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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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Lab-scaled performance evaluation of novel water-lean solvents for post combustion CO 2 capture

Here, this work focuses on demonstrating the energetic performance and operational reliability in a continuous system of RTI's water-lean solvents for post-combustion CO 2 capture applications. RTI's Non-Aqueous Solvent, NAS-1A was subjected to 100 h of continuous, CO 2 capture and regeneration operation using a Lab-scale Gas Absorption System (LsGAS) while the CO 2 capture efficiency, mass balance, and total energy inputs were monitored. Throughout the test period, NAS-1A demonstrated stable operation with 90% CO 2 capture while requiring about 15% lower total energy input for solvent regeneration compared to 30 wt% monoethanolamine (MEA) solution. The use of a slipstream of CO 2 -rich solvent from the absorber sump reduced the regenerated CO 2 temperature before the gas was further cooled by the overhead condenser at the top of the desorber. The rich-split setup combined with a wash section may be an effective approach to remove water and solvent vapor from the regenerated CO 2 as well as to recover heat at the top of the desorber. NAS-1B was later developed and included a modifier component that lowers the heat of CO 2 absorption and reduces the vapor pressure of the amine component. The total energy inputs for 90% CO 2 capture with NAS-1B was found to be 25% less than that of the MEA. A gas chromatograph was used to monitor the amine concentration in the gas leaving the absorber wash section. It was found that under similar operating conditions, the presence of the modifier in NAS-1B reduces the amine in the absorber off-gas from 143 ppm in NAS-1A to 20 ppm.

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

Analysis and Testing of Parsons NGS Solvent Formulation

Three drums containing solvent used during the Next Generation Solvent Test (NGST) conducted by Parsons in 2014-2015 were received at SRNL. After homogenization, samples from each drum were removed, and a composite sample prepared. This composite was analyzed to determine current SRNL characterization method efficacy, and to determine if the 1,3-dicyclohexyl-2- (isotridecyl) guanidine (DCiTG) suppressor could be selectively removed. The results of this work indicate that the titration analytical method currently employed at SRNL is effective at quantitating the DCiTG. The nuclear magnetic resonance (NMR) method at SRNL can detect the DCiTG, as well its amine and urea decomposition products. However, further development work will be required to allow the 1 H NMR method to quantitate these species. A series of three washing tests were performed on composite samples of the solvent. The results show that up to 67% of the DCiTG was removed from the solvent by simple washing, at multiple ratios of solvent: aqueous phase. This may indicate that a simple pathway exists to wash out the DCiTG and reclaim the solvent (~150 gallons) for future use at the Salt Waste Processing Facility (SWPF).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Dependency of solvation effects on metal identity in surface reactions

Solvent interactions with adsorbed moieties involved in surface reactions are often believed to be similar for different metal surfaces. However, solvents alter the electronic structures of surface atoms, which in turn affects their interaction with adsorbed moieties. To reveal the importance of metal identity on aqueous solvent effects in heterogeneous catalysis, we studied solvent effects on the activation free energies of the O–H and C–H bond cleavages of ethylene glycol over the (111) facet of six transition metals (Ni, Pd, Pt, Cu, Ag, Au) using an explicit solvation approach based on a hybrid quantum mechanical/molecular mechanical (QM/MM) description of the potential energy surface. A significant metal dependence on aqueous solvation effects was observed that suggests solvation effects must be studied in detail for every reaction system. The main reason for this dependence could be traced back to a different amount of charge-transfer between the adsorbed moieties and metals in the reactant and transition states for the different metal surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Spectroelectrochemical determination of thiolate self-assembled monolayer adsorptive stability in aqueous and non-aqueous electrolytes

Self-assembled monolayers (SAM) are ubiquitous in studies of modified electrodes for sensing, electrocatalysis, and environmental and energy applications. However, determining their adsorptive stability is crucial to ensure robust experiments. Here, in this work, the stable potential window (SPW) in which a SAM-covered electrode can function without inducing SAM desorption was determined for aromatic SAMs on gold electrodes in aqueous and non-aqueous solvents. The SPWs were determined by employing cyclic voltammetry, attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), and surface plasmon resonance (SPR). The electrochemical and spectroscopic findings concluded that all the aromatic SAMs used displayed similar trends and SPWs. In aqueous systems, the SPW lies between the reductive desorption and oxidative desorption, with pH being the decisive factor affecting the range of the SPW, with the widest SPW observed at pH 1. In the non-aqueous electrolytes, the desorption of SAMs was observed to be slow and progressive. The polarity of the solvent was the main factor in determining the SPW. The lower the polarity of the solvent, the larger the SPW, with 1-butanol displaying the widest SPW. This work showcases the power of spectroelectrochemical analysis and provides ample future directions for the use of non-polar solvents to increase SAM stability in electrochemical applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Conversion of lignin into a water-soluble polyacid using a MOF catalyst

A process for valorization of lignin includes the steps of mixing lignin; a MOF catalyst metalated with a metal atom selected from the group consisting of Fe, Mn, Co, Cu, or Ni, and combinations thereof; an oxidizing agent; and an aqueous solvent. The product of this process, a charged polyacid-containing species derived from lignin, may be included in a dispersion with a dispersible particulate material, and an aqueous dispersing medium.

09 BIOMASS FUELS↗
DOE OSTI2022

The pH and Potential Dependence of Pb–Catalyzed Electrochemical CO 2 Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte

The conversion of waste CO 2 to value-added chemicals through electrochemical reduction is a promising technology for mitigating climate change while simultaneously providing economic opportunities. The use of non-aqueous solvents like methanol allows for higher CO 2 availability and novel products. In this work, the electrochemistry of CO 2 reduction in acidic methanol catholyte at a Pb working electrode was investigated while using a separate aqueous anolyte to promote a sustainable water oxidation half-reaction. The selectivity among methyl formate (a product unique to reduction of CO 2 in methanol), formic acid, and formate was critically dependent on the catholyte pH, with higher pH conditions leading to formate and low pH favoring methyl formate. Furthermore, the potential dependence of the product distribution in acidic catholyte was also investigated, with a faradaic efficiency for methyl formate as high as 75% measured at -2.0 V vs Ag/AgCl.

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

Cooperative Role of Mixed Solvent in the Evaporation-Induced Self-Assembly of Polypeptoid Nanocrystals

Peptoids, or polypeptoids, are biomimetic polymers that can self-assemble into nanocrystals for biomedical and biotechnological applications. Polypeptoid nanocrystals can be prepared by evaporation-induced self-assembly, but the roles of solvent components for this process have long been overlooked at the molecular level, leaving a tunable parameter for improving self-assembly protocols. This work utilized molecular dynamics simulations to study the effects of water and the commonly used tetrahydrofuran (THF) on the assembly of nanosheets from molecules of acetylated diblock polypeptoid, poly-(N-decylglycine)-b-poly-(N-2-(2-(2-methoxyethoxy)-ethoxy) ethylglycine), abbreviated as Ac-Ndc10-Nte10. To probe the stages of self-assembly, isolated molecules and preassembled nanofibers/nanosheets were simulated in pure THF, water, and their mixtures, respectively. The assembly energies show that the THF/water mixture has a greater tendency to form nanosheets than pure water. In a THF/water mixture, polypeptoids were found more uncoiled in isolated states, less compact in disordered agglomerates, and with reduced requirement for the Nte block to cover hydrophobic Ndc surfaces in the nanocrystals. Mixed solvent is vital to initiating self-assembly, as THF assists in the opening of coiled polypeptoid molecules, while water provides the thermodynamics to aggregate and ultimately form nanocrystals. To obtain wider nanosheets, it is recommended that some THF be maintained in the aqueous solvent before it becomes exhausted by evaporation. Near the nanosheet surface, the THF concentration is higher than that in bulk solution (3-4 times in 4 M THF/water). The strong adsorption of THF indicates the self-assembly in a de facto mixed solvent. These results are expected to guide the refinement of evaporation-induced self-assembly protocols for polypeptoid nanocrystals.

Luo, Xubo↗
DOE OSTI2023

Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)

This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2026

Dual-loop Solvent-based CCS for Net Negative CO 2 Emissions with Lower Cost

This final technical report details the successful design, construction, and operational validation of an innovative dual-loop CO 2 capture technology designed to achieve deep decarbonization (>99%) from Natural Gas Combined Cycle (NGCC) power plants that results in the electricity with carbon intensity of approximate 42 kg CO 2 -eq/MWh, less than the electricity produced by solar PV. The integrated process couples a primary aqueous solvent (in this project, a water lean solvent – WLS) absorption loop for bulk CO 2 removal with a secondary potassium hydroxide (KOH) polishing loop featuring electrochemical regeneration. This architecture leverages the higher exergy efficiency of the primary loop while utilizing the fastest kinetic of the secondary loop to capture dilute residual CO 2 , achieving an overall capture rate of 99.9% and co-producing pure hydrogen after moisture being condensed and dehydrated. Technical feasibility was established through a comprehensive 2,000-hour experimental campaign on a bench-scale fully-integrated unit (using 4” absorber and 4” stripper) with the feeding flue gas flowrate in the range of 8-20 cfm, confirming the attainment of Technology Readiness Level (TRL) 4. The project executed extensive parametric testing followed by 1,000 hours of continuous steady-state testing, demonstrating exceptional process stability with the electrochemical regenerator exhibiting less than a 10% reduction in electrical conductivity over the duration of the campaign. Operational characterization gathering on the bench unit revealed distinct energy profiles for the hybrid system: the primary loop required approximately 280 kJ mol -1 for bulk removal, while the polishing loop required approximately 1,600 kJ mol -1 specifically when reducing dilute CO 2 concentrations from ~740 ppm down to <50 ppm. (Please note those energy values/numbers can only be viewed as relative relationship and should not be extrapolated as absolute values required for CO 2 capture). Furthermore, dynamic testing validated the system’s flexibility for utility applications, demonstrating a rapid process response time of <30 minutes to changes in flue gas flowrate. Emission monitoring confirmed that the dual-loop architecture effectively mitigates solvent losses, utilizing a water wash to remove entrained aerosols to <1 ppm. The Techno-Economic Analysis (TEA) indicates a cost of capture of $\$$59.3/tonne and a Levelized Cost of Electricity (LCOE) of 71.7 $\$$/MWh at the overall capture efficiency of 99.8% of total carbon in the flue gas stream, with sensitivity analysis identifying an economic optimum when the primary loop captures 97% of the total CO 2 . A Life Cycle Assessment (LCA) confirms the technology’s potential for net-negative emissions, determining a Global Warming Potential (GWP) of 52 kg CO 2 -eq/MWh—significantly lower than the baseline—which further decreases to 42 kg CO 2 -eq/MWh when crediting the displacement of conventional hydrogen production.

03 NATURAL GAS↗
DOE OSTI2020

A Method for Obtaining Liquid–Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H 2 O

Adsorption is an important step in heterogeneous catalysis as it predetermines how many reactant molecules can participate in a surface reaction per unit time. While the rate of adsorption processes is well studied in gas–solid adsorption in both theory and experiment, such rates are still not well studied for liquid–solid adsorption. This is partly because the ever-changing configurations of liquid-phase solvent molecules impede the ability to study a molecule approaching a surface from a liquid phase by either experiment or theory. In this work, we develop a method using molecular dynamics (MD) simulations to study the rate of adsorption in liquid–solid adsorption processes. Specifically, we use MD to model the diffusion of a methanol molecule in aqueous solvent and its adsorption to a Pt(111) surface. We find that by approximating the solute motion as following the same displacement rates as a random walk model, the adsorbed and non-adsorbed states of the methanol molecule near the Pt(111) surface can be discerned and quantified. In particular, this methodology enables extracting a sticking coefficient and a macroscopically relatable adsorption rate. This method can be applied to arbitrary types of reactants and surfaces, as well as different liquid environments, thus providing a general tool for predicting quantitative adsorption rates of liquid–solid adsorption systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

In-Situ Ligand-Induced Chirality Transfer in Emissive CdSe Nanoplatelets

Terminating semiconductor nanocrystals with chiral organic ligands can induce chiroptical properties that combine the chiral character of the ligands with the strong and tunable optical properties of the nanocrystal. However, the synthesis of such chiral-modified nanocrystals is currently limited by solvent incompatibility between polar chiral ligands and nonpolar traditional ligands, as well as by ligand dissolution behavior that ultimately compromises nanocrystal quality and the degree to which chiroptical properties can be manipulated. In this work, we demonstrate a single-step synthesis of chiral cadmium selenide (CdSe) nanoplatelets (NPLs) that eliminates the need for postsynthetic ligand exchange in aqueous solvents, resulting in highly emissive chiral CdSe NPLs. By directly incorporating chiral aminodecanoic acid ligands during synthesis, we achieve in situ ligand binding and chirality transfer to CdSe NPLs. This approach produces CdSe NPLs with high photoluminescence quantum efficiencies of 50% and circular dichroism dissymmetry factors (gCD) on the order of 10 –4 .

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

Sustainable lead management in halide perovskite solar cells

Despite the rapid development of perovskite solar cells (PSCs) toward commercialization, the toxic lead (Pb) ions in PSCs pose a potential threat to the environment, health and safety. Managing Pb via recycling represents a promising approach to mitigating its toxicity. However, managing Pb from commonly used organic solvents has been challenging due to the lack of suitable Pb adsorbents. Here, we report a new adsorbent for both separation and recovery of Pb from PSC pollutants. The synthesized iron-incorporated hydroxyapatite possesses a strongly negatively charged surface that improves electrostatic interaction through surface-charge delocalization, thus leading to enhanced Pb adsorption. Finally, we demonstrate the feasibility of a complete Pb management process, including the purification of Pb-containing non-aqueous solvents below 15 parts per 10 9 , a level compliant with the standards of the US Environmental Protection Agency, as well as recycling of 99.97% of Pb ions by forming lead iodide.

14 SOLAR ENERGY↗
DOE OSTI2024

Reactive capture and electrochemical conversion of CO 2 with ionic liquids and deep eutectic solvents

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO 2 due to their wide electrochemical stability window, low volatility, and high CO 2 solubility. There is environmental and economic interest in the direct utilization of the captured CO 2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO 2 , eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO 2 with aqueous electrolytes presents limited CO 2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO 2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO 2 , often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO 2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra

In this paper, we report the rational design and synthesis of a new, water-stable metal-organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe3+-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based con-struction, Fe-HAF-1 displays exceptional chemical stability in organic and aqueous solvents over a wide pH range (pH 1-14), including in the presence of 5 M NaOH. Despite the charge-neutrality of the Fe 3+ -tris(hydroxamate) centers, Fe-HAF-1 crystals are negatively charged above pH 4. This unex-pected property is attributed to the formation of defects during crystallization that results in uncoordinated hydroxamate ligands or hydroxide-coordinated Fe centers. The anionic na-ture of Fe-HAF-1 crystals enables selective adsorption of pos-itively charged ions in aqueous solution, resulting in efficient separation of organic dyes and other charged species in a size-selective fashion. Fe-HAF-1 presents a new addition to a small group of chelate-based MOFs and provides a rare framework whose 3D connectivity is exclusively formed by metal-hydroxamate coordination.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Stable electrospray signal on a microfabricated glass chip with three-dimensional open edge and tiered depth geometries

This paper presents the microfabrication and performance of a three-dimensional electrospray ionization (ESI) emitter tip made from glass, which achieves stable current signals important for chemical analysis. Our novel microfabrication process and custom-built signal conditioning hardware provides the advantage of providing accurate features and steady signals. The fabrication process relies on standard microfabrication techniques (i.e., deposition, photolithography, and wet etching). This fabrication method involves the novel application of two layers of positive and negative photoresists in addition to Parafilm® wax tape. Open edge and tiered depth details were successfully created from a multilayer planar mask. This is a benefit for integrated miniaturized and microfluidic systems that often require micro features for their functionality but relatively large millimeter size features for their physical periphery. We demonstrate the fundamental performance of electrospray with this microfluidic chip. The emitter tip was fixed on a linear axis stage with high resolution (10 μm) to finely control the tip distance from a metal counter electrode plate. Further, a custom printed circuit board system was built to safely control four voltages applied to the microchip ports from a single high voltage power supply. To readily form the electrospray, non-aqueous solvents were used for their low viscosity and a constant voltage of +2.7 kV was applied to the sheath electrospray microchannel. The liquid being sprayed was 80/20 (v/v) methanol/acetonitrile with 0.1% acetic acid in the sheath microchannel and with ammonium acetate (10–40 mM) in its remaining microchannels. The electrospray signal was measured in response to varying the distance (1.4 to 1.6mm) between the electrospray emitter tip and a metal counter electrode plate in addition to the varying concentration of the background electrolyte, ammonium acetate. Stable and repeatable electrospray signal showed linear relationships with emitter tip distance and concentration (r 2 ≥ 0.95).

42 ENGINEERING↗
DOE OSTI2023

CO 2 adsorption mechanisms at the ZIF-8 interface in a Type 3 porous liquid

Porous liquids (PLs) are an attractive material for gas separation and carbon sequestration due to their permanent internal porosity and high adsorption capacity. PLs that contain zeolitic imidazole frameworks (ZIFs), such as ZIF-8, form PLs through exclusion of aqueous solvents from the framework pore due to its hydrophobicity. The gas adsorption sites in ZIF-8 based PLs are historically unknown; gas molecules could be captured in the ZIF-8 pore or adsorb at the ZIF-8 interface. To address this question, ab initio molecular dynamics was used to predict CO 2 binding sites in a PL composed of a ZIF-8 particle solvated in a water, ethylene glycol, and 2-methylimidazole solvent system. Further, the results show that CO 2 energetically prefers to reside inside the ZIF-8 pore aperture due to strong van der Waals interactions with the terminal imidazoles. However, the CO 2 binding site can be blocked by larger solvent molecules that have greater adsorption interactions. CO 2 molecules were unable to diffuse into the ZIF-8 pore, with CO 2 adsorption occurring due to binding with the ZIF-8 surface. Therefore, future design of ZIF-based PLs for enhanced CO 2 adsorption should be based on the strength of gas binding at the solvated particle surface.

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

Complexation of Astatine(III) with Ketones: Roles of NO 3 – Counterion and Exploration of Possible Binding Modes

Ketones have been proven effective in extracting astatine(III) from aqueous solvents. Previous theoretical studies suggested a mechanism where the “sp 2 ” lone pair on the carbonyl oxygen donates electron density into the π system of the AtO + molecular cation to form a dative-type bond. In this study, co-extraction of NO 3 – as AtO(NO 3 )·(O=CR 1 R 2 ) species into the organic phase appears to be a key factor. Adjusting the electronic properties of the ketone, by having an aryl group instead of an alkyl group in the alpha position of the ketone, increased the electron density on C=O, increased the bond strength between the ketone and AtO + , and in turn increased the extraction of 211 At into the organic phase. Extraction with diketones shows dependence on the bridging distance between the two carbonyl moieties, where a C 3 or longer bridge results in a 10-fold increase in extraction into the organic phase. Furthermore, DFT calculations show the longer bridge allows for the chelation of AtO(NO 3 ) by either the second carbonyl or the phenyl ring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Prediction of Redox Potentials for U, Np, Pu, and Am in Aqueous Solution

The redox properties of the actinides in aqueous solution are important for fuel production/reprocessing and understanding the environmental impact of nuclear waste. The redox potentials for U, Np, Pu, and Am in oxidation states from 0 up to VII (as appropriate) in aqueous solutions have been predicted at the density functional theory level with the B3LYP functional, Stuttgart small core pseudopotential basis sets for the actinides, and explicit (30H 2 O molecules)/implicit treatment of the aqueous solvent using the self-consistent reaction field COSMO and SMD approaches for the implicit solvation. The predictions of the structural parameters of clusters incorporating first and second solvation shells are consistent with the available experimental data., Our results are typically within 0.2 V of the available experimental data using two explicit solvation shells with an implicit solvent model. The use of the PW91 functional substantially improved the prediction of the Pu(VI/V) redox couple. The redox couples for An(VI/IV) and An(V/IV) which involve the addition of protons and removal of the actinyl oxygens led to slightly larger differences from experiment. Here, the An(IV/0) and An(III/0) couples were reliably predicted with our approach. Predictions of the unknown An(II/I) redox potentials were negative, consistent with expectations, and predictions for unknown An(VII/VI), An(III/II), and An(II/0) redox couples improve prior estimates.

Actinides↗