Engineering topics
Boglaienko, Daria
Publications and source records attributed to Boglaienko, Daria.
Strategically Modified Ligand Incorporating Mixed Phosphonate and Carboxylate Groups to Enhance Performance in All-Iron Redox Flow Batteries
Iron redox flow batteries (Fe-RFBs) hold significant promise for achieving cost-effectiveness and utilizing abundant materials for stationary energy storage applications. Here, a design of a novel Fe complex utilizing a nitrogenous phosphonate/carboxylate mixed ligand, N,N-Bis(phosphonomethyl)glycine (BMPG), is presented to achieve high performance Fe anolyte. Compared to its all-phosphonate form, nitrilotri(methylphosphonic acid) (NTMPA), the new complex Fe(BPMG) 2 demonstrates a negatively shifted redox potential, resulting in ≈0.07 V (≈10%) increase in battery output voltage. Full battery testing paired with ferrocyanide catholyte demonstrates stable cycling (capacity degradation <0.0001%/cycle) over 730 consecutive charge/discharge cycles with Coulombic Efficiency of 100% at a current density of 20 mA cm -2 under near neutral pH (≈8). Of particular interest, density functional theory (DFT) studies and operando Raman measurements provide strong evidence supporting a molecular structure in BPMG, which reveals the mixed phosphonate/carboxylate groups in BPMG maintain the octahedral coordination of the Fe ion center with phosphonates exclusively, while leaving the carboxylate unbound for both Fe(II) and Fe(III) complexes. This structural similarity between BPMG-based Fe(II) and Fe(III) complexes effectively mitigates the slow redox reaction kinetics observed in Fe(NTMPA) 2 anolyte, where significant ligand reorientation occurs between Fe(II) and Fe(III) complexes.
Ruthenium speciation and distribution in the environment: A review
Here, the review focuses on speciation and migration of anthropogenic ruthenium (Ru) originated from nuclear industry releases and presents updated information regarding Ru in the environment. It provides analysis of the main pathways of Ru species distribution in the aqueous and terrestrial environment, starting from its natural occurrence, generation and release from anthropogenic sources, predominant speciation, and ending with bioaccumulation, which can be directly or indirectly related to human health. Literature sources belonging to the post-Chernobyl time frame were preferentially considered, in which Ru-103 and Ru-106 are the major fission isotopes studied due to their traceability in the environment and their relatively long half-lives.
Process Intensification for Recovery of Uranium from Spent Fuel Using DEHiBA
Two approaches are being pursued to intensify the DEHiBA process for recovery of U from used nuclear fuel. For the traditional solvent extraction approach in which the fuel is first dissolved in hot nitric acid, the DEHiBA concentration was adjusted to 1.5 M. This allows for increased loading in the organic phase, but the organic phase U concentration should remain below 100 g/L to avoid unfavorable physicochemical properties that would upset the hydrodynamics in contacting equipment such as centrifugal contactors. Direct extraction of U into the 1.5 M DHEiBA solvent is another intriguing approach to intensifying the process. In this case, the hot nitric acid dissolution step is avoided, a potential significant simplification of the process. Strategies for routing Tc, Np, and Pu to the HLW stream will likely need to be developed to avoid contamination of the U product with these undesirable species.
Laser-Induced Photoreduction of Iron(III) Oxide Nanoparticles Enhanced by the Presence of Organic Chromophores
Light-induced electron transfer between chromophoric organic matter and Fe(III)-oxides lies at the heart of aqueous Fe(II) fluxes in the photic zone of natural systems. Understanding this photoreductive dissolution process is also essential for developing water purification techniques based on this class of materials. Previously, optical transient absorption spectroscopy (TAS) measurements revealed that sub-picosecond relaxation times of photo-excited rhodamine B (RhB) dye increased when sorbed onto hematite nanoparticles (HNPs), consistent with electron transfer to the oxide. Here, in the present study, we exploit time-resolved X-ray absorption spectroscopy (XAS) at the Fe K-edge to follow the Fe oxidation state for this same process to (i) confirm that RhB photoexcitation leads to interfacial electron transfer and Fe reduction; and (ii) quantify the lifetime of injected electrons as a function of solution conditions. Regardless of RhB dye availability and pH, direct band gap photoexcitation of HNPs yields an Fe(II)-like small polaronic absorption signature with a lifetime of ~ 1 ns, an order of magnitude longer than previously reported. However, when RhB is present at low pH under conditions where dye favorably interacts with the positively charged hematite surface, a second relaxation process approaching microsecond timescales is observed that likely represents back-reaction with the photoexcited adsorbed dye. At pH above neutral, the efficiency of the interfacial electron transfer is diminished by weaker interaction between sorbed dye and particle surfaces.
Increasing Al-Pair Abundance in SSZ-13 Zeolite via Zeolite Synthesis in the Presence of Alkaline Earth Metal Hydroxide Produces Hydrothermally Stable Co-, Cu- and Pd-SSZ-13 Materials
Replacing alkaline for alkaline-earth metal hydroxide in the synthesis gel during the synthesis of siliceous SSZ-13 zeolite (Si/Al~10) yields SSZ-13 with novel, advantageous properties. Its NH 4 -form ion-exchanges higher amount of isolated divalent M(II) ions than the conventional one: this is the consequence of an increased number of Al pairs in the structure induced by the +2 charge of Sr(II) cations in the synthesis gel that force two charge-compensating AlO 4 – motives to reside closer together. We characterize the +2 state of Co(II) ions in these materials with infra-red spectroscopy and X-ray absorption spectroscopy measurements and show their utility for NOx pollutant adsorption from ambient air: the ones derived from SSZ-13 with higher Al pair content contain more isolated cobalt(II) and, thus, perform better as ambient-air NOx adsorbers. Notably, Co(II)/SSZ-13 with an increased number of Al pairs is significantly more hydrothermally stable than its NaOH-derived analogue. Loading Pd(II) into Co-SSZ-13(Sr) produces an active NOx adsorber (PNA) material that can be used for NOx adsorption from simulated diesel engine exhaust. The critical issue for these applications is hydrothermal stability of Pd-zeolites. Pd/SSZ-13 synthesized in the presence of Sr(OH) 2 does not lose its PNA capacity after extremely harsh aging at 850 and 900 °C (10 h in 10% H 2 O/air flow) and loses only ~55% capacity after hydrothermal aging at 930 °C. This can be extended to other divalent metals for catalytic applications, such as copper: we show that Cu/SSZ-13 catalyst can survive hydrothermal aging at 920 °C without losing its catalytic properties, metal dispersion and crystalline structure. Thus, we provide a new, simple, and scalable strategy for making remarkably (hydro)thermally stable metal-zeolite materials/catalysts with a number of useful applications.
Accumulation mechanisms for contaminants on weak-base hybrid ion exchange resins
Mechanism of hexavalent chromium removal (Cr(VI) as CrO 4 2- ) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO 3 - ), uranium (U as uranyl UO 2 2+ ), and technetium-99 (as TcO 4 - ), and common environmental anions sulfate (SO 4 2- ) and chloride (Cl-). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO 4 2- concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO 4 2- at the protonated amine sites. These U–SO 4 2- complexes are integral to U(VI) removal, as confirmed by the decrease in U(VI) removal (<40%) when the acid chloride form of SIR-700 was used instead. Solid phase characterization revealed that CrO 4 2- is removed by IX with SO 4 2- complexes and/or reduced to amorphous Cr(III)(OH) 3 at secondary alcohol sites. Tc(VII)O 4 - and I(V)O 3 - also undergo chemical reduction, following a similar removal mechanism. Oxyanion removal preference is determined by the anion reduction potential (CrO 4 2 - >TcO 4 - >IO 3 - ), geometry, and charge density. For these reasons, 39% and 69% of TcO 4 - and 17% and 39% of IO 3 - are removed in the presence and absence of Cr(VI), respectively.
Part I: Predicting performance of Purolite A532E resins for remediation of comingled contaminants in groundwater
Ion exchange (IX) resins are used in pump-and-treat (P&T) facilities to remove soluble groundwater contaminants. However, natural anions present at concentrations orders of magnitude higher than contaminants can compete for IX sites and impact resin lifecycles. Here, the Hanford Site’s 200 West Area P&T facility (Washington State, USA) was selected as a case study because it currently uses two IX resins: Purolite® A532E (A532E) to remove pertechnetate (TcO 4 - ) and DOWEX 21K (DOWEX) to remove uranium from groundwater. Nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ) anions have been identified to potentially compete for A532E and DOWEX IX sites. Hanford-relevant anion groundwater concentrations were used to design a series of laboratory-scale batch experiments to evaluate the impact of competing anions on resin performance and potential kinetic effects. These data are then modeled to obtain Cl--normalized equilibrium exchange coefficients (K) needed to predict IX resin performance. The work is presented in two parts, with IX performance evaluated for A532E in Part I and DOWEX in Part II. Part I results demonstrate that TcO 4 - uptake is not impacted by NO 3 - , SO 4 2- , Cl - , CO 3 2- (as HCO 3 - ) and U(VI) carbonate anions, with K TcO4-/Cl- > 4,000, likely due to the high selectivity of A532E trihexylammonium sites for the large, weakly hydrated TcO 4 - anion. Other anion K values were K NO3-/Cl- = 20, K SO4--/Cl- = 0.2, K HCO3-/Cl- = 0.09, K U/Cl- = 370–1000. These K values provide conservative parameters for predicting A532E performance, and demonstrate that, under these test conditions, A532E will remove TcO 4 - from current and future influent streams to meet groundwater treatment objectives.
Part II: Predicting performance of $\mathrm{DOWEX 21K}$ resin for remediation of comingled contaminants in groundwater
The selectivity of ion exchange (IX) resins for aqueous contaminant removal can be impacted by changing concentrations of competing natural groundwater ions. In a two-part investigation, the Hanford Site 200 West Area pump-and-treat (P&T) facility in Washington State, USA is used as a case study to evaluate the performance of two IX resins for groundwater treatment: Purolite® A532E for pertechnetate (TcO 4 - ) removal, explored in Part I, and DOWEX 21K (DOWEX) for uranium (U) removal. In Part II, DOWEX selectivity for U, as uranyl carbonate species, and uptake kinetics is quantified in a series of laboratory-scale aqueous batch experiments containing Hanford-relevant concentrations of competing anions nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ), as well as co-mingled contaminant TcO 4 - . Here the results demonstrate that DOWEX trimethylammonium functional groups are highly selective for U carbonate species (85–100 % uptake) under all conditions investigated. Only NO 3 - concentrations of 100 mM were shown to decrease U removal, with the extent (85–99 %) depending on competing anion concentrations present in solution. However, at the highest NO 3 - concentrations reported for groundwaters treated at the P&T facility (25 mM), the effect on U uptake is minimal. The batch sorption results are modeled to obtain chloride normalized equilibrium exchange coefficients (K) for predicting DOWEX performance: K SO4--/Cl- = 2.0, K NO3-/Cl- = 5.0, K HCO3-/Cl- = 1.5, K TcO4-/Cl- = 2,000, and K U/Cl- = 50,000. These K values predict little effect of current and future influent chemistries on U removal by DOWEX, where both uranyl carbonate species and TcO 4 - are removed such that effluent concentrations meet groundwater treatment requirements.
Reductive removal of pertechnetate and chromate by zero valent iron under variable ionic strength conditions
Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and the environment. This research comparatively evaluated efficiency of zero valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and Na 2 SO 4 electrolyte solutions under aerobic conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV)). In the absence of Cr(VI), no such delay was observed in the analogous systems. At low ionic strength, retarded ZVI oxidation inhibited Tc(VII) reduction in part due to the competing thermodynamically more favorable reduction of Cr(VI) to Cr(III); this effect was particularly pronounced in the chloride medium at the ionic strength ? 0.1. Higher ionic strength favored reduction of both Tc(VII) and Cr(VI), which followed a second-order reaction rate in both electrolytes attributed to the more efficient iron oxidation as evident from x-ray diffraction and electron microscopy measurements. Magnetite was the primary iron oxide phase, and its higher fraction in the SO 4 2- solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl- matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO 4 2- solutions.
The role of amorphous ZIF in ZIF-8 crystallization kinetics and morphology
Understanding the composition and structure of amorphous precursor phases is fundamental for elucidating two-step crystallization mechanisms and designing shape- and size-controlled nanomaterials. However, that understanding is largely lacking for metal–organic framework compounds despite their growing significance as functional materials. Here, in this study, we report the crystallization of zeolite imidazolate frameworks-8 (ZIF-8, Zn(C 4 H 5 N 2 ) 2 ) via an amorphous ZIF (am-ZIF) solid precursor phase with a rough stoichiometric composition of Zn(C 4 H 5 N 2 ) 1.78 (C 4 H 6 N 2 ) 0.17 (CH 3 COO) 0.22 . The formation of am-ZIF is attributed to the incomplete deprotonation of 2-Methylimidazole (HmIm) and the involvement of the hydrogen bond between CH 3 COO– and –HN, which can further transform into the dense Dia(Zn) structure with a diamondoid crystal topology in pure water. Taking am-ZIF as a precursor, the tunable dissolution and recrystallization kinetics of am-ZIF into ZIF-8, due to the addition of EtOH and CTAB, allows the selective fabrication of dodecahedral, cubic, and hollow ZIF-8. Overall, an in-depth understanding of the differences in composition and structure of am-ZIF from ZIF-8 and the resulting crystallization kinetics suggests a novel approach to designing metal–organic frameworks with controlled crystal morphology.
Water Defect Stabilizes the Bi 3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure
In this work, the aqueous hydration structure of Bi 3+ is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and of condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi 3+ ion is dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multi-modal distribution of waters in the first shell that are separated by about 0.2Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi 3+ plays a major role in the binding of water and ligands in aqueous solutions.
Removable coatings: Thermal stability and decontamination of steel surfaces from 241 Am
This study presents a comparative analysis of several strippable materials for decontamination of steel surfaces from 241 Am. The strippable coatings were chosen to have a history of application, to be commercially available, easily handled and have different composition and formulation. Carbon steel and stainless steel surfaces (coupons) were utilized as the most representative industrial materials, and the experimental series were expanded to include the rusting treatment of these surfaces as it is common for decommissioned old nuclear facilities. The experiments followed the path of pre-screening of the strippable materials (easiness of application, peeling etc.), their characterization with Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), decontamination factors (DF) or removal efficiencies for different types of steel surfaces, and enhancement of the removal efficiencies of the select strippable coatings via amendment with EDTA. As a result, DF and removal efficiencies for stainless steel (both pristine and with rusting treatment) are higher than for pristine carbon steel, and decontamination factors and removal efficiencies are higher for pristine than for rusted carbon steel across all the coatings. It is also shown that EDTA amendment can improve DF and removal efficiency for a strippable coating (i.e., CC Strip), however other factors should also be considered. Thus, the coating CC Strip exhibited easiness in handling and high DF (up to 97% when EDTA-amended), but its drying period was the longest among the rest of the materials and its thermal decomposition indicates on a risk of intense release of heat in case of a fire event.
X-ray absorption spectroscopy of trivalent Eu, Gd, Tb, and Dy chlorides and oxychlorides
Growing interest in next generation molten salt nuclear reactors necessitates a fundamental understanding of the chemical and physico-chemical properties of fission products, including elements of the lanthanide series. In this study, we probed coordination environment of Eu, Gd, Tb, and Dy in their chloride salts with both laboratory and synchrotron scale X-ray absorption spectroscopy (XAS). Here the aerobic melting was carried out with LnCl 3 ·nH 2 O, where Ln is Eu, Gd, Tb, and Dy, and yielded predominant formation of oxychlorides (LnOCl), that was confirmed by extended X-ray absorption fine structure (EXAFS) analysis and X-ray diffraction (XRD). Density functional theory (DFT) and time-dependent density functional theory (TDDFT) computations were performed to obtain ground state structures, lattice parameters, and to simulate L 3 -edge XANES (X-ray absorption near edge structure) spectra of the LnCl 3 ·nH 2 O and LnOCl. A blue shift, initially predicted by our calculations, was also observed for the experimental Ln L 3 -edge XANES spectra of the hydrated trichlorides vs oxychlorides, highlighting the power of combining the predictive ability of theory with experiment to elucidate the properties of the compounds of interest. The blue shift is indicative of structural stabilization of LnCl 3 ·nH 2 O due to higher symmetry compared with LnOCl. To the best of knowledge, this is a first study providing the framework for fundamental insights into the structure of Ln trichlorides and oxychlorides in support of future characterization of lanthanides in the molten salt environment.
Time dependent zero valent iron oxidation and the reductive removal of pertechnetate at variable pH
Elemental iron Fe 0 is a promising reductant for removal of radioactive technetium-99 (Tc) from complex aqueous waste streams that contain sulfate, halides, and other inorganic anions generated during processing of legacy radioactive waste. The impact of sulfate on the kinetics of oxidation and reduction capacity of Fe 0 in the presence of Tc has not been examined. We investigated the oxidative transformation of Fe 0 and reductive removal of TcO 4 - in 0.1 M Na 2 SO 4 as a function of initial pH (i.e., pH i 4, 7, and 10) under aerobic conditions up to 30 days. Tc reduction was the fastest at pH i 7 and slowest at pHi 10 (Tc reduction rate pHi 7 > 4 > 10). Aqueous fraction of Tc was measured at 0.4% at pH i 7 within 6 h, whereas ≥ 97% of Tc was removed from solutions at pH i of 4 and 10 within 24 h. Solid phase characterization showed that magnetite was the only oxidized crystalline phase for the first 6 h regardless of initial pH. Lepidocrocite was the most abundant oxidized product for pH i 10 after 5 days, but was not observed at pH of 4 or 7.
Elemental iron: reduction of pertechnetate in the presence of silica and periodicity of precipitated nano-structures
Enhanced TcO 4 − reduction by metallic Fe 0 in the presence of particulate and structural Si. Rhythmical precipitation of dissolved iron leads to formation of layered structures related to geological phenomena such as orbicular rocks and Liesegang rings.
Spontaneous redox continuum reveals sequestered technetium clusters and retarded mineral transformation of iron
Abstract not provided
Characterization of Spent Purolite A530E Resin with Implications for Long-Term Radioactive Contaminant Removal
Direct removal of pertechnetate anion (TcO4-) from the subsurface contaminated plumes at legacy nuclear weapons production sites, is effective remediation strategy to prevent their spread to adjacent aquifers but is also challenging because TcO4- is a trace component of the contaminated groundwater typically containing large access of other anionic constituents, such nitrate, sulfate, chloride and others. It can be achieved through ion exchange treatment using Purolite A530E resin which to date however has only been evaluated under laboratory conditions and many questions regarding its long-term operational performance remain. To address this need, here we report comprehensive characterization of the spent Purolite A530E resin which processed over 5.38x109 L of contaminated groundwater and successfully removed about 3.78 Ci of Tc-99 during four years of operation at the 200 West Pump & Treat facility at the US DOE Hanford site. This Tc-99 loading constitutes however only about 0.034% of the theoretical capacity of the resin which retained significant amounts of sulfate. Among other radioactive contaminants, small quantities of U-238, Co-60, and I-129 were retained by the resin. The total loading of iodine (combined 1-127 and I-129) on the spent resin exceeded that of Tc-99. To elucidate the mechanism of iodine retention, ion exchange behavior of iodide and iodate was investigated. Purolite A530E resin exhibited highly efficient uptake of iodide and only moderate affinity for iodate in accord with their Gibbs energy of hydration. Sorption isotherms for both anions obeyed Freundlich model.