Condition-Dependent Pd Speciation and NO Adsorption in Pd/Zeolites
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99 GENERAL AND MISCELLANEOUS↗
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Results for “H 2 O”
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Conformally coated scaffold design using water-tolerant Pr 1.8 Ba 0.2 NiO 4.1 for protonic ceramic electrochemical cells with 5,000-h electrolysis stability
Protonic ceramic electrochemical cells (PCECs) have potential as long-duration energy storage systems. However, their operational stability is limited under industrially relevant conditions due to the intrinsic chemical instability of doped barium cerate-based electrolytes and oxygen electrodes against H 2 O, as well as the poor electrode–electrolyte interfacial contact. Here, in this study, we present a conformally coated scaffold (CCS) design to comprehensively address these issues. A porous proton-conducting scaffold is constructed and conformally coated with Pr 1.8 Ba 0.2 NiO 4.1 electrocatalyst, which has high chemical stability against H 2 O, triple conductivity and hydration capability, and protects vulnerable electrolytes from H 2 O. The CCS structure consolidates the electrode–electrolyte interfacial bonding to enable fast proton transfer in the percolated network. This design enables PCECs to reach electrolysis stability for 5,000 h at −1.5 A cm−2 and 600 °C in 40% H 2 O. This work provides a general strategy to stabilize PCECs and offers guidance for designing resilient and stable solid-state energy storage systems.
Protonic ceramic electrochemical cell↗
Metal–Oxo Cluster Formation Using Ammonium and Sulfate to Differentiate M IV (Th, U, Ce) Chemistries
Isolating isostructural compounds of tetravalent metals M IV (Zr, Hf, Ce, Th, U, Pu, Np) improves our understanding of metal hydrolysis and coordination behavior across the periodic table. These metals form polynuclear clusters typified by the hexamer [M IV 6 O 4 (OH) 4 ] 12+ . Exploiting the ammonium M IV -sulfate (Ce IV , Th IV , and U IV ) phase space targeting rapid crystallization, we isolate the common hexamer [M IV 6 (OH) 4 (O) 4 ] 12+ but with different numbers of capping sulfates and water molecules for Ce IV , Th IV , and U IV . Furthermore, these phases allowed a direct comparison of bonding trends across the series. Upon cocrystallization with the hexamers, higher complex structures can be identified. Thorium features assemblies with monomer-linked hexamer chains. Uranium features assemblies with sulfate-bridged hexamers and the supramolecular assembly of 14 hexamers into the U 84 , [U 6 (OH) 4 (O) 4 ) 14 (SO 4 ) 120 (H 2 O) 42 ] 72– . Last, cerium showcases the isolation from monomers to the Ce 62 , [Ce 62 (OH) 30 (O) 58 (SO 4 ) 71 (H 2 O) 33.25 ] 41– . Furthermore, small-angle X-ray scattering (room temperature) shows ammonium-induced cluster assembly for Ce IV but minimal reactivity for U IV and Th IV . In this study, because the phases crystallized at elevated temperature demonstrates favorable cluster assembly, these solution phase results were surprising and suggest some other characteristics such as Ce’s facile redox behavior, contributes to its solution-phase speciation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Revealing the atomic and electronic mechanism of human manganese superoxide dismutase product inhibition
Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O 2 •– ) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of H 2 O 2 , a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O 2 2– ) or hydroperoxide (HO 2 – ) species bound to Mn ion and formed from an unknown PCET mechanism. PCET mechanisms of proteins are typically not known due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center. To shed light on the mechanism, we combine neutron diffraction and X-ray absorption spectroscopy of the product-bound, trivalent, and divalent states of the enzyme to reveal the positions of all the atoms, including hydrogen, and the electronic configuration of the metal ion. The data identifies the product-inhibited complex, and a PCET mechanism of inhibition is constructed.
59 BASIC BIOLOGICAL SCIENCES↗
Theoretical understanding of stability of the oxygen electrode in a proton-conductor based solid oxide electrolysis cell
The oxygen electrode in a proton-conductor based solid oxide cells is often a triple-conducting material that enables the transport and exchange of electrons (e - ), oxygen ions (O 2- ), and protons (H + ), thus expanding active areas to enhance the oxygen electrode activity. In this work, a theoretical model was developed to understand stability of tri-conducting oxygen electrode by studying chemical potentials of neutral species (i.e., μ o 2 , μ H 2 , and μ H 2 O ) as functions of transport properties, operating parameters, and cell geometry. Our theoretical understanding shows that (1): In a conventional oxygen-ion based solid oxide cell, a high μ o 2 (thus high oxygen partial pressure) exists in the oxygen electrode during the electrolysis mode, which may lead to the formation of cracks at the electrode/electrolyte interface. Further, while in a proton-conductor based solid oxide cell, the μ o 2 is reduced significantly, suppressing the crack formation, and resulting in improved performance stability (2). In a typical proton-conductor based solid oxide electrolyzer, the dependence of μ o 2 on the Faradaic efficiency is negligible. Hence, approaches to block the electronic current can improve the electrolysis efficiency while achieving stability (3). The difference of the μ o 2 (thus p o 2 ) between the oxygen electrode and gas phase can be reduced by using higher ionic conducting components and improving electrode kinetics, which lead to further improvement of electrode stability.
08 HYDROGEN↗
Snapshots of Ce 70 Toroid Assembly from Solids and Solution
Crystallization at the solid–liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [Ce IV 70 (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4– , part of a larger emerging family of M IV 70 -materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by the X-ray scattering (small-angle scattering and total scattering) of solutions and solids as well as crystallizing and identifying fragments of Ce 70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce 5 , [Ce 5 (O) 3 (SO 4 ) 12 ] 10- ) and modular assembly from hexamer (Ce 6 ) building units (Ce 13 , [Ce 13 (OH) 6 (O) 12 (SO 4 ) 14 (H 2 O) 14 ] 6– and Ce 62 , [Ce 62 (OH) 30 (O) 58 (SO 4 ) 58 ] 14- ). Ce 62 , an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH 4 + , a structural motif not observed before in inorganic systems. The room temperature rapid assemblies of both Ce 70 and Ce 62 , respectively, by the addition of Li + and NH 4 + , along with ion-exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors
Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.
atomic layer deposition↗
Elucidating ion capture and transport mechanisms of Preyssler anions in aqueous solutions using biased MACE-accelerated MD simulations
Equilibrium and biased multi-atomic cluster expansion (MACE) accelerated molecular dynamics (MD) simulations in aqueous solutions are performed to investigate the ion capture and transport mechanisms of the {P 5 W 30 } Preyssler anion (PA) as the smallest representative member of the extended polyoxometalate (POM) family with an internal cavity. The unique interatomic interactions present in the internal cavity vs the exterior of PA are carefully investigated using equilibrium MACE MD simulations for two representative Na(H 2 O)@PA and Na@PA complexes in aqueous solutions. Our careful analyses of radial distribution functions and coordination numbers show that the presence of confined water in Na(H 2 O)@PA has profound modulating effects on the nature of the interactions of the encapsulated ion with the oxygens of the PA cavity. Using well-converged MACE-accelerated multiple walker well-tempered metadynamics simulations with nanosecond timescales, two different associative (ion exchange) and dissociative (ion ejection) ion transport mechanisms were carefully investigated for Na + as one of the most abundant and representative ions present in seawater and saline solutions. By comparing systems with and without confined water, it was found that the presence of only one pre-encapsulated confined water in Na(H 2 O)@PA dramatically changes the free energy landscape of ion transport processes. It was also found that the contraction and dilation of the two windows present in PA directly influence the Na + and H 2 O transport. Furthermore, the results from this work are helpful, as they show a viable path toward tuning the ion exchange and transport phenomena in aqueous solutions of POM molecular clusters and frameworks.
25 ENERGY STORAGE↗
Optimizing Magnetic Force Microscopy Resolution and Sensitivity to Visualize Nanoscale Magnetic Domains
Magnetic force microscopy (MFM) enables mapping local magnetic fields across a sample surface with nanoscale resolution. To perform MFM, an atomic force microscopy (AFM) probe whose tip has been magnetized vertically (i.e., perpendicular to the probe cantilever) is oscillated at a fixed height above the sample surface. The resultant shifts in the oscillation phase or frequency, which are proportional to the magnitude and sign of the vertical magnetic force gradient at each pixel location, are then tracked and mapped. Although the spatial resolution and sensitivity of the technique increases with decreasing lift height above the surface, this seemingly straightforward path to improved MFM images is complicated by considerations such as minimizing topographical artifacts due to shorter range van der Waals forces, increasing the oscillation amplitude to further improve sensitivity, and the presence of surface contaminants (in particular water due to humidity under ambient conditions). In addition, due to the orientation of the probe's magnetic dipole moment, MFM is intrinsically more sensitive to samples with an out-of-plane magnetization vector. Here, high-resolution topographical and magnetic phase images of single and bicomponent nanomagnet artificial spin-ice (ASI) arrays obtained in an inert (argon) atmosphere glovebox with <0.1 ppm O 2 and H 2 O are reported. Further, optimization of lift height and drive amplitude for high resolution and sensitivity while simultaneously avoiding the introduction of topographical artifacts is discussed, and detection of the stray magnetic fields emanating from either end of the nanoscale bar magnets (~250 nm long and <100 nm wide) aligned in the plane of the ASI sample surface is shown. Likewise, using the example of a Ni-Mn-Ga magnetic shape memory alloy (MSMA), MFM is demonstrated in an inert atmosphere with magnetic phase sensitivity capable of resolving a series of adjacent magnetic domains each ~200 nm wide.
47 OTHER INSTRUMENTATION↗
Modeling a High-Temperature Electrochemically Driven Water-Gas-Shift Process Using a Mixed-Conducting Membrane without External Electrical Power
This paper develops a model to predict and interpret the performance of an elevated-temperature, electrochemical, membrane-assisted, water-gas-shift process. The process uses separated feed streams of H 2 O and CO to produce separated streams of H 2 and CO 2 , without an external electrical power source. The dense ceramic membrane is mixed ionic-electronic-conducting (MIEC) gadolinium-doped ceria (GDC) and the porous composite electrodes are Ni-YSZ. At elevated temperature, GDC conducts both oxygen ions and small polarons. The present process uses chemical potential to drive the process. Electrochemical oxidation of CO proceeds within the composite anode and H 2 O reduction proceeds within the composite cathode. At high temperature (e.g., T > 700 °C), GDC has significant electronic leakage in the form of a reduced-cerium small polaron, which supports the charge-transfer reactions. In a typical electrolyzer or fuel cell, this leakage is significantly problematic. However, the present process depends on the leakage current to complete the electrochemical circuit. Model development and validation is based on measured material properties and reactor performance. Potential applications include using CO-rich blast-furnace off gases in steel processing, producing separated streams of H 2 and CO 2 .
Zhu, Huayang↗
Collaborative Research: Natural Organic Matter and Microbial Controls on Mobilization/Immobilization of I and Pu in Soils and Waters Affected by Radionuclide Releases in USA and Japan
In this project, the relationship between natural organic matter (NOM) and two radioactive elements that are relevant to nuclear waste disposal were studied: Plutonium (Pu) and Iodine. The human and environmental risks associated with Pu stem mainly from the very long half-lives of several of its isotopes ( 238 Pu, 88 yr; 239 Pu, 24,100 yr; 240 Pu, 6560 yr) and its radiotoxicity. Understanding Pu biogeochemical behavior in both near-field (>10-11M) and far-field scales (<10-11M) is imperative to the development of approaches for reprocessing Pu, remediation of Pu contamination and accurate assessment of risks posed by disposal practices for Pu-bearing wastes. The environmental mobility of Pu can be affected by redox potential, pH, adsorption, precipitation, complexation, colloid formation, and microbial activity, of which the first characteristic has the most profound influence. Numerous studies have shown high affinity of Pu towards NOM, as well as to mineral phases. NOM is ubiquitous in the environment, e.g., both fulvic and humic acids are able to reduce Pu(V,VI) to Pu(IV) and the redox potential of NOM is positively related to the abundance of phenolic/acidic OH groups. NOM can either facilitate or limit actinide migration, depending on specific biogeochemical conditions including pH, mineral and organic matter characteristics, etc. The other radionuclide of interest is radioiodine ( 129 I). 129I is a major by-product of nuclear fission and of serious concern to the Department of Energy (DOE) as it is among the top risk drivers at existing and potential radiowaste-contaminated sites. The risk of 129 I stems largely from its high bioconcentration factor (90% of the body’s iodine is accumulated in the thyroid), a high inventory at source terms, a very long-half life (16M years), and rapid mobility in the subsurface environment. As a consequence, 129 I has the lowest drinking water standard (1 pCi/L) among all radionuclides in the Federal Register. With a novel and sensitive gas chromatography-mass spectrometry (GC-MS) method developed in our lab, it is possible to quickly and simultaneously determine the distribution of 129 I and stable 127 I forms in environments, as low as 2 pCi/L for 129 I. This method was subsequently validated using accelerator mass spectroscopy, AMS. IO 3 - and organo-I were determined as major species in the groundwater of SRS and the Hanford Site, contrary to thermodynamic predictions that I- should be the dominant species at these sites. Mobility of 129 I was also demonstrated to depend greatly on the I species and its concentration, sediment pH, and redox state, with times to achieve equilibrium taking up to 12 weeks. Along the groundwater pathway in the F-Area of SRS, 129 I- supplied from the seepage basins was transformed to 129 IO 3 - and organo- 129 I with increasing iodine sediment sorption, causing the lower total 127 I and 129 I concentrations along the gradient transect of the waste plume. By contrast, groundwater 129 I concentrations in the wetlands (as high as 1617.3 pCi/L) were greatly elevated with respect to the source term (159.3 pCi/L). While the NOM promoted the uptake of 129 I to the wetland sediment, it also promoted the formation of soluble organic fraction. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source. Iodide was enzymatically incorporated into NOM, whereas both iodide and iodate were abiotically bound to NOM, under certain conditions. Iodate removal from the mobile aqueous phase can also occur through incorporation into carbonate (e.g., at the Hanford Site, USA). Thus immobilization and re-mobilization of iodine species were influenced by pH, Eh and the presence of NOM and metal oxides, which adds to the complexity of site remediation action. A ground-breaking result was to elucidate the products (i.e. organo-iodine moieties formed via enzymatic and non-enzymatic processes) at the molecular level by nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). We found that iodine-NOM interactions may be influenced by NOM hydrophobic aliphatic moieties. From the perspective of ESI-FTICRMS, organo-iodine formulas were ascribed to the groups of unsaturated hydrocarbons, lignins and proteins. Iodate is likely abiotically reduced to reactive iodine species by lignin- and tannin-like compounds or carboxylic-rich alicyclic molecules (CRAM). We also investigated microbial mechanisms in iodine incorporation into NOM. We established that soil bacteria isolated from F-Area of SRS did not accumulate significant amounts of I- (0.2-2%). Intracellular uptake of I- decreases with increasing pH when pH ranged from 4 to 6. In contrast, 44 out of 84 strains isolated from the F-Area of SRS can transform I- to IO 3 - and organo-iodine. In some cases, oxidation was facilitated in the presence of H 2 O 2 . Microbes can also excrete organic acids that enhance I- oxidation by lowering the ambient pH and reacting with H 2 O 2 to form peroxy carboxylic acids. At lower pH values (≤5), H 2 O 2 hydrolysis was the driving force for iodide-oxidation; whereas, at pH ≥ 6, spontaneous decomposition of peroxy carboxylic acids, originating from H 2 O 2 and organic acids were the primary cause of iodide oxidation. Lastly, it was determined that microbial processes involved in Mn (II) are capable of directly oxidizing I- via enzymatic catalysis (i.e., multicopper oxidases), or indirectly through the formation of reactive oxygen species (ROS) and/or biogenic manganese oxides. ROS-mediated oxidation of I- was found to predominate at pH >5, whereas the enzymatic and Mn oxide pathways were more active at pH < 5. Together, this project has resulted in 9 publications in high-impact journals, and the training of 1 Ph.D and 4 undergraduate students.
54 ENVIRONMENTAL SCIENCES↗
Deuterated water as a substrate-agnostic isotope tracer for investigating reversibility and thermodynamics of reactions in central carbon metabolism
Stable isotope tracers are a powerful tool for the quantitative analysis of microbial metabolism, enabling pathway elucidation, metabolic flux quantification, and assessment of reaction and pathway thermodynamics. 13 C and 2 H metabolic flux analysis commonly relies on isotopically labeled carbon substrates, such as glucose. However, the use of 2 H-labeled nutrient substrates faces limitations due to their high cost and limited availability in comparison to 13 C-tracers. Furthermore, isotope tracer studies in industrially relevant bacteria that metabolize complex substrates such as cellulose, hemicellulose, or lignocellulosic biomass, are challenging given the difficulty in obtaining these as isotopically labeled substrates. In this study, we examine the potential of deuterated water ( 2 H 2 O) as an affordable, substrate-neutral isotope tracer for studying central carbon metabolism. We apply 2 H 2 O labeling to investigate the reversibility of glycolytic reactions across three industrially relevant bacterial species -C. thermocellum, Z. mobilis, and E. coli-harboring distinct glycolytic pathways with unique thermodynamics. We demonstrate that 2 H 2 O labeling recapitulates previous reversibility and thermodynamic findings obtained with established 13 C and 2 H labeled nutrient substrates. Furthermore, we exemplify the utility of this 2 H 2 O labeling approach by applying it to high-substrate C. thermocellum fermentations -a setting in which the use of conventional tracers is impractical-thereby identifying the glycolytic enzyme phosphofructokinase as a major bottleneck during high-substrate fermentations and unveiling critical insights that will steer future engineering efforts to enhance ethanol production in this cellulolytic organism. This study demonstrates the utility of deuterated water as a substrate-agnostic isotope tracer for examining flux and reversibility of central carbon metabolic reactions, which yields biological insights comparable to those obtained using costly 2 H-labeled nutrient substrates.
09 BIOMASS FUELS↗
Corrosion of U233-Doped Uranium Oxide using Microfluidics Methods
The aim of work this year has been to investigate the role of alpha (α)-radiation and hydrogen (H 2 ) on the corrosion of uranium oxide (UO 2 ) using a microfluidic device. The microfluidic device, termed the Particle-Attached Microfluidic Electrochemical Cell, (PAMEC), enables monitoring of the UO 2 electrochemical corrosion potential (E corr ) under different environments, including de-aerated conditions and in the presence of dissolved H 2 . The Si 3 N 4 window allows us to study morphological and chemical changes under an electron microscope. We have previously demonstrated that the PAMEC matches the results from bulk electrochemical tests with UO 2 [1]. We used the high specific activity uranium (U) isotope, 233 U, (t 1/2 = 160,000 years) incorporated into UO 2 , to generate a localized a-field. The objective of the experiments were to mimic the radiation environment that would be experience at the surface of aged spent nuclear fuel (SNF) during long-term geologic disposal under anoxic conditions. Wittman et al. [2] predicted that in the presence of a pure a-radiation field and under H 2 conditions, the concentration of the radiolytic oxidant H 2 O 2 would be suppressed or even eliminated. In a UO 2 corrosion experiment this would be exhibited through a lowering of the measured UO 2 corrosion potential compared to identical conditions in the absence of dissolved H 2 . We found that the predictions of Wittman and co-workers were supported and that the corrosion potential of the 233 U-doped UO 2 in solution lowered with presence of H 2 gas and increased in the absence of H 2 , when under anoxic conditions. The PAMEC experiments indicate that H 2 O 2 has been eliminated in a solution sparged with H 2 while exposed to an a-radiation field. The corrosion potential of the a-doped 233 U(10%)- 238 UO 2 in a solution sparged with Ar/H 2 matched the corrosion potential of 238 UO 2 in solution sparged with air. This clearly demonstrated that the H 2 O 2 had been eliminated and that the only oxidant present was O 2 in this system in complete agreement with the modeling results of Wittman et al. These results point to the need to improve the Fuel Matrix Degradation (FMD) Process Model training data set that is being used in the FMD surrogate model that is being developed for the repository program. The incorporation of realistic radiation chemistry will improve the scientific basis for the FMD Model.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
A Goldilocks Approach to Water Management: Hydrochannel Porous Transport Layers for Unitized Reversible Fuel Cells
Abstract This work presents a novel porous transport layer (PTL), the hydrochannel PTL, that enables improved water management and record high round trip efficiency in unitized reversible fuel cells (URFCs). URFCs require rapid transport of O 2 and H 2 O to provide high performance in both fuel cell and water electrolyzer operation, but cell design is complicated by conflicting water management requirements: electrolyzers perform best with high liquid water saturation, whereas fuel cells perform best when liquid water saturation is as low as possible while still maintaining effective ionomer hydration. The hydrochannel PTL circumvents this obstacle by providing hydrophilic channels for water transport through an otherwise hydrophobic PTL, enabling optimal performance in both fuel cell and water electrolyzer modes. Neutron radiography measurements of water content in both operating modes confirm that the hydrochannel PTL enables high performance due to its improved water management capabilities.
25 ENERGY STORAGE↗
Differences in the response of two light guide technologies and two readout technologies after an exchange of liquid argon in the dewar
In this investigation the response to the scintillation light generated by through-going cosmic muons in liquid argon (LAr) was measured by two light guide technologies and two readout technologies after five weeks of running in the TallBo dewar at Fermilab. The response was remeasured after the dewar was drained of LAr, refilled, and then run again for an additional four weeks. After the dewar was refilled, there was clear evidence that the scintillation signal had dropped significantly. The two light guide technologies were developed at Indiana University and MIT/Fermilab. The two readout technologies were boards that passively or actively ganged 12 Hamamatsu MPPCs. Two possible explanations were identified for the degraded signal: the response of the two light guide technologies degraded due to damage caused by thermal cycling, and/or unknown differences in the trace residual Xe contamination in the fills of LAr led to the observed drop in scintillation light. Neither absorption nor quenching by N 2 , O 2 , and H 2 O contamination can account for the degradation. Neither the individual Hamamatsu MPPCs nor the passive/active ganging boards appear to have been affected by the thermal cycling. The path length distributions of the cosmics traversing the dewar appear quite similar in both event samples.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Achieving superior carbon transfer efficiency and pH control using membrane carbonation with a wide range of CO 2 contents for the coccolithophore Emiliania huxleyi
The economic viability of microalgal-derived products relies on rapid CO 2 transfer in a cost-effective manner. Many industrial gas streams contain concentrated CO 2 that, if converted to useful products, would lower greenhouse gas emissions and valorize the wasted CO 2 . Membrane carbonation (MC) uses non-porous hollow-fiber gas-transfer membranes to deliver CO 2 without bubble formation, which makes it possible to achieve a high carbon-transfer efficiency (CTE). However, inert gasses in the industrial streams (e.g., N 2 , O 2 , and H 2 O) can significantly lower the CO 2 -delivery rate. The means to overcome the buildup of inert gases in the membrane lumen is to manage the distal end of the membranes to sweep out inert gases while not wasting significant CO 2 . A MC-venting strategy was evaluated for CO 2 inputs from 5% to 100%. Abiotic tests using a restricted exit flow could achieve >95% CTE abiotic for industrial CO 2 streams. When integrated with semi-continuous cultivation of a marine coccolithophore, Emiliania huxleyi , CO 2 delivery and venting were on-demand based on a pH set points and pH-actuated feed and venting valves. MC using the venting strategy achieved 100% CTE biotic when delivering 100% and 50% CO 2 , which was better than 50% CTE biotic obtained from pH-controlled sparging of 100% CO 2 -sparging. E. huxleyi consistently fixed ~80% of the delivered CO 2 into biomass, and the remaining ~20% to calcite coccoliths. Finally, the compact size of MC modules, stable pH control, and no shear forces from bubble agitation during the CO 2 delivery made MC an ideal match for cultivation of coccolithophores, which are sensitive to shear forces and pH fluctuations.
54 ENVIRONMENTAL SCIENCES↗
Contrasting Trivalent Lanthanide and Actinide Complexation by Polyoxometalates via Solution-State NMR
Deciphering the solution chemistry and speciation of actinides is inherently difficult due to radioactivity, rarity, and cost constraints, especially for transplutonium elements. In this context, the development of new chelating platforms for actinides and associated spectroscopic techniques is particularly important. In this study, we investigate a relatively overlooked class of chelators for actinide binding, namely, polyoxometalates (POMs). We provide the first NMR measurements on americium–POM and curium–POM complexes, using one-dimensional (1D) 31 P NMR, variable-temperature NMR, and spin-lattice relaxation time (T 1 ) experiments. The proposed POM–NMR approach allows for the study of trivalent f-elements even when only microgram amounts are available and in phosphate-containing solutions where f-elements are typically insoluble. The solution-state speciation of trivalent americium, curium, plus multiple lanthanide ions (La 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Yb 3+ , and Lu 3+ ), in the presence of the model POM ligand PW 11 O 39 7– was elucidated and revealed the concurrent formation of two stable complexes, [M III (PW 11 O 39 )(H 2 O) x ] 4– and [M III (PW 11 O 39 ) 2 ] 11– . Interconversion reaction constants, reaction enthalpies, and reaction entropies were derived from the NMR data. The NMR results also provide experimental evidence of the weakly paramagnetic nature of the Am 3+ and Cm 3+ ions in solution. Furthermore, the study reveals a previously unnoticed periodicity break along the f-element series with the reversal of T 1 relaxation times of the 1:1 and 1:2 complexes and the preferential formation of the long T 1 species for the early lanthanides versus the short T 1 species for the late lanthanides, americium, and curium. Furthermore, given the broad variety of POM ligands that exist, with many of them containing NMR-active nuclei, the combined POM–NMR approach reported here opens a new avenue to investigate difficult-to-study elements such as heavy actinides and other radionuclides.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Expanding the Transuranic Metal–Organic Framework Portfolio: The Optical Properties of Americium(III) MOF-76
Reported here is the synthesis, crystal structure, and solid-state characterization of a new americium containing metal–organic framework (MOF), [Am(C 9 H 3 O 6 )(H 2 O)], MOF-76(Am). This material is constructed from Am 3+ metal centers and 1,3,5-tricarboxylic acid (BTC) ligands, forming a porous three-dimensional framework that is isostructural with several known trivalent lanthanide (Ln) analogs (e.g., Ce, Nd, and Sm–Lu). The Am 3+ ions have seven coordinates and assume a distorted, capped trigonal prismatic geometry with C1 symmetry. The Am 3+ –O bonds were studied via infrared spectroscopy and compared to several MOF-76(Ln) analogs, where Ln = Nd 3+ , Eu 3+ , Tb 3+ , and Ho 3+ . The results show that the strength of the ligand carboxylate stretching and bending modes increase with Nd 3+ < Eu 3+ < Am 3+ < Tb 3+ < Ho 3+ , suggesting the metal–oxygen bonds are predominantly ionic. Optical absorbance spectroscopy measurements reveal strong f–f transitions; some exhibit pronounced crystal field splitting. The photoluminescence spectrum contains weak Am 3+ -based emission that is achieved through direct and indirect metal center excitation. The weak emissive behavior is somewhat surprising given that ligand-to-metal resonance energy transfer is efficient in the isoelectronic Eu 3+ (4f 6 ) and related Tb 3+ (4f 8 ) analogs. The optical properties were explored further within a series of heterometallic MOF-76(Tb 1–x Am x ) (x = 0.8, 0.2, and 0.1) samples, and the results reveal enhanced Am 3+ photoluminescence.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗