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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Adsorption and activation of CO 2 on Pt/CeOx/TiO 2 (110): Role of the Pt-CeO x interface

The adsorption and dissociation of CO 2 on TiO 2 (110), CeO x /TiO 2 (110) and Pt/CeO x /TiO 2 (110) surfaces has been examined using Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS). The substrates under study exhibited different degrees of complexity which were tested for the binding of the adsorbate and the cleavage of C-O bonds. The surfaces were prepared by depositing CeO x (0.1 ML) onto TiO 2 (110) to form a mixed oxide support, onto which Pt nanoparticles (0.2 ML) were deposited. This configuration yields a complex set of interfaces between metal and oxides and we have systematically titrated the active role of each component (Pt 4f, Ce 3d and Ti 2p regions) and the arising surface intermediates (C 1s and O 1s regions). CO 2 barely bonds to stoichiometric TiO 2 (110). It heals oxygen vacancies of this oxide surface (CO 2,gas → CO gas + O a ) and does not form stable carbonates. A stable carbonate was seen upon adsorption of CO 2 on CeO x /TiO 2 (110) and on this type of substrate the adsorbate also removed O vacancies leading to the oxidation of Ti 3+ and Ce 3+ sites. Pt nanoparticles dispersed on CeO x /TiO 2 (110) were highly effective for the binding and dissociation of CO 2 , with the formation of CO 3 , CO, C and CH x species on the Pt/CeO x /TiO 2 (110) system. The results of theoretical calculations based on density-functional theory (DFT) show that Pt/CeOx/TiO2(110) binds CO2 much stronger than surfaces of bulk platinum {(111), (100), (110)} or other late transition metals. On a Pt-CeO x interface, the molecule adsorbs with a bent configuration (~ 130° O-C-O bond angle) and with a substantial elongation (~ 0.1 Å) of the C-O bonds, facilitating its transformation into high value chemicals.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Efficient SABRE-SHEATH Hyperpolarization of Potent Branched-Chain-Amino-Acid Metabolic Probe [1-13C]ketoisocaproate

Efficient 13C hyperpolarization of ketoisocaproate is demonstrated in natural isotopic abundance and [1-13C]enriched forms via SABRE-SHEATH (Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei). Parahydrogen, as the source of nuclear spin order, and ketoisocaproate undergo simultaneous chemical exchange with an Ir-IMes-based hexacoordinate complex in CD3OD. SABRE-SHEATH enables spontaneous polarization transfer from parahydrogen-derived hydrides to the 13C nucleus of transiently bound ketoisocaproate. 13C polarization values of up to 18% are achieved at the 1-13C site in 1 min in the liquid state at 30 mM substrate concentration. The efficient polarization build-up becomes possible due to favorable relaxation dynamics. Specifically, the exponential build-up time constant (14.3 ± 0.6 s) is substantially lower than the corresponding polarization decay time constant (22.8 ± 1.2 s) at the optimum polarization transfer field (0.4 microtesla) and temperature (10 °C). The experiments with natural abundance ketoisocaproate revealed polarization level on the 13C-2 site of less than 1%—i.e., one order of magnitude lower than that of the 1-13C site—which is only partially due to more-efficient relaxation dynamics in sub-microtesla fields. We rationalize the overall much lower 13C-2 polarization efficiency in part by less favorable catalyst-binding dynamics of the C-2 site. Pilot SABRE experiments at pH 4.0 (acidified sample) versus pH 6.1 (unaltered sodium [1-13C]ketoisocaproate) reveal substantial modulation of SABRE-SHEATH processes by pH, warranting future systematic pH titration studies of ketoisocaproate, as well as other structurally similar ketocarboxylate motifs including pyruvate and alpha-ketoglutarate, with the overarching goal of maximizing 13C polarization levels in these potent molecular probes. Finally, we also report on the pilot post-mortem use of HP [1-13C]ketoisocaproate in a euthanized mouse, demonstrating that SABRE-hyperpolarized 13C contrast agents hold promise for future metabolic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗
DOE OSTI2022

Titrating Controlled Defects into Si-LTA Zeolite Crystals Using Multiple Organic Structure-Directing Agents

Controlling defects in zeolites is crucial for tuning their adsorption and catalytic properties. In this work, we have performed an integrated zeolite synthesis, spectroscopy, and density functional theory study to test the limit of F– as a charge-balancing agent that mitigates defects in siliceous zeolites. We focused on the synthesis of siliceous zeolite LTA at 150 °C with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the primary organic structure-directing agent (OSDA) and tetramethyl ammonium (TMA) as the secondary OSDA. By varying the amount of TMA in the synthesis gel, positive charges were titrated into the resulting as-made Si-LTA. Surprisingly, we found that greater TMA concentration does not induce more F– to enter into the zeolite. 29Si solid-state MAS NMR, Raman spectroscopy, and density functional theory suggest that this system has surpassed its capacity for F– to balance OSDA charge, and additional positive charge is balanced by Si–O– framework defects. The number of defects in the as-made Si-LTA can be precisely titrated by the amount of TMA in the zeolite structures. For the Si-LTA synthesized without TMA, framework defects formed in the early stage of crystal growth were found to heal during later crystallization, leading to defect-free Si-LTA. However, for the Si-LTA synthesized with TMA, the defects formed in early stages do not heal. A DFT thermodynamic analysis explains that crowding of Si-LTA pores by TMA impedes defect healing; this prediction is corroborated by synthesis experiments at an elevated temperature (170 °C). These results indicate that F– can have a limited capacity to balance OSDA charge in zeolite synthesis, opening up a third route to zeolite synthesis intermediate between the fluoride and hydroxide routes.

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

Stoichiometric Lanthanide Compounds with Diglycolamides: A Synthetic Approach toward Understanding Rare-Earth Speciation in Solution

A fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining the chemical behavior of rare-earth metals in complex liquid–liquid extraction processes. Probing the exact bonding between the extractant and the metal is sometimes done through the synthesis of solid-state compounds that can serve as models for metal speciation in solution. In the case of diglycolamide (DGA), a commonly used neutral diamide extractant, extensive studies identify the stepwise formation of 1:1 [Ln(DGA)(H 2 O) 6 ] 3+ , 1:2 [Ln(DGA) 2 (H 2 O) 3 ] 3+ , and 1:3 [Ln(DGA) 3 ] 3+ complexes in solution. The crystallographic reports, however, exclusively show a 1:3 [Ln(DGA) 3 ] 3+ moiety in the solid state, while the structures of 1:1 and 1:2 complexes are yet to be isolated and comprehensively studied. In this work, we report the synthesis and characterization of three new families of stoichiometric N,N,N′,N’ -tetramethyldiglycolamide (TMDGA) compounds: [Ln(TMDGA)(H 2 O) 5 Cl]Cl 2 ·2H 2 O, [Ln(TMDGA) 2 (H 2 O) 3 ]Cl 3 ·3H 2 O, and [Ln(TMDGA) 3 ]Cl 3 ·7H 2 O, where Ln = Nd, Eu, Gd, with Ln:TMDGA ratios of 1:1, 1:2, and 1:3, respectively. Further, the compounds have been analyzed using vibrational spectroscopy (both Raman and FT-IR), as well as variable temperature fluorescence spectroscopy. A spectrophotometric titration of Eu(III) was performed to confirm the presence of the [Eu(TMDGA) n ] 3+ ( n = 1, 2, and 3) species in solution and to compare the individual solid-state emission spectra to their respective analogues in solution.

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

Distinguishing Desirable and Undesirable Reactions in Multicomponent Systems for Redox Activation of the Uranyl Ion

Although it has been established that covalent functionalization of the U–O bonds in the uranyl dication (UO 2 2+ ) generally requires use of strong reductants and electrophiles, little work has examined how interactions between the individual reaction components could affect final outcomes in solution. Here, the patterns of such reactivity have been studied in a UO 2 2+ -containing model system supported by a workhorse pentadentate ligand, 2,2′-[(methylimino)bis(2,1-ethanediylnitrilomethylidyne)]bis-phenol. Oxo activation and functionalization have been tested with (i) electrochemical and chemical reduction, and (ii) coordinating and noncoordinating solvents. In acetonitrile, uranyl reduction was achieved cleanly, but treatment of the reduced species with tris(pentafluorophenyl)borane (BCF) resulted in a mixture of products arising from direct electron transfer to BCF. In dichloromethane (CH 2 Cl 2 ), electrochemical reduction of uranyl was achieved cleanly, but clean chemical reactivity was inaccessible. Despite these challenges, one trinuclear and oxo-deficient uranium-containing product was crystallized from CH 2 Cl 2 solution and characterized; thus, desirable electrophilic reactivity can proceed to some degree in CH 2 Cl 2 with BCF. Computational studies were used to investigate the properties of the trinuclear uranium product and the changes that could be inducible by further reduction. Here, taken together, the reactivity patterns identified here could inform design of improved systems for actinyl oxo functionalization.

cations↗
NASA NTRS2022

Limitations in Representation of Physical Processes Prevents Successful Simulation of PM2.5 During KORUS-AQ

High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea United States-Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. At the surface, the model underestimates sulfate by -64% but overestimates nitrate by +36%. The largest underestimate in sulfate occurs during the pollution event, where models typically struggle to generate elevated sulfate concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by +100% against aircraft observations. We hypothesize that this is due to a large missing sink, which we implement here as a factor of five increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model’s inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66% to 54%. Locally-produced sulfate increased from 1% to 25% of locally-produced PM2.5, implying that local emissions controls would have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction which affects the aerosol liquid water abundance and chemistry driving sulfate-nitrate-ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30% less sulfate due to 40% less nitrate and aerosol water, and results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and nighttime boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate+nitrate+ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements.

Katherine R. Travis↗
NASA NTRS2004

Montmorillonite, oligonucleotides, RNA and origin of life

Na-montmorillonite prepared from Volclay by the titration method facilitates the self-condensation of ImpA, the 5'-phosphorimidazolide derivative of adenosine. As was shown by AE-HPLC analysis and selective enzymatic hydrolysis of products, oligo(A)s formed in this reaction are 10 monomer units long and contain 67% 3',5'-phosphodiester bonds (Ferris and Ertem, 1992a). Under the same reaction conditions, 5'-phosphorimidazolide derivatives of cytidine, uridine and guanosine also undergo self-condensation producing oligomers containing up to 12-14 monomer units for oligo(C)s to 6 monomer units for oligo(G)s. In oligo(C)s and oligo(U)s, 75-80% of the monomers are linked by 2',5'-phosphodiester bonds. Hexamer and higher oligomers isolated from synthetic oligo(C)s formed by montmorillonite catalysis, which contain both 3',5'- and 2',5'-linkages, serve as catalysts for the non-enzymatic template directed synthesis of oligo(G)s from activated monomer 2-MeImpG, guanosine 5'-phospho-2-methylimidazolide (Ertem and Ferris, 1996). Pentamer and higher oligomers containing exclusively 2',5'-linkages, which were isolated from the synthetic oligo(C)s, also serve as templates and produce oligo(G)s with both 2',5'- and 3',5'-phosphodiester bonds. Kinetic studies on montmorillonite catalyzed elongation rates of oligomers using the computer program SIMFIT demonstrated that the rate constants for the formation of oligo(A)s increased in the order of 2-mer < 3-mer < 4-mer ... < 7-mer (Kawamura and Ferris, 1994). A decameric primer, dA(pdA)8pA bound to montmorillonite was elongated to contain up to 50 monomer units by daily addition of activated monomer ImpA to the reaction mixture (Ferris, Hill and Orgel, 1996). Analysis of dimer fractions formed in the montmorillonite catalyzed reaction of binary and quaternary mixtures of ImpA, ImpC, 2-MeImpG and ImpU suggested that only a limited number of oligomers could have formed on the primitive Earth rather than equal amounts of all possible isomers (Ertem and Ferris, 2000). Formation of phosphodiester bonds between mononucleotides by montmorillonite catalysis is a fascinating discovery, and a significant step forward in efforts to find out how the first RNA-like oligomers might have formed in the course of chemical evolution. However, as has been pointed out in several publications, these systems should be regarded as models rather than a literal representation of prebiotic chemistry (Orgel, 1998; Joyce and Orgel, 1999; Schwartz, 1999).

RNA/chemical synthesis↗
DOE OSTI2020

Benzenesulfonamide Derivatives as Complexants and Extractants for Addressing the Mercury Problem at the Savannah River Site

Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Its widespread use in medicinal and industrial applications makes it a common chemical exposure and environmental pollutant. It can exist in several forms which include: Metallic mercury (Hg{sup 0}), mercurous (Hg{sub 2}{sup 2+}), mercuric salts (Hg{sup 2+}), and organic mercury (e.g. CH{sub 3}Hg{sup +}), with the latter being the most toxic of all the species. Due to mercury's high toxicity, new approaches towards its detection has received significant attention in the scientific community. Mercury exposure at the Savannah River Site (SRS) has been a recent concern especially with increasing amounts of organic mercury in the saltstone. It originates mainly from its use as an acidic dissolution catalyst of aluminum cladding from target fuels within the uranium and plutonium processing operations [1]. It is present to an amount of about 60 metric tons in the high-level waste (HLW) tanks. Organic Mercury species have been found in low activity waste (LAW) at the site that eventually ends up in the saltstone. Therefore, there is a need for: i) Converting organic mercury to other less toxic forms and ii) Complexation and removal of Hg prior of disposal of LAW in saltstone. Various methods have been developed for selective sensing of mercury in the presence of other toxic metals. These methods include using ligands that can form organo-soluble metal complexes with different optical and spectroscopic properties that can be used for toxic metal sensing. In 2005, our group pioneered an ion-exchange extraction method, in which o-phenylenediamine-derived disulfonamides were used to complex and selectively extract and sense Pb{sup 2+} from aqueous solutions into an organic phase [2,3]. Herein, a disulfonamide and a bis-dansylamide have been shown to extract, complex and sense Hg(II). Ligand 1: The crystal structure of the disulfonamide-Hg complex confirms the complexation of Hg(II) with the ligand. Complexation was corroborated by the {sup 1}H-NMR spectra obtained after contacting solutions of various concentrations of Hg{sup 2+} with 2 mM ligand in chloroform. Distinct resonances are observed at Hg/L ratio of 0.5 that are also observed for the isolated 1:2 complex. In the presence of excess mercury, new resonances, as well as the movement of Et{sub 3}N resonances indicate the formation of a different Hg-sulfonamide-triethylamine complex, presumably having 1:1 Hg:L stoichiometry. The electronic spectra of aqueous phases after extraction show that there was no free ligand absorption at 0.5 eq of Hg, indicating a complete complexation. Complexation was also confirmed by the UV-visible titrations with Hg{sup 2+} at constant ligand concentration. pH-dependent extraction carried out shows that extraction of Hg(II) by ligand 1 was over 90% for most alkaline pHs. Ligand 2: The crystal structure of the Ligand 2 complex formed with Hg(OAc){sub 2} shows a remarkable coordination pattern with 4:2 metal:ligand stoichiometry. The fluorescent bis-dansyl disulfonamide derivative was found to complex and sense HgCl{sub 2} and Hg(OAc){sub 2} by demonstrating fluorescence quenching upon Hg(II) addition in comparison with other metals (Zn(II), Cd(II), Pb(II)). No were observed for Cu(II), Ag(I) and Co(II). We have shown the complexation of Hg(II) by a disulfonamide and a bis-dansyl disulfonamide ligand using several spectroscopic methods. Ligand 1 was able to extract mercury into chloroform and form a complex in the presence of excess mercury by synergistic complexation with triethylamine acting as a co-ligand. X-ray and NMR both confirm a 1:2 HgL{sub 2} stoichiometry. Ligand 2 can be used for sensing of Hg(II) as fluorescence quenching was observed after addition of Hg(II)

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

Oxide-catalyzed self- and cross-condensation of cycloketones. Kinetically relevant steps that determine product distribution

Metal oxides with acid-base properties can be used to catalyze aldol condensation and potentially obtain valuable chemicals from biomass-derived oxygenates. Understanding the reaction mechanisms could enable the development of effective catalysts with controllable selectivity. In this work, we investigate the reaction parameters that affect the kinetics and product distribution of self- and cross-aldol condensation of cyclopentanone (CPO) and cyclohexanone (CHO) over CeO 2 and ZrO 2 catalysts by combining detailed analysis of experiments and DFT calculations. It is well-known that either the deprotonation of an α-C–H that generates an enolate or the C–C coupling that produces the dimers can be rate-limiting step. Indeed, the detailed kinetics analysis shows that the observed data can be fitted by unimolecular or bimolecular Langmuir-Hinshelwood models. Specifically, on the ZrO 2 catalyst, the unimolecular α-C–H activation is the rate limiting step for the CPO self-condensation, while the bimolecular C–C coupling limits the CHO self-condensation. By contrast, on CeO 2 , the bimolecular C–C coupling step seems to be rate-limiting for both CPO and CHO self-condensation reactions. The adsorption parameters derived from kinetics fitting indicate that when the two reactants are co-fed, the surface is preferentially covered by CHO. So, the condensation rate of [CPO]-activated products ([CPO]CPO + [CPO]CHO) decreases in the presence of CHO, due to the competitive adsorption. However, despite a higher surface coverage, CHO is not an effective electrophile because it imposes stronger steric constraints to the formation of the C–C bond than CPO. Therefore, for a given enolate, the product distribution shows that [CPO]CPO > [CPO]CHO and, similarly [CHO]CPO > [CHO]CHO. Likewise, the yields of [CPO]- and [CHO]-activated products in mixed CPO/CHO feeds are similar because the higher surface coverage and stability of the [CHO] enolate is counterbalanced by the inhibition of C–C coupling by steric constraints when CHO is involved. In summary, the overall rank of products observed experimentally can be explained in terms of a combination of the following effects: relative surface coverage of the reactants, steric constraints for the C–C coupling, stability of the enolate, and effectiveness of the electrophile to accept an electron.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗