Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “conversion”

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 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Aqueous Synthesis of Concave Rh Nanotetrahedra with Defect-Rich Surfaces: Insights into Growth-, Defect-, and Plasmon-Enhanced Catalytic Energy Conversion

The control of morphology in the synthesis of Rh nanocrystals can be used to precisely tailor the electronic surface structure; this in turn directly influences their performance in catalysis applications. Many works have brought attention to the development of Rh nanostructures with low-index surfaces, but limited effort has been devoted to the study of high-index and surface defect-enriched nanocrystals as they are not favored by thermodynamics because of the involvement of high-energy surfaces and increased surface-to-volume ratios. Here, we demonstrate an aqueous synthesis of concave Rh nanotetrahedra (CTDs) serving as efficient catalysts for energy conversion reactions. CTDs are surface defect-rich structures that form through a slow growth rate and follow the four-step model of metallic nanoparticle growth. Via the tuning of the surfactant concentration, the morphology of Rh CTDs evolved into highly excavated nanotetrahedra (HETDs) and twinned nanoparticles (TWs). Unlike the CTD surfaces with abundant adatoms and vacancies, HETDs and TWs have more regular surfaces with layered terraces. Each nanocrystal type was evaluated for methanol electrooxidation and hydrogen evolution from hydrolysis of ammonia borane, and the CTDs significantly showed the best catalytic performance because of defect enrichment, which benefits the surface reactivity of adsorbates. In addition, both CTDs and HETDs have strong absorption near the visible light region (382 and 396 nm), for which they show plasmon-enhanced performance in photocatalytic hydrogen evolution under visible light illumination. CTDs are more photoactive than HETDs, likely because of more pronounced localized surface plasmon resonance hot spots. Lastly, this facile aqueous synthesis of large-surface-area, defect-rich Rh nanotetrahedra is exciting for the fields of nanosynthesis and catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Noble-Metal-Free, Nickel-Based Dual Functional Materials for Improved Methane Production from In Situ Carbon Dioxide Capture and Conversion

Promoters for dual functional materials have not been well explored, but promoters could improve the efficiency of the process by improving the selectivity of the CO 2 methanation process. Utilizing integrated capture and conversion, where CO 2 is captured and converted to useful products, would allow for a useful avenue to control CO 2 emissions. One such way to accomplish this would be to utilize materials that can both capture and convert CO 2 to useful products. However, these materials are often based on costly noble metals, like ruthenium and platinum, decreasing their viability on an industrial scale. Less expensive metals, for example, nickel, would allow for dual functional materials to be more readily utilized in industrial settings. Nickel-based dual functional materials often do not react with the captured CO 2 and merely desorb the CO 2 rather than form a useful product. However, promoters have not been well explored for these types of materials to improve the catalytic properties, which would be beneficial to improve nickel-based materials. Herein, we report the addition of ytterbium on a nickel-based dual functional material and the improvements to the production of methane from captured CO 2 with the incorporated ytterbium promoter. The ytterbium promoter improves the selectivity of the catalysts for the hydrogenation of captured CO 2 to methane and increases the ability for the material to capture CO 2 due to additional basic sites being formed on the surface of alumina. As a result, the 12%Ni/4%Yb/6%Na 2 O/Al 2 O 3 catalyst was utilized to capture carbon dioxide and then convert the captured CO 2 to methane over five cycles, where both the amount captured and the amount converted remained stable, indicating the stability of the material over long-term use.

Catalysts↗
DOE OSTI2016

Enhanced Acid-Catalyzed Biomass Conversion to Hydroxymethylfurfural Following Cellulose Solvent- and Organic Solvent-Based Lignocellulosic Fractionation Pretreatment

Cellulose is a promising, sustainable source of reduced carbon for producing fuels and chemicals to displace petroleumderived products. One hurdle to realizing this potential is the recalcitrance of cellulose to enzymatic and acid catalytic depolymerization. Numerous pretreatments to enhance the reactivity of cellulose prior to enzymatic hydrolysis have been developed for the production of fermentatively derived biofuels. However, little work has been published on the effects of pretreatment on acid-catalyzed hydrolysis of cellulose combined with the catalytic conversion of the resultant glucose to products [e.g., 5-hydroxymethylfurfural (HMF), $γ$-valerolactone (GVL), etc.].

09 BIOMASS FUELS↗
DOE OSTI2020

Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural

5-hydroxymethylfurfural (HMF) and furfural are promising platform molecules which can be converted to fuel intermediates and hydrocarbon fuels. Herein, one-step, direct conversion of the carbohydrates in never treated biomass to HMF and furfural in a microwave reactor was investigated. The influence of reaction temperature, time, feedstock, addition of Lewis and Bronsted acids, solvent and solvent to aqueous ratio were studied to find the optimum process conditions to maximize the yields of furfurals. The reaction conditions of 200 degrees C for 5 min with 33 mM HCl and 8 mM AlCl 3 using a dioxane/water (4:1) miscible solvent system were found to be the most conducive for direct dehydration of the glucan and hemicelluloses present in untreated poplar wood to furfural and HMF in yields of 91 and 69%, respectively. Furfural could be easily produced in yields greater than 80%, and once formed, it was found to be stable under the various process conditions explored. In contrast, HMF yields varied with both reaction time and temperature, as it readily underwent rehydration to levulinic acid in yields approaching 25-30% at increased reaction severity. The additions of both Bronsted (HCl) and Lewis (AlCl 3 ) acids in catalytic amounts, i.e., 33 and 8 mM, respectively, were required to maximize the yield of furfurals. Reactions were also performed on other feedstocks (corn stover, switchgrass, loblolly pine, and pure cellulose) to investigate the effect of feedstock type on furfurals yields. Results showed that HMF and furfural yields were primarily dependent on hexosan and pentosan loading regardless of the type of feedstock. In addition, biomass physical features, such as crystallinity or the presence of other biomass constituents, such as lignin, had little influence on furfurals yields.

09 BIOMASS FUELS↗
DOE OSTI2016

The Role of Iron-Bearing Minerals in NO 2 to HONO Conversion on Soil Surfaces

Nitrous acid (HONO) accumulates in the nocturnal boundary layer where it is an important source of daytime hydroxyl radicals. Although there is clear evidence for the involvement of heterogeneous reactions of NO2 on surfaces as a source of HONO, mechanisms remain poorly understood. We used coated-wall flow tube measurements of NO2 reactivity on environmentally relevant surfaces [Fe (hydr)oxides, clay minerals, and soil from Arizona and the Saharan Desert] and detailed mineralogical characterization of substrates to show that reduction of NO2 by Fe-bearing minerals in soil can be a more important source of HONO than the putative NO2 hydrolysis mechanism. The magnitude of NO2-to-HONO conversion depends on the amount of Fe2+ present in substrates and soil surface acidity. Studies examining the dependence of HONO flux on substrate pH revealed that HONO is formed at soil pH < 5 from the reaction between NO2 and Fe2+(aq) present in thin films of water coating the surface, whereas in the range of pH 5–8 HONO stems from reaction of NO2 with structural iron or surface complexed Fe2+ followed by protonation of nitrite via surface Fe-OH2+ groups. Reduction of NO2 on ubiquitous Fe-bearing minerals in soil may explain HONO accumulation in the nocturnal boundary layer and the enhanced [HONO]/[NO2] ratios observed during dust storms in urban areas.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Adsorption of selenite onto Bacillus subtilis: the overlooked role of cell envelope sulfhydryl sites in the microbial conversion of Se(IV)

Microbial activities play a central role in the global cycling of selenium. Microorganisms can reduce, methylate and assimilate Se, controlling the transport and fate of Se in the environment. However, the mechanisms controlling these microbial activities are still poorly understood. In particular, it is unknown how the negatively-charged Se(IV) and Se(VI) oxyanions that dominate the aqueous Se speciation in oxidizing environments bind to negatively-charged microbial cell surfaces in order to become bioavailable. Here, we show that the adsorption of selenite onto Bacillus subtilis bacterial cells is controlled by cell envelope sulfhydryl sites. Once adsorbed onto the bacteria, selenite is reduced, and forms reduced organo-Se compounds (e.g., R1S-Se-SR2). Because sulfhydryl sites are present within cell envelopes of a wide range of bacterial species, sulfhydryl-controlled adsorption of selenite likely represents a general mechanism adopted by bacteria to make selenite bioavailable. Therefore, sulfhydryl binding of selenite likely occurs in a wide range of oxidized Se-bearing environments, and because it is followed by microbial conversion of selenite to other Se species, the process represents a crucial step in the global cycling of Se.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Cobalt(II) Phthalocyanine Substituents Tune the Electrocatalytic CO 2 Conversion to Methanol

Cobalt phthalocyanine (Co(II)Pc) and its derivatives are promising molecular electrocatalysts for the electrochemical reduction of CO 2 to CO and methanol (CH 3 OH). Despite increasing interest, a detailed mechanistic understanding of how ligand substituents influence catalytic activity, selectivity, and efficiency remains limited. In this study, we employ density functional theory (DFT) to systematically investigate the influence of electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the electronic structure and redox properties of the Co(II)Pc electrocatalyst, and to elucidate CO 2 RR mechanistic pathways. Our results reveal that EWGs cause a positive shift in the reduction potentials, favor CO 2 binding over protonation of the Co metal center and promote downstream methanol formation at mild potentials. EDGs show opposite trends including favorable protonation steps, promoting a negative shift in the reduction potential, and facilitating the hydrogen evolution reaction (HER), which competes with the desired CO 2 RR pathway. Notably, CO dissociation is thermodynamically and kinetically unfavorable across all systems, positioning the redox potential versus CO dissociation energy as a key factor for methanol selectivity. Furthermore, these insights provide a predictive framework for rational catalyst design and underscore the critical role of electronic tuning in advancing molecular electrocatalysts for sustainable CO 2 conversion.

Alcohols↗
DOE OSTI2026

Catalytic Ambient Temperature Dinitrogen Conversion to a Bis(silyl)amine by Mononuclear Group 4 Aryloxide Complexes

The homogeneous conversion of ambient dinitrogen to amine products via the N2 reduction reaction (N2RR) remains a prized yet challenging feat for d-block complexes and is scarcely reported for f-block complexes. New, mononuclear TiIV and ZrIV aryloxide complexes Ti(DP)2 (1Ti), Zr(DP)2 (1Zr), and DP = [2-(OC6H2-2-tBu,4-Me)2CHPh] produce up to 51 eq. and up to 7.0 eq. of HN(SiMe3)2 per Ti/Zr, from N2, K0, weak acid, and chlorotrimethylsilane. Complex 1Ti exhibits more than double the activity toward N2-silylation of any previously reported Ti N2RR catalyst and can also catalyze the formation of up to 19 eq. of NH3, a new feature in early metal N2RR chemistry. The mononuclear 1Zr is the most active Zr catalyst for N2-silylation to date. [KSm(DP)2(THF)3] (1Sm), the mononuclear analogue of our previously reported dinuclear A-Sm complex, displays only stoichiometric N2-silylation due to its vulnerability to deleterious side reactions. DFT calculations confirm the catalysis can proceed via a monomeric Ti complex with a terminally bound, activated N2, agreeing with experimental 1H DOSY NMR measurements; the N-H bond is formed first, directing the catalyst selectivity. The isolable reduction product [K3(THF)Ti(DP)(DP-)(N2)] is also an active catalyst, and an intermediate in the calculated cycle.

Hernandez, Matthew↗
DOE OSTI2024

CH 3 Radical Generation in Microplasmas for Up-Conversion of Methane

The conversion of methane, CH 4 , into higher value chemicals using low temperature plasmas is challenged by both improving efficiency and selectivity. One path towards selectivity is capturing plasma produced methyl radicals, CH 3 , in a solvent for aqueous processing. Due to the rapid reactions of methyl radicals in the gas phase, the transport distance from production of the CH 3 to its solvation should be short, which then motivates the use of microplasmas. The generation of CH 3 in Ar/CH 4 /H 2 O plasmas produced in nanosecond pulsed dielectric barrier discharge microplasmas is discussed using results from a computational investigation. The microplasma is sustained in the channel of a microfluidic chip in which the solvent flows along one wall or in droplets. CH 3 is primarily produced by electron-impact of and dissociative excitation transfer to CH 4 , as well as CH 2 reacting with CH 4 . CH 3 is rapidly consumed to form C 2 H 6 which, in spite of being subject to these same dissociative processes, accumulates over time, as do other stable products including C 3 H 8 and CH 3 OH. The gas mixture and electrical properties were varied to assess their effects on CH 3 production. CH 3 production is largest with 5% CH 4 in the Ar/CH 4 /H 2 O mixture due to an optimal balance of electron-impact dissociation, which increases with CH 4 percentage, and dissociative excitation transfer and CH 2 reacting with CH 4 , which decrease with CH 4 percentage. Design parameters of the microchannels were also investigated. Increasing the permittivity of the dielectrics in contact with the plasma increased the ionization wave intensity which increased CH 3 production. Increased energy deposition per pulse generally increased CH 3 production as does lengthening pulse length up to a certain point. The arrangement of the solvent flow in the microchannel can also affect the CH 3 density and fluence to the solvent. The fluence of CH 3 to the liquid solvent is increased if the liquid is immersed in the plasma as a droplet or is a layer on the wall where the ionization wave terminates. The solvation dynamics of CH 3 with varying numbers of droplets was also examined. Here, the maximum density of solvated methyl radicals CH 3aq occurs with a large number of droplets in the plasma. However, the solvated CH 3aq density can rapidly decrease due to desolvation, emphasizing the need to quickly react the solvated species in the solvent.

03 NATURAL GAS↗
DOE OSTI2015

Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A

For this research, we have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Q y , the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors (NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Q x occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Lastly, our present analysis can be considered as a general approach allowing identification of a reduced subset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.

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

Configurational-Bias Monte Carlo Back-Mapping Algorithm for Efficient and Rapid Conversion of Coarse-Grained Water Structures into Atomistic Models

Coarse-grained molecular dynamics (MD) simulations represent a powerful approach to simulate longer time scale and larger length scale phenomena than those accessible to all-atom models. The gain in efficiency, however, comes at the cost of atomistic details. The reverse transformation, also known as back-mapping, of coarse grained beads into their atomistic constituents represents a major challenge. Most existing approaches are limited to specific molecules or specific force-fields and often rely on running a long time atomistic MD of the back-mapped configuration to arrive at an optimal solution. Such approaches are problematic when dealing with systems with high diffusion barriers. Here, we introduce a new extension of the configurational-bias-Monte-Carlo (CBMC) algorithm, which we term the crystalline-configurational-bias-Monte-Carlo (C-CBMC) algortihm, that allows rapid and efficient conversion of a coarse-grained model back into its atomistic representation. Although the method is generic, we use a coarse-grained water model as a representative example and demonstrate the back-mapping or reverse transformation for model systems ranging from the ice-liquid water interface to amorphous and crystalline ice configurations. A series of simulations using the TIP4P/Ice model are performed to compare the new CBMC method to several other standard Monte Carlo and Molecular Dynamics based back-mapping techniques. In all the cases, the C-CBMC algorithm is able to find optimal hydrogen bonded configuration many thousand evaluations/steps sooner than the other methods compared within this paper. For crystalline ice structures such as a hexagonal, cubic, and cubic-hexagonal stacking disorder structures, the C-CBMC was able to find structures that were between 0.05 and 0.1 eV/water molecule lower in energy than the ground state energies predicted by the other methods. Detailed analysis of the atomistic structures show a significantly better global hydrogen positioning when contrasted with the existing simpler back-mapping methods. The error in the RDFs of backmapped relative to reference configuration for the CCBMC, MD, and MC were found to be 6.9, 8.7, and 12.9 respectively for the hexagonal system. For the cubic system the relative error of the RDFs for the CCBMC, MD, and MC were found to be 18.2, 34.6, and 39.0 respectively. Finally, our results demonstrate the efficiency and efficacy of our new back-mapping approach, especially for crystalline systems where simple force-field based relaxations have a tendency to get trapped in local minima.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO 2 (101)

Understanding thermochemical transformations of formic acid (FA) on metal oxide surfaces is important for many catalytical reactions. Here we study thermally induced reactions of FA on a single-crystalline and nanocrystalline anatase TiO 2 (101). We employ a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) to follow the FA surface intermediates and reaction products above room temperature. We find that the primary reaction products desorbing at about 300, 480, and 515 K are molecular water, carbon monoxide, and formaldehyde, respectively. Bidentate (BD) formate and bridging hydroxyl (HO b ) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (V O ) are also likely participants despite their low stability at the surface. In conclusion, the parallel studies on single crystals and faceted TiO 2 (101) nanoparticles reveal the spectroscopic commonalities of surface species and of the thermal conversion of molecular and deprotonated forms of FA.

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

Soft X-ray Emission Spectroscopy of Phosphorus Compounds for Energy Conversion and Storage

Phosphorus (P) is a ubiquitous component of materials for energy conversion and storage. Despite the effectiveness of soft X-ray emission spectroscopy (XES) to characterize these complex materials, XES studies of P-containing compounds are still largely missing. In this investigation, the electronic structure and XES signatures from the P L 2,3 -edge are probed for nine solid-state P-containing compounds characterized by various oxidation states and chemical environments: GaP (3−) , InP (3−) , red-P (0) , H 3 P (3+) O 3 , Na 2 H 2 P 2 (4+) O 6 , H 3 P (5+) O 4 , KH 2 P (5+) O 4 , Na 2 HP (5+) O 4 , and InP (5+) O 4 . The XES spectrum of each material exhibits distinct spectral fingerprints, which provide a robust basis for the speciation of complex P-containing samples. Density functional theory calculations shed light on the electronic structure of selected materials and particularly on the effect of phosphorus-oxygen hybridization. This study provides a comprehensive understanding of P L 2,3 XES spectral fingerprints across a wide range of oxidation states and chemical environments. These data sets and insights pave the way for dedicated future work, such as in situ and operando investigations of P-containing compounds in energy-related applications, where speciation of P compounds is needed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO 2 Anodes During Lithiation Using LiPF 6 Salt

Titanium dioxide has been identified as a prospective anode material for use in lithium ion batteries. The higher lithiation potential of TiO 2 versus other common anodes is more electrochemically compatible with most organic electrolytes, thus leading to reduced solid electrolyte interphase formation and overall more stable battery systems. However, in this study TiO 2 has exhibited poor cycling stability with common electrolytes containing lithium hexafluorophosphate (LiPF 6 ) salt. Combined electrochemical and spectroscopic analyses have revealed this to be due to the onset of reversible fluorination of the anode and chemical conversion of TiO 2 to TiOF 2 during lithiation. Comparison of electrochemical cycling of atomic-layer-deposited TiO2 anodes using LiPF6 with and without a hydrofluoric acid scavenger, tributylamine, to cycling using a nonfluorinated lithium perchlorate (LiClO 4 ) salt indicates that the in situ formation of hydrofluoric acid in the electrolyte from decomposition of the PF$_{6^–}$ anion alters the lithiation electrochemistry. X-ray photoelectron spectroscopy (XPS) analysis and time-of-flight secondary-ion mass spectrometry (ToF SIMS) depth profiling measurements confirmed the presence of TiF 2 and TiOF surface and bulk phases, respectively, in the electrode upon lithiation.

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

Hydrogen and Electric Power Generation from Liquid Microjets: Design Principles for Optimizing Conversion Efficiency

Historically, Liquid water microjets have been successfully employed for both electrical power generation and gaseous hydrogen production, but the demonstrated efficiencies have been low. Here, we employ a combination of a modified Poisson-Boltzmann description, continuum hydrodynamic equations, and microjet electrokinetic experiments to gain detailed insight into the origin of the streaming currents produced in pure water. We identify the contributions to the streaming current from specific ion adsorption at the solid/liquid interface and from long-ranged electrostatic interactions, finding that the portion originating from the latter dominate at charged surfaces. The detailed understanding afforded by theory and the close agreement with experimental results elucidates design principles for optimizing hydrogen production and power generation. Changing the sign of the surface charge density through targeted use of surface coatings via silanization switches the primary charge carrier between hydronium and hydroxide and therefore switches the corresponding production of molecular hydrogen to oxygen at the target electrode. Moreover, hydrophobic surface coatings reduce dissipation due to fluid/solid friction, thereby increasing the conversion efficiency.

08 HYDROGEN↗
DOE OSTI2017

Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface

We study methyl formate formation during methanol conversion on the fully oxidized and partially reduced ceria (111) surface using density functional theory. Starting from methanol and formaldehyde adsorbed on the surface, we consider two pathways of methyl formate production. Pathway 1 consists of formaldehyde dehydrogenation followed by oxygen–carbon bond formation. Along pathway 2, the oxygen–carbon bond is established prior to intermediate dehydrogenation. Formaldehyde production is observed at elevated temperature at which we expect both pathways to be energetically attainable on the fully oxidized surface. However, the probability of both reactants being adsorbed next to each other is low. This probability can be increased by the reduction of the surface. The partially reduced ceria surface is modeled by the introduction of an oxygen vacancy in the surface. If formaldehyde adsorbs over a vacancy, both pathways potentially contribute to methyl formate formation. In contrast, if methoxide that is obtained by dissociative adsorption of methanol is placed in the vacancy, methyl formate production becomes energetically highly demanding. Still, dehydrogenation of methoxide or methoxide exchange with coadsorbates converts methoxide in a vacancy to an active species for methyl formate formation while increasing the residence time of methoxide on the surface. Importantly, the preference of pathway 1 is due to the promotion of surface-bound formaldehyde dehydrogenation by methoxide.

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

Internal Conversion between Bright (1 1 B $^+_u$) and Dark (21 A $^-_g$) States in s- trans -Butadiene and s- trans -Hexatriene

Internal conversion (IC) between the two lowest singlet excited states, 1 1 B$_u^+$ and 2 1 A$_g^–$, of s-trans-butadiene and s-trans-hexatriene is investigated using a series of single- and multi- reference wave function and density functional theory (DFT) methodologies. Three independent types of the equation-of-motion coupled-cluster (EOMCC) theory capable of providing an accurate and balanced description of one- as well as two-electron transitions, abbreviated as δ-CR-EOMCC(2,3), DIP-EOMCC(4h2p){N o }, and DEA-EOMCC(4p2h){N u } or DEA-EOMCC(3p1h,4p2h){N u }, consistently predict that the 1 1 B$_u^+$/2 1 A$_g^–$ crossing in both molecules occurs along the bond length alternation coordinate. However, the analogous 1 1 B$_u^+$ and 2 1 A$_g^–$ potentials obtained with some multireference approaches, such as CASSCF and MRCIS(D), as well as with the linear-response formulation of time-dependent DFT (TDDFT), do not cross. Hence, caution needs to be exercised when studying the low-lying singlet excited states of polyenes with conventional multiconfigurational methods and TDDFT. The multistate many-body perturbation theory methods, such as XMCQDPT 2 , do correctly reproduce the curve crossing. Among the simplest and least expensive computational methodologies, the DFT approaches that incorporate the contributions of doubly excited configurations, abbreviated as MRSF (mixed reference spin-flip) TDDFT and SSR( 4,4 ), accurately reproduce our best EOMCC results. This is highly promising for nonadiabatic molecular dynamics simulations in larger systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO 2

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO 2 R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO 2 mass transport, and ECO 2 R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗