An Integrated Neutrino-AMReX framework for industry-significant chemically reactive flows
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09 BIOMASS FUELS↗
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Mo Atom Rearrangement Drives Layer-Dependent Reactivity in Two-Dimensional MoS 2
Two-dimensional (2D) materials offer a valuable platform for manipulating and studying chemical reactions at the atomic level, owing to the ease of controlling their microscopic structure at the nanometer scale. While extensive research has been conducted on the structure-dependent chemical activity of 2D materials, the influence of structural transformation during the reaction has remained largely unexplored. In this work, we report the layer-dependent chemical reactivity of MoS 2 during a nitridation atomic substitution reaction and attribute it to the rearrangement of Mo atoms. Our results show that the chemical reactivity of MoS 2 decreases as the number of layers is reduced in the few-layer regime. In particular, monolayer MoS 2 exhibits significantly lower reactivity compared with its few-layer and multilayer counterparts. Atomic-resolution transmission electron microscopy (TEM) reveals that MoN nanonetworks form as reaction products from monolayer and bilayer MoS 2 , with the continuity of the MoN crystals increasing with layer number, consistent with the local conductivity mapping data. The layer-dependent reactivity is attributed to the relative stability of the hypothetically formed MoN phase, which retains the number of Mo atomic layers present in the precursor. Specifically, the low chemical reactivity of monolayer MoS 2 is attributed to the high energy cost associated with Mo atom diffusion and migration necessary to form multilayer Mo lattices in the thermodynamically stable MoN phase. In conclusion, this study underscores the critical role of lattice rearrangement in governing chemical reactivity and highlights the potential of 2D materials as versatile platforms for advancing the understanding of materials chemistry at the atomic scale.
Chemical reactivity↗
Chemical depth profiles of the GaAs/native oxide interface
The final-state oxidation products and their distribution in thin native oxides (30-40 A) on GaAs have been studied using X-ray photoelectron spectroscopy in conjunction with chemical depth profiling. Extended room-temperature-oxidation conditions have been chosen to allow the native oxide to attain its equilibrium composition and structure. The work emphasizes the use of chemical depth-profiling methods which make it possible to examine the variation in chemical reactivity of the oxide structure. A minimum of two distinct regions of Ga2O3 with differing chemical reactivity is observed. Chemical shift data indicate the presence of As2O3 in the oxide together with an elemental As overlayer at the interface. A change in relative charge transfer between oxygen and both arsenic and gallium-oxide species is observed in the region of the interface.
Grunthaner, P. J.↗
Dynamics and chemical mode analysis of plasma thermal-chemical instability
The stability of the weakly ionized plasma and the transition from a stable homogeneous discharge to unstable filaments play an important role in gas laser physics, plasma-assisted combustion, chemical reforming, and material synthesis. Here, theoretical stability analysis and thermal-chemical mode analysis were performed to understand the mechanism of plasma thermal-chemical instability by using a zero-dimensional plasma system with both simplified and detailed chemical kinetics of H 2 /O 2 /N 2 mixtures. The plasma dynamic and kinetic models accounted for multiple physical mechanisms in the chemically-reactive weakly ionized plasma, including ionization, attachment/detachment, recombination, vibrational and electronic energy relaxation, convective and diffusive species/heat removal, Joule heating, and detailed chemical kinetics. An analytical criterion and the explosive mode species/temperature pointers were formulated while the representative active species were identified for different thermal-chemical modes. The results showed that in addition to the classical thermal-ionization mechanism, various chemical modes from chemical heat imbalance and elementary kinetics significantly modified the time dynamics and the stability of the weakly ionized plasma. The present analysis provides insights and guidance to control plasma instability using chemical kinetics.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Chemical processes in SiC formation by reactive deposition and chemical conversion.
Chemical processes in silicon carbide due to reactive deposition and chemical conversion, noting silicon growth mechanism involving outward diffusion
Haq, K. E.↗
Integrated low carbon H 2 conversion with in situ carbon mineralization from aqueous biomass oxygenate precursors by tuning reactive multiphase chemical interactions
Meeting our rising demand for clean energy carriers such as H 2 from renewable biomass resources is challenged by the co-emission of CO 2 and CH 4 . To address this challenge, we design novel reactive separation pathways that integrate multiphase chemical reactions by harnessing Ca and Mg bearing minerals as a sorbent to capture CO 2 released during the hydrothermal deconstruction of aqueous biomass oxygenates to produce H 2 and solid carbonates via low temperature aqueous phase reforming and thermodynamically downhill carbon mineralization. Earth abundant catalysts such as Ni/Al 2 O 3 are effective in producing H 2 yields as high as 79% and 74% using ethylene glycol and methanol in the presence of Ca(OH) 2 as an alkaline sorbent, without contaminating or deactivating the catalyst. H 2 yields with in situ carbon mineralization using a Ni or Pt/Al 2 O 3 catalyst are enhanced based on the following order of reactivity: acetate < glycerol < methanol < formate < ethylene glycol. These studies demonstrate that the multiphase chemical interactions can be successfully tuned to enhance H 2 yields through the selective cleavage of C–C bonds using Ni/Al 2 O 3 catalysts to deconstruct biomass oxygenates for producing H 2 and CO 2 , and in situ carbon mineralization by harnessing abundant alkaline materials, as demonstrated using ladle slag. This approach unlocks new scientific possibilities for harnessing multiple emissions including abundant organic-rich wastewater streams and alkaline industrial residues to co-produce low carbon H 2 and carbonate-bearing materials for use in construction by using renewable solar thermal energy resources.
09 BIOMASS FUELS↗
Advances in predictive chemistry enable a multi-scale rational design approach for biofuels with advantaged properties
Process of building predictive gas-phase chemical mechanisms faster and less computationally intensive using state of the art automated chemical tools and linking the predicted chemical reactivity to underlying chemical structure information.
09 BIOMASS FUELS↗
A Gas-Kinetic Scheme for Reactive Flows
In this paper, the gas-kinetic BGK scheme for the compressible flow equations is extended to chemical reactive flow. The mass fraction of the unburnt gas is implemented into the gas kinetic equation by assigning a new internal degree of freedom to the particle distribution function. The new variable can be also used to describe fluid trajectory for the nonreactive flows. Due to the gas-kinetic BGK model, the current scheme basically solves the Navier-Stokes chemical reactive flow equations. Numerical tests validate the accuracy and robustness of the current kinetic method.
Lian,Youg-Sheng↗
The nanosphere iron mineral(s) in Mars soil
A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.
Banin, A.↗
Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor
Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
The nanophase iron mineral(s) in Mars soil
A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.
NASA Program Exobiology↗
A04-0491 - Reduced Electrolyte Reactivity of Pitch-Carbon Coated Si Nanoparticles for Li-Ion Battery Anodes
Silicon-based anodes for Li-ion batteries (LIB) have the potential to increase the energy density over graphite-based LIB anodes. However, silicon anodes exhibit poor cycle and calendar lifetimes due to mechanical instabilities and high chemical reactivity with the carbonate-based electrolytes that are typically used in LIBs. In this work, we synthesize a pitch-carbon coated silicon nanoparticle composite active material for LIB anodes that exhibits reduced chemical reactivity with the carbonate electrolyte compared to an uncoated silicon anode. Silicon primary particle sizes <10 nm minimize micro-scale mechanical degradation of the anode composite, while conformal coatings of pitch-carbon minimized the parasitic reactions between the silicon and the electrolyte. When matched with a high voltage NMC622 cathode, the pitch-carbon coated Si anode retains -75% of its initial capacity over 1000 cycles. Efforts to increase the areal loading of the pitch-carbon coated silicon anodes to realize real energy density improvements over graphite anodes results in severe mechanical degradation on the electrode level. Developing procedures to engineer the architecture of the composite silicon anode may be a solution to this mechanical challenge.
DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
Impacts of molecular architecture on the radiation-induced degradation and reaction kinetics of hydrophobic diglycolamides with the solvated electron and the dodecane radical cation
Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (e solv − ) and the corresponding dodecane radical cation (RH˙ + ) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10 −3 , (4.19 ± 0.09) × 10 −3 , and (4.65 ± 0.09) × 10 −3 kGy −1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.
Arrhenius parameters↗
Atom-by-Atom Direct Writing
Direct-write processes enable the alteration or deposition of materials in a continuous, directable, sequential fashion. Here, in this work, we demonstrate an electron beam direct-write process in an aberration-corrected scanning transmission electron microscope. This process has several fundamental differences from conventional electron-beam-induced deposition techniques, where the electron beam dissociates precursor gases into chemically reactive products that bond to a substrate. Here, we use elemental tin (Sn) as a precursor and employ a different mechanism to facilitate deposition. The atomic-sized electron beam is used to generate chemically reactive point defects at desired locations in a graphene substrate. Temperature control of the sample is used to enable the precursor atoms to migrate across the surface and bond to the defect sites, thereby enabling atom-by-atom direct writing.
36 MATERIALS SCIENCE↗
Chemical and Reactive Transport Processes Associated with Hydraulic Fracturing of Unconventional Oil/Gas Shales
Hydraulic fracturing of unconventional oil/gas shales has changed the energy landscape of the U.S.. Recovery of hydrocarbons from tight, hydraulically fractured shales is a highly inefficient process, with estimated recoveries of < 25% for natural gas and < 5% for oil. This review focuses on the complex chemical interactions of additives in hydraulic fracturing fluid (HFF) with minerals and organic matter in oil/gas shales. These interactions are intended to increase hydrocarbon recovery by increasing porosities and permeabilities of tight shales. However, fluid-shale interactions result in the dissolution of shale minerals and the release and transport of chemical components. They also result in mineral precipitation in the shale matrix, which can reduce permeability, porosity, and hydrocarbon recovery. Competition between mineral dissolution and mineral precipitation processes influences the amounts of oil and gas recovered. We review the temporal/spatial origins and distribution of unconventional oil/gas shales from mudstones and shales, followed by discussion of their global and U.S. distributions and compositional differences from different U.S. sedimentary basins. We discuss the major types of chemical additives in HFF with their intended purposes, including drilling muds. Fracture distribution, porosity, permeability, and the identity and molecular-level speciation of minerals and organic matter in oil/gas shales throughout the hydraulic fracturing process are discussed. Also discussed are analysis methods used in characterizing oil/gas shales before and after hydraulic fracturing, including permeametry and porosimetry measurements, X-ray diffraction/Rietveld refinement, X-ray computed tomography, scanning/transmission electron microscopy, and laboratory- and synchrotron-based imaging/spectroscopic methods. Reactive transport and spatial scaling are discussed in some detail in order to relate fundamental molecular-scale processes to fluid transport. Furthermore, our review concludes with a discussion of potential environmental impacts of hydraulic fracturing and important knowledge gaps that must be bridged to achieve improved mechanistic understanding of fluid transport in oil/gas shales.
04 OIL SHALES AND TAR SANDS↗
Protein Electric Fields Enable Faster and Longer-Lasting Covalent Inhibition of β-Lactamases
The widespread design of covalent drugs has focused on crafting reactive groups of proper electrophilicity and positioning towards targeted amino-acid nucleophiles. In this work, we found that environmental electric fields projected onto a reactive chemical bond, an overlooked design element, play essential roles in the covalent inhibition of TEM-1 beta-lactamase by avibactam. Using the vibrational Stark effect, the magnitudes of the electric fields that are exerted by TEM active sites onto avibactam’s reactive C=O were measured and demonstrate an electrostatic gating effect that promotes bond formation yet relatively suppresses the reverse dissociation. These results suggest new principles of covalent drug design and off-target site prediction. Unlike shape and electrostatic complementary which address binding constants, electrostatic catalysis drives reaction rates, essential for covalent inhibition, and deepens our understanding of chemical reactivity, selectivity, and stability in complex systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Hybrid Additive Manufacturing and Electric Field-Assisted Sintering of High-temperature Heat Exchangers via Sacrificial Channel Molds
A hybrid manufacturing approach, integrating additive manufacturing (AM) with powder methodology via electric field-assisted sintering (EFAS), was developed for the fabrication of high-temperature compact heat exchangers (CHX) from refractory metals. The methodology employed additively manufactured sacrificial channel molds (SCMs) as shapeholders for CHX channels, which were embedded in metal powders using EFAS. Following embedding, the SCMs were chemically dissolved to form the internal channel network. SCMs were fabricated using both digital light processing (DLP) and direct ink writing (DIW) from chemically reactive, calcium-based ceramic feedstocks with varying ratios of Al2O3 reinforcement. The microstructure, phase composition, and dissolution behavior of both as-printed and embedded SCMs were investigated. The shrinkage behavior of the SCMs embedded in refractory metals, as well as the interfacial characteristics between the SCMs and metal matrix, were studied. The results showed that the SCMs containing sufficient chemical reactive ceramics dissolved effectively before and after embedding. The as-printed SCMs retained the phase composition of their feedstocks, but the embedded SCMs containing calcium-based ceramics and Al2O3 exhibited the formation of calcium aluminates due to high temperature exposure during embedding. Most SCMs exhibited a cellular Al2O3 network filled with Ca-rich ceramics. Shrinkage after embedding was strongly dependent on SCM density, with lower density SCMs exhibiting greater shrinkage. A thin SCM-affected zone was observed at the metal matrix surface, characterized by increased porosity compared to the bulk matrix. This effect was attributed to infiltration of the SCM materials into powder particle boundaries under pressure, followed by their removal during dissolution. This study demonstrates the feasibility of manufacturing CHXs from hard-to-process refractory metals for use in harsh environments.
36 - MATERIALS SCIENCE↗
Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions
The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.
Neumann, Julia↗