Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “EXPERIMENTATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Co-Hydrotreatment of Yellow Greases and the Water-Insoluble Fraction of Pyrolysis Oil. Part I: Experimental Design to Increase Kerosene Yield and Reduce Coke Formation

Here, this paper reports the co-hydrotreatment of Biomass Technology Group commercial pyrolysis oil water-insoluble (WIS) phase (also known as pyrolytic lignin) and yellow greases (waste cooking oil), aiming to produce sustainable aviation fuels (SAFs). We use a sulfided NiMo/Al 2 O 3 blend with 16 wt % WIS and a central composite experimental design to identify processing conditions increasing kerosene yield and reducing coke formation. The input variables were: (1) reaction temperature (320, 350, and 380 °C), (2) initial hydrogen pressure (5, 6, and 7 MPa), and (3) amount of catalyst (0.7, 1.0, and 1.3 g). The hydrotreated oily phases were distilled to obtain gasoline (<150 °C), kerosene (150–250 °C), diesel (250–350 °C), and residual oil (>350 °C). The reaction temperature is the main factor affecting the yield of gaseous, solid, and liquid products. Meanwhile, a higher initial hydrogen pressure and catalyst loading increased the yield of kerosene and other distillates and decreased the coke formation. A high temperature correlated with a lower content of oxygenates in kerosene cuts. Based on our experimental results, we propose to conduct hydrotreatment studies at 380 °C, initial H 2 pressure of 7 MPa, and 1.3 g of catalyst. Under the identified conditions, it was possible to improve the kerosene yield to more than 20 wt % and reduce the yield of coke to close to 2.0 wt %. The chemical composition and fuel properties of the gasoline, kerosene, and diesel cuts were thoroughly analyzed. The content of aromatics and phenols in the kerosene fraction produced at the conditions identified in this project exceeded the recommended values for SAFs. New strategies (such as blending and more intense hydrotreatment to remove oxygenated compounds) need to be implemented to reduce the content of these molecules in our final product.

09 BIOMASS FUELS↗
DOE OSTI2024

High-Temperature Fe-Based Fischer–Tropsch Synthesis: Experimentally Validated Kinetic Models Implemented at Pellet and Reactor Scales

Pellet- and reactor-scale models for Fischer–Tropsch synthesis (FTS) with a Fe–K/silica catalyst were developed to investigate the sensitivity of the hydrocarbon products and carbon dioxide selectivity to process conditions and feed composition at high temperature (350–400 °C), moderate pressure (1–10 bar), and a range of H 2 /CO ratios (3–1). The major objective of this paper is to develop, validate, and evaluate a high-temperature FTS model that is then used to assess the feasibility of process integration with syngas production. Since there is limited kinetic data available, in literature at these conditions, bench-scale reactor tests were conducted to obtain operational data for parameter fitting of kinetic expressions used in the model. This resulting kinetic model demonstrated agreement with the experimental data with an R 2 of 0.97 to the testing data set and, thus, was feasible to apply at pellet and reactor scales. Here, multiple pellet sizes were modeled to detail the role of transport limitations as the sphere’s diameter approached and exceeded 1 mm. Application of the reactor model indicated that hydrocarbon selectivity depended strongly on temperature, whereas the ratio of olefin to paraffin products decreased with increasing temperature, pressure, and H 2 /CO ratio. Product selectivity was not sensitive to the conversion of carbon monoxide. Furthermore, the roles of the pressure and H 2 /CO ratio were closely coupled. At a H 2 /CO ratio of 3, only slight variations in selectivity occurred over a pressure range of 1–20 bar, whereas at a ratio of 1, selectivity could vary by as much as 30% over the same pressure range. At pressures below 5 bar and temperatures above 350 °C, minimal selectivity to heavy hydrocarbons (C 12+ ) is obtained, and selectivity to midrange products (C 5–11 ) rapidly declined as pressure dropped below 5 bar, which indicated that an operational pressure of at least 5 bar is needed to achieve reasonable yields in this temperature range. These results, while tentative, provide guidelines for further experimentation and evaluation of integrated FTS processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Experimental and Theoretical Insights into the Structure of Tellurium Chloride Glasses

Here, the structure of the binary chalcohalide glasses Te 1-x CL x (0.35 <= x <= 0.65) is considered by combining experimental and theoretical results. The structural network properties are influenced by a competition between ionic and covalent bonding in such glasses. At first, a focus is placed on the detailed information available by using the complementary high-energy X-ray and the neutron diffractions in both the reciprocal and real spaces. The main characteristic suggested by the structure factors S(Q) concerns the presence of three length scales in the intermediate range order. The total correlation function T(r) lets us also suppose that the structure of these glasses is more complicated than Te-chain fragments with terminal Cl as demonstrated in crystalline Te 3 Cl 2 . Molecular dynamics simulations were subsequently performed on Te 3 Cl 2 and Te 2 Cl 3 , and coupled with the experimental data, a highly reticulated network of chalcogen atoms, with a fair amount of chlorine atoms bonded in a bridging mode, is proposed. The simulations clearly lead to a glass description that differs markedly from the simple structural model based on only Te atom chains and terminal Cl atoms. Solidstate NMR experiments and NMR parameters calculations allowed validation of the presence of Te highly coordinated with chlorine in these glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Experimentally Verified Alkane Adsorption Isotherms in Nanoporous Materials from Literature Meta-Analysis

Identification of independent experimental replicate measurements of well-defined physical properties provides a useful way to assess the reproducibility of literature reports of these properties. Prior meta-analysis of this kind for single-component adsorption of CO 2 and alcohols in nanoporous materials showed that ~20% of reported isotherms for these molecules were inconsistent with available replicate measurements. Here, we extend this analysis to the single-component adsorption of alkanes in nanoporous materials using a collection of 2998 experimental isotherms. Among these isotherms, 846 replicates were identified and analyzed. Many more replicates are available for CH 4 adsorption than for any other alkane. Our analysis finds that 15% of the replicate alkane isotherms are inconsistent with other replicate measurements. Furthermore, after discarding these outlier isotherms we report graphical and numerical consensus isotherms for 93 independent combinations of adsorbate, adsorbent, and temperature as well as an assessment of another 124 independent systems for which two replicate isotherms are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Assessment of Molten Eutectic LiF-NaF-KF Density through Experimental Determination and Semiempirical Modeling

Molten salts have favorable material properties for use in high-temperature energy systems, including thermal energy storage systems, concentrating solar power plants, nuclear reactors, and various industrial manufacturing processes. Knowledge of chemical and thermophysical property data is essential for the design and optimization of these systems, yet data are often limited or uncertain for many candidate salts due to the difficulty of thermophysical property measurements at relevant temperatures (e.g., 500–900 °C). Here, the density of molten LiF-NaF-KF eutectic is reassessed through review of previous experimental data, new density measurements from 470 to 800 °C, and semiempirical modeling. Additionally, the density was measured using the displacement technique. Compositional and temperature-dependent density estimates were calculated with a multidimensional Redlich–Kister model. The results of the new experimental measurements agree within 2% of the modeled density of molten eutectic LiF-NaF-KF. The Redlich–Kister model’s prediction shows a near-ideal density behavior for the LiF-NaF-KF system and is promising for the estimation of off-eutectic LiF-NaK-KF densities. Finally, through review of the existing literature and comparison to new measurements, recommendations are made for the density of LiF-NaF-KF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Paired Simulations and Experimental Investigations into the Calcium-Dependent Conformation of Albumin

Serum albumin is the most abundant protein in blood plasma, and it is involved in multiple biological processes. Serum albumin has recently been adapted for improving biomaterial integration with bone tissue, and studies have shown the importance of this protein in bone repair and regeneration. However, the mechanism of action is not yet clear. In stark contrast, other studies have demonstrated that albumin blocks cell adhesion to surfaces, which is seen as a limitation to its bone healing role. These apparent contradictions suggest that the conformation of albumin facilitates its bioactivity, leading to enhanced bone repair. Serum albumin is known to play a major role in maintaining the calcium ion concentration in blood plasma. Due to the prevalence of calcium at bone repair and regeneration sites, it has been hypothesized that calcium binding to serum albumin triggers a conformational change, leading to bioactivity. In the current study, molecular modeling approaches including molecular docking, atomic molecular dynamics (MD) simulation, and coarse-grained MD simulation were used to test this hypothesis by investigating the conformational changes induced in bovine serum albumin by interaction with calcium ions. The computational results were qualitatively validated with experimental Fourier-transform infrared spectroscopy analysis. We find that free calcium ions in solution transiently bind with the three major loops in albumin, triggering a conformational change where N-terminal and C-terminal domains separate from each other in a partial unfolding process. The separation distance between these domains was found to correlate with the calcium ion concentration. The experimental data support the simulation results showing that albumin has enhanced conformational heterogeneity upon exposure to intermediate levels of calcium, without any significant secondary structure changes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Minimal Experimental Bias on the Hydrogen Bond Greatly Improves Ab Initio Molecular Dynamics Simulations of Water

Experiment Directed Simulations (EDS) is a method within a class of techniques seeking to improve molecular simulations by minimally biasing the system Hamiltonian to reproduce certain experimental observables. In a previous application of EDS to ab initio molecular dynamics (AIMD) simulation based on electronic density functional theory (DFT), the AIMD simulations of water were biased to reproduce its experimentally derived solvation structure. In particular, by solely biasing the O-O pair correlation functions, other structural and dynamical properties that were not biased were improved. In this work, the hypothesis is tested that directly biasing the OH pair correlation (and hence the H-O∙∙∙H hydrogen bonding), will provide an even better improvement of DFT-based water properties in AIMD simulations. The logic behind this hypothesis is that for most electronic DFT descriptions of water the hydrogen bonding is known to be deficient due to anomalous charge transfer and over polarization in the DFT. Using recent advances to the EDS learning algorithm, we thus train a minimal bias on AIMD water that reproduces the O-H radial distribution function derived from the highly accurate MB-pol model of water. Finally, it is then confirmed that biasing the O-H pair correlation alone can lead to improved AIMD water properties, with structural and dynamical properties in even closer to experiment than the previous EDS-AIMD model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Interaction of Th with H 0/–/+ : Combined Experimental and Theoretical Thermodynamic Properties

In this work, high-level electronic structure calculations of the lowlying energy electronic states for ThH, ThH – , and ThH + are reported and compared to experimental measurements. The inclusion of spin–orbit coupling is critical to predict the ground-state ordering as inclusion of spin–orbit switches the coupled-cluster CCSD(T) ordering of the two lowest energy states for ThH and ThH + . At the multireference spin–orbit SO-CASPT2 level, the ground states of ThH, ThH – , and ThH + are predicted to be the 2 Δ 3/2 , 3 Φ 2 , and 3 Δ 1 states, respectively. The adiabatic electron affinity is calculated to be 0.820 eV, and the vertical detachment energy is calculated to be 0.832 eV in comparison to an experimental value of 0.87 ± 0.02 eV. The observed ThH – photoelectron spectrum has many transitions, which approximately correlate with excitations of Th + and/or Th. The adiabatic ionization energy of ThH including spin–orbit corrections is calculated to be 6.181 eV. The natural bond orbital results are consistent with a significant contribution of the Th + H – ionic configuration to the bonding in ThH. The bond dissociation energies for ThH, ThH – , and ThH + using the Feller–Peterson–Dixon approach were calculated to be similar for all three molecules and lie between 259 and 280 kJ/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –

We report here the results of a combined experimental and computational study of the negative ion photoelectron spectroscopy (NIPES) of the recently synthesized, planar, aromatic, HCPN3– ion. The adiabatic electron detachment energy of HCPN3– (electron affinity of HCPN3•) was measured to be 3.555 ± 0.010 eV, a value that is intermediate between the electron detachment energies of the closely related (CH)2N3– and P2N3– ions. High level electronic structure calculations and Franck–Condon factor (FCF) simulations reveal that transitions from the ground state of the anion to two nearly degenerate, low-lying, electronic states, of the neutral HCPN3• radical are responsible for the congested peaks at low binding energies in the NIPE spectrum. The best fit of the simulated NIPE spectrum to the experimental spectrum indicates that the ground state of HCPN3• is a 5π-electron 2A" π radical state, with a 6π-electron, 2A', σ radical state being at most ~1.0 kcal/mol higher in energy. This assignment contrasts with our recent finding that the ground state of P2N3• is a 6π-electron σ radical state

Environmental Molecular Sciences Laboratory↗
DOE OSTI2026

Improved Accuracy in Semi-Experimental Structure Determination by Resolving Problems Associated with Rotation of Principal Inertial Axes of Isotopologues: Structures of 1,3-Oxazole ( c -C 3 H 3 NO)

The rotational spectrum of the normal isotopologue of 1,3-oxazole (c-C 3 H 3 NO) was observed from 43 to 750 GHz. Over 3900 transitions for the ground vibrational state are measured, assigned, and least-squares fit to sextic centrifugally distorted-rotor Hamiltonians. The measured frequencies and resulting spectroscopic constants from this extended spectral range, combined with previous measurements of the nuclear quadrupole coupling constants, will facilitate astronomical searches for oxazole across the majority of the range of modern radiotelescopes. Spectra for a set of 30 oxazole isotopologues, which include multiple isotopic substitutions of each atom, are used to determine the first semi-experimental equilibrium ($r$$^{SE}_{e}$) structure and semi-experimental substitution structure ($r$$^{SE}_{e}$), each using CCSD(T) computed values for the vibration–rotation interaction and electron-mass corrections. The large number of isotopologues, including 21 isotopologues observed for the first time, and the redundant substitutions of each atom provide sufficient spectroscopic information to determine the $r$$^{SE}_{e}$ structure with the expected high level of accuracy and precision (0.0001 or 0.0002 Å in bond distances and 0.013 to 0.025° in bond angles). In the course of this study, we analyzed a known issue for some $r$$^{SE}_{e}$ structure determinations of near-oblate asymmetric tops in which inclusion of individual isotopologues degrades the structure determination. We demonstrate that this problem primarily arises from the difference in the values of the computed vibration–rotation interaction corrections as evaluated at the computed re geometry vs the $r$$^{SE}_{e}$ geometry of the “real” molecule. Our solution to this problem substantially improves the $r$$^{SE}_{e}$ structure of oxazole and likely can be generalized to many other molecules.

Chemical structure↗
DOE OSTI2017

An experimental and theoretical study of the thermal decomposition of C 4 H 6 isomers

The chemistry of small unsaturated hydrocarbons, such as 1,3–butadiene (1,3–C 4 H 6 ), 1,2–butadiene (1,2–C 4 H 6 ), 2–butyne (2–C 4 H 6 ) and 1–butyne (1–C 4 H 6 ), is of central importance to the modeling of combustion systems. These species are important intermediates in combustion processes, and yet their high-temperature chemistry remains poorly understood, with various dissociation and isomerization pathways proposed in the literature. Here we investigate the thermal decompositions of 1,3–C 4 H 6 , 1,2–C 4 H 6 , 2–C 4 H 6 and 1–C 4 H 6 inside a diaphragmless shock tube, at post shock total pressures of 26–261 Torr and temperatures ranging from 1428–2354 K, using laser schlieren densitometry. The experimental work has been complemented by high-level ab initio calculations, which collectively provide strong evidence that formally direct dissociation is the major channel for pyrolysis of 1,3–C 4 H 6 and 2–C 4 H 6 ; these paths have not been previously reported but are critical to reconciling the current work and disparate literature reports. The reaction mechanism presented here simulates the current experiments and experimental data from the literature very well. As a result, pressure and temperature dependent rate coefficients are given for the isomerization, formally direct and direct dissociation paths.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Probing Molecular Assembly of Small Organic Molecules during Meniscus-Guided Coating Using Experimental and Molecular Dynamics Approaches

Evaporation-based thin-film coating processes are ubiquitous in fields such as organic electronics, dye coatings, and the pharmaceutical industry. Based on experimental observations of enhanced thin-film alignment during meniscus-guided coating (MGC), a molecular dynamics simulation was developed to describe the thin-film formation that occurs due to the interplay between evaporation and fluid dynamics. The process of solvent evaporation from solution is first examined, which leads to the formation of a solid thin film after evaporation is complete. Next, an MGC process was simulated by introducing a flow profile coupled with the evaporative system. In this work, we gain insights into how molecules respond and reorient in the presence of a flow profile. These results indicate that both the evaporation and the flow profile have an impact on orienting small molecules in a thin film during the MCG process. Combining experimental techniques with simulations helps enhance the understanding of the forces that are significant in directing molecular aggregation during coating processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Integrated Experimental and Computational K-Edge X-ray Absorption Near-Edge Structure Analysis of Vanadium Catalysts

X-ray Absorption Near-Edge Structure (XANES) spectroscopy is a powerful tool to reveal key structural and electronic features of isolated catalytic sites, yet insights into molecular structure and more detailed orbital analysis through a combination of experimental and computed XANES analysis are necessary for accurate interpretation of the spectra, especially when significant heterogeneity exits among the catalytic sites. Herein, we present an integrated computational and experimental strategy to determine both primary and secondary bonding interactions within the XANES pre-edge region for organovanadium complexes, which was developed using a series of well-defined molecular vanadium complexes and then applied to the characterization of a supported organovanadium olefin hydrogenation catalyst. Time-dependent density functional theory is used to predict the energy of pre-edge XANES features for a series of vanadium complexes with a variety of oxidation states and local coordination environments. Further, a calibration scheme incorporating different density functionals and basis sets is established, resulting in an optimized scheme that accurately predicts pre-edge energies with a mean absolute error of 0.40 eV. Second-shell coordination (e.g., V---V) effects within XANES are identified through the analysis of the computed dominant orbital contributions for multi-vanadium complexes. Orbital analysis also provided confirmation that the vanadium-hydride formation combined with the heterogeneity of the catalytic active species in ole-fin hydrogenation caused the energy shift and broadening of the pre-edge peak after hydrogen treatment of the silica-supported organovanadium pre-catalyst. This work further elucidates computational XANES simulations and techniques potentially guiding characterization in surface organometallic chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterization of Lanthanum Monazite Surface Chemistry and Crystal Morphology through Density Functional Theory and Experimental Approaches

Monazite is a rare earth element (REE)-containing mineral that consists of (REE)PO 4 formal units and is one of the most important sources of these critical materials. The concentration of REEs from mined monazite ore often involves froth flotation, which is a beneficiation process that enhances the efficiency of downstream processing. The effectiveness of froth flotation is largely governed by the ability of collector agents to selectively bind to monazite particles. Thus, a molecular-level understanding of monazite interfacial chemistry is integral to the design of effective collector agents. To address this need, we performed density functional theory (DFT) calculations and a variety of experimental techniques to characterize La-monazite and elucidate its crystal morphology. Interestingly, we find minimal differences in the predicted morphologies of La-monazite for hydrous and anhydrous environments, which are largely dominated by low-index facets (e.g., {110}, {100}, and {010}). Indexing of synthesized La-monazite crystals via X-ray diffraction also uncovers {110} and {100} as the predominant facets. The average surface energies of 0% and 100% water coverage La-monazite crystals were predicted to be 0.87 and 0.76 J/m 2 , respectively, while calorimetry suggests values of 1.30 and 1.15 J/m 2 , respectively. The apparent discrepancies between the theoretical and experimental values are expected and attributed to defects present in physical crystals, in contrast to the perfect mineral surfaces in simulations. The difference in surface energy between the 0% and 100% water coverage morphologies predicted by theory is consistent with the value measured via calorimetry. DFT reveals a wide range of adsorption energies for water across the studied facets, but in all cases, water is predicted to strongly bind to monazite surfaces with an average adsorption energy of -92.7 kJ/mol for a La-monazite single crystal. Finally, this study provides the groundwork necessary for the rational design of froth flotation collector agents by granting molecular-level insight into the predominant facets of monazite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Vacancy-Dependent Diffusion Mechanism in Oxygen-Defective SrFeO 3 Perovskite Materials: First-Principles Density Functional Theory and Experimental Approach

Understanding oxygen diffusion at the atomic scale in SrFeO 3−δ perovskites is crucial for developing oxygen storage materials with optimal performance. Such materials are required to have high stability, corrosion resistance, and acceptable oxygen storage capacity at moderate operating temperatures and pressures. Here, in this study, we used first-principles density functional theory and thermogravimetric analysis to study the vacancy-dependent oxygen diffusion in oxygen-deficient SrFeO 3−δ (δ = 0, 0.065, 0.125, 0.25, 0.5) perovskites. The electronic structures, including the partial- and spin-resolved density of states, for different SrFeO 3−δ phases were calculated and compared with available experimental and theoretical results. By mapping the migration pathways, we investigated diffusion mechanisms and calculated the energy barriers for oxygen diffusion in cubic, orthorhombic, and brownmillerite phases of SrFeO 3−δ perovskites. Using the calculated energy barriers, we deduced the diffusion time scales and diffusion coefficients within SrFeO 3−δ . A diffusion coefficient on the order of 10 –8 m 2 /s was obtained for SrFeO 2.875 . We experimentally investigated the roles of temperature and oxygen partial pressures on the redox kinetics and deduced the kinetics rate and diffusion density, which agreed well with the calculated values for the density of diffusing oxygen vacancy in the lattice. Our results showed that the energy barrier tends to reduce at higher oxygen concentrations. Our results serve as an important guideline for designing oxygen storage materials with optimal redox kinetics.

chemical looping with oxygen uncoupling (CLOU)↗
DOE OSTI2015

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes

The LiNi 0.5 Mn 1.5 O 4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li + ). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi 0.5 Mn 1.5 O 4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi 0.5 Mn 1.5 O 4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni 2+ and Mn 2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi 0.5 Mn 1.5 O 4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Joint Theoretical and Experimental Study of the Electronic, Magnetic, and Lattice Phonon Dynamics Properties of Ca x Fe y O z Compounds Applied to CO 2 Capture

Unleashing energy innovation ensures a resilient and reliable energy supply. There is a critical need for the development of new carbon dioxide (CO 2 ) captors that have improved energy efficiency accompanied by lower capital and operational costs to ensure abundant, affordable, and secure energy. Among solid materials, CaO is a good CO 2 sorbent for capture technology due to its wide availability and low cost. However, CaO also suffers from some disadvantages, such as high calcination temperature, decreasing capability due to sintering, attrition, and reaction with SO x and NO x . In this study, we employed an ab initio thermodynamic approach and experimental measurements to improve its CO 2 capture performance during the cycles. To do so, we explored the electronic, magnetic, and lattice dynamic properties of a series of calcium ferrites (Ca x Fe y O z ) and applied them for CO 2 capture. Our results showed that all of them can thermodynamically react with CO 2 to form CaCO 3 and iron oxides. Compared to pure CaO capturing CO 2 , CaFe 3 O 4 , CaFe 2 O 4 , and Ca 2 Fe 2 O 5 could shift the CO 2 regeneration temperature to a lower range. The experimental measurements showed that CaFeO 2 is a good CO 2 captor with or without the presence of an O 2 presence. The calculated thermodynamic properties of Ca x Fe y O z capturing the CO 2 reactions can be used to find their operational temperature ranges for different CO 2 capture technologies.

CO2 capture↗
DOE OSTI2018

Experimental and Computational Investigation of Lanthanide Ion Doping on BiVO 4 Photoanodes for Solar Water Splitting

N-type bismuth vanadate (BiVO4) has emerged as one of the most promising photoanodes for use in water-splitting photoelectrochemical cells in recent years. However, its photoelectrochemical properties may be further enhanced by optimizing its band gap and its charge-transport properties. Doping at the V5+ and O2- sites of BiVO4 has proven to be an effective strategy to alter the oxide electronic band structure and/or charge-transport properties, but the effect of doping at the Bi3+ site is not nearly as well understood. In this study, we performed a combined experimental and theoretical study of BiVO4 doped with lanthanide (Ln) elements (La, Ce, Sm, and Yb) at the Bi3+ site, and we elucidated the effect of doping on the electronic band structure and charge-transport properties of BiVO4. Furthermore, we performed density functional theory calculations to investigate the combined effect of the Ln doping and oxygen vacancies, which are intrinsic defects in BiVO4. Our results showed that for some cases, the simultaneous consideration of Ln doping and O vacancy leads to changes that cannot be obtained by the sum of the changes caused by Ln doping alone and O vacancy alone, which was critical for understanding the experimental results. The various ways that the Ln dopants modified the electronic band structure and charge-transport properties of BiVO4 demonstrated in this study can provide useful guidelines for the tuning of the composition of oxide-based photoelectrodes.

Govindaraju, Gokul V.↗