were defined. Finally, the reaction chemistry of a new platform designed for oxygen evolution and reduction reactions. The hexacarboxamide cryptands was shown to be an ideal binucleating ligand for studies of oxygen. The electron transfer reaction of native oxygen in the absence of protons and metals was enabled for the first time, thus allowing us to observe new reactions of reduced oxygen with carbon dioxide. These results have had important consequence in shedding light on Li air batteries, and why these batteries cannot be recharged. This is the key issue impeding the technology development of Li-air batteries and therefore these results should be enlightening to the commercial development of Li-air batteries. Together, this portfolio of experiments provides a powerful insight to the crucial steps for the efficient conversion of small molecules to fuels and their subsequent use. To this end, the research program provides basic science to enable the low cost solar production of hydrogen from water and the reverse fuel cell reaction.

25 ENERGY STORAGE↗

DOE OSTI2022

Accelerated Discovery of Solar Thermochemical Hydrogen Production Materials via High-Throughput Computational and Experimental Methods

In this project, combinatorial synthesis and testing methods were combined with high-throughput materials theory calculations to greatly accelerate the discovery of thermodynamically suitable candidates for green hydrogen production via a two-stage solar thermochemical water splitting (STCH) process. Over the course of the project, more than 8000 quinary and higher oxide compositions were computationally screened for STCH viability, and detailed stability calculations were performed for more than 30 of the most promising identified compositional archetypes. As a result, three new STCH capable compositional families were discovered and experimentally verified. The first, Ce x Sr 2-x MnO 4 (CSM), represents the first known Ruddlesden-Popper compound to show STCH activity, and thus demonstrates that perovskite-related structures may hold promise for this application. The second family, Sr 1-x Ce x MnO 3 (SCM), is the simple perovskite sister-analog to CSM. Sr 0.7 Ce 0.3 MnO 3 (SCM30), a member of this compositional family, was found to produce the highest hydrogen yields of any compound tested in this project, exceeding the end of project milestone target of > 150 μmol H 2 /gram oxide at a reduction temperature of 1350 °C, although only at steam-to-hydrogen ratios greater than 1000:1. Finally, we proved that a third novel Sr-and Mn-containing family, Sr 1-x Ca x Ti 1-y Mn y O 3 (SCTM), which was identified by Materials Project tools, also splits water. The behavior of the SCTM system was found to be similar to the previously discovered Sr 1-x La x Al 1-y Mn y O 3 (SLMA) family, albeit with lower H 2 yields. Across the three thrusts of the project (computational, combinatorial, and bulk testing), five journal articles were published. As part of Program End Analysis and Data Dissemination, relevant data used for the publications was uploaded to the HydroGEN Data Hub for public access, and in certain cases, results were added to public materials databases.

08 HYDROGEN↗

DOE OSTI2023

Mixed Ionic Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen

The innovative research conducted by Arizona State University and Princeton University in the project "Mixed Ionic-Electronic Conducting Quaternary Perovskites: Materials by Design for Solar Thermochemical Hydrogen" marks a significant stride forward in thermochemical water splitting. Through an intricate blend of computational design and experimental validation, the project delved into the promising potential of Mixed Ionic Electronic Conducting (MIEC) perovskites. These complex materials, characterized by their unique redox-active nature and adaptability in stoichiometry, present a promising frontier for efficient solar thermochemical hydrogen production. Firstly, the research enhanced the science by utilizing state-of-the-art computational methodologies to unravel the nuanced chemical potentials of MIEC perovskites. By simulating various off-stoichiometric scenarios and redox conditions, the team was able to predict material behaviors under diverse environmental conditions, a feat unachievable through conventional experimental methodologies alone. This approach not only fast-tracks the material screening process, significantly reducing the time from laboratory re-search to practical application, but also uncovers trends and correlations that are pivotal for future materials innovation. Regarding technical effectiveness, the project stands out in its economic feasibility. Traditional methods of materials discovery are often marred by high costs and extensive timeframes, owing to the iterative nature of experimental processes. However, by employing theoretical computations and validating these findings with targeted experiments, the project introduced a cost-effective paradigm for materials discovery and the first ever prediction, synthesis, and preliminary validation of a material solely from computational and theoretical considerations. This synergy between computation and experimentation expedites the discovery of optimal materials conducive to high-efficiency solar-to-hydrogen conversion processes. Furthermore, the public stands to benefit substantially from this research. The success of MIEC perovskites in solar thermochemical applications heralds a shift towards lower cost and lower electricity input for clean hydrogen production, hence potentially impacting climate and energy resilience. By improving the efficiency of solar-to-hydrogen conversions, the research paves the way for reduced dependency on fossil fuels, addressing the urgent global need for accessible and renewable energy sources. Moreover, the project's advancements contribute to scientific literacy in renewable energy technologies, empowering society through knowledge and spurring future innovations. In essence, this research project demonstrates significant progress in the realm of advanced water splitting through solar thermochemistry. Through its groundbreaking approaches in computational materials science and its implications for real-world applications, it holds the promise of a cleaner, more energy-resilient future.

08 HYDROGEN↗

DOE OSTI2026

Scalable Solar Fuels Production in A Reactor Train System by Thermochemical Redox Cycling of Novel Nonstoichiometric Perovskites

Hydrogen production via two-step thermochemical water splitting redox cycles using nonstoichiometric redox-active metal oxides has the potential to dramatically increase fuel production rates. At moderate-to-low water splitting temperatures, surface reaction kinetics co-limit the process. In such cases, stable and high surface area microstructures that allow exploitation of the full thermodynamic potential of the materials are essential as is tight thermal integration of the reactor module. This project’s goals were the development of novel nonstoichiometric perovskite oxides with high stability and favorable thermodynamic and kinetic properties, to optimize their microstructure for maximizing the fuel productivity, and to build a prototype reactor train system (RTS) comprising at least one reactor to meet specific performance targets: (1) capable of an in-house solar thermochemical hydrogen (STCH) productivity ≥ 12 mL g -1 for stable continuous operation ≥ 20 cycles; and (2) demonstration of scalable solar fuels production at practical solar reactor level in an industrial-scale concentrated solar tower (CST) using developed perovskites to achieve a hydrogen production rate ≥ 1 g h -1 .

08 HYDROGEN↗

DOE OSTI2026

Towards Spatial Control of Reaction Selectivity on Photocatalysts using Area Selective Atomic Layer Deposition on Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost H2; however, this approach is currently limited by solar-to-hydrogen (STH) conversion efficiencies in the sub-10% range. Z-scheme water splitting, in which H2 and O2 evolving particles are operated in separate compartments and electronically coupled by a soluble redox mediator, offers improvements in STH efficiency but introduces high rates of undesired side and back reactions. Nanoscopic oxide coatings (e.g., CrOx, and SiOx) have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as the particle can no longer facilitate both half reactions. In contrast to photodeposition, which may produce non-uniform overlayers due to the difficulty of controlling local electrochemical reactivity on the surface, area-selective atomic layer deposition (AS-ALD) can be used to deposit conformal ultrathin oxide coatings while preserving access to non-growth areas of a substrate surface. To develop this technique for Z-scheme photocatalysts, we performed AS-ALD of TiO2 on a dual site planar electrocatalyst based on interdigitated arrays of Pt and Au. Self-assembled monolayers of 1-octadecanethiol (ODT) were used to block growth on the Au array, resulting in a patterned surface in which only the Pt sites were encapsulated with TiO2. These electrocatalysts demonstrated localized reaction selectivity for hydrogen evolution reaction (HER) over the TiO2/Pt sites, while the uncoated Au sites retained activity towards Fe(II)/Fe(III) redox (FeRR). Under independent potential control, these microelectrodes showed that selectively deposited TiO2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared to uncoated control samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Solar enhanced oxygen evolution reaction with transition metal telluride

The photo-enhanced electrocatalytic method of oxygen evolution reaction (OER) shows promise for enhancing the effectiveness of clear energy generation through water splitting by using renewable and sustainable source of energy. However, despite benefits of photoelectrocatalytic (PEC) water splitting, its uses are constrained by its low efficiency as a result of charge carrier recombination, a large overpotential, and sluggish reaction kinetics. Here, we illustrate that Nickel telluride (NiTe) synthesized by hydrothermal methods can function as an extremely effective photo-coupled electrochemical oxygen evolution reaction (POER) catalyst. In this study, NiTe was synthesized by hydrothermal method at 145°C within just an hour of reaction time. In dark conditions, the NiTe deposited on carbon cloth substrate shows a small oxygen evolution reaction overpotential (261 mV) at a current density of 10 mA cm –2 , a reduced Tafel slope (65.4 mV dec -1 ), and negligible activity decay after 12 h of chronoamperometry. By virtue of its enhanced photo response, excellent light harvesting ability, and increased interfacial kinetics of charge separation, the NiTe electrode under simulated solar illumination displays exceptional photoelectrochemical performance exhibiting overpotential of 165 mV at current density of 10 mA cm -2 , which is about 96 mV less than on dark conditions. In addition, Density Functional Theory investigations have been carried out on the NiTe surface, the results of which demonstrated a greater adsorption energy for intermediate -OH on the catalyst site. Since the -OH adsorption on the catalyst site correlates to catalyst activation, it indicates the facile electrocatalytic activity of NiTe owing to favorable catalyst activation. DFT calculations also revealed the facile charge density redistribution following intermediate -OH adsorption on the NiTe surface. This work demonstrates that arrays of NiTe elongated nanostructure are a promising option for both electrochemical and photoelectrocatalytic water oxidation and offers broad suggestions for developing effective PEC devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Enhancing Absorption Bandwidth through Vertically Oriented Metamaterials

Metamaterials research has developed perfect absorbers from microwave to optical frequencies, mainly featuring planar metamaterials, also referred to as metasurfaces. In this study, we investigated vertically oriented metamaterials, which make use of the entire three-dimensional space, as a new avenue to widen the spectral absorption band in the infrared regime between 20 and 40 THz. Vertically oriented metamaterials, such as those simulated in this work, can be experimentally realized through membrane projection lithography, which allows a single unit cell to be decorated with multiple resonators by exploiting the vertical dimension. In particular, we analyzed the cases of a unit cell containing a single vertical split-ring resonator (VSRR), a single planar split-ring resonator (PSRR), and both a VSRR and PSRR to explore intra-cell coupling between resonators. We show that the additional degrees of freedom enabled by placing multiple resonators in a unit cell lead to novel ways of achieving omnidirectional super absorption. Our results provide an innovative approach for controlling and designing engineered nanostructures.

36 MATERIALS SCIENCE↗

DOE OSTI2014

New Whole-House Solutions Case Study: Hood River Passive House

The Hood River Passive Project was developed by Root Design Build of Hood River Oregon using the Passive House Planning Package (PHPP) to meet all of the requirements for certification under the European Passive House standards. The Passive House design approach has been gaining momentum among residential designers for custom homes and BEopt modeling indicates that these designs may actually exceed the goal of the U.S. Department of Energy's (DOE) Building America program to "reduce home energy use by 30%-50%" (compared to 2009 energy codes for new homes). This report documents the short term test results of the Shift House and compares the results of PHPP and BEopt modeling of the project. The design includes high R-Value assemblies, extremely tight construction, high performance doors and windows, solar thermal DHW, heat recovery ventilation, moveable external shutters and a high performance ductless mini-split heat pump. Cost analysis indicates that many of the measures implemented in this project did not meet the BA standard for cost neutrality. The ductless mini-split heat pump, lighting and advanced air leakage control were the most cost effective measures. The future challenge will be to value engineer the performance levels indicated here in modeling using production based practices at a significantly lower cost.

BA-PIRC↗

DOE OSTI2021

Ab Initio Study of Atomic and Electronic Structure of Promising Ba4XMn3O12 (X = Nb, Ce, Pr) Oxides for Solar Thermochemical Hydrogen Production

The two-step metal oxide water-splitting cycle is one of the most viable approach for Solar Thermochemical Hydrogen (STCH) production. Challenges exist in finding suitable oxides that can satisfy thermodynamics of the STCH redox cycle under viable range of temperatures and partial pressures. Recently, BXM family members, i.e., Ba4NbMn3O12 (BNM), Ba4CeMn3O12 (BCM), Ba4PrMn3O12 (BPM) are discovered to exhibit promising STCH performance. However, the magnetic degrees of freedom of their experimental crystal structures is not characterized, and only hypothetical models exist for their electronic structure. We performed Monte-Carlo sampling for the magnetic spin arrangement of Mn atoms to provide explicit atomic structure models for their ground state 12R polytype and determined the most stable spin configuration for each member after structure relaxation using density functional theory (DFT) calculations. We also elucidate the most stable charge configuration (Mn3+/Mn4+ arrangement) for BNM among the existing hypothesis in literature. We investigate these strongly correlated oxides using different levels of theory (DFT+U, Hybrid-DFT) to develop better understanding of their electronic structure. These calculations allowed us to develop a model based on molecular orbital interactions that help explain the observed changes in their experimental x-ray spectroscopy measurements. Thereby, help link differences in electronic structure of BXM family members to their varying water-splitting behavior. These structure models will further facilitate future in-depth defect studies to model STCH redox cycle of these oxides.

atomic and magnetic structure↗