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DOE OSTI2022

Energy-resolved mass spectrometry as a tool for identification of lignin depolymerization products

Lignin is the largest source of bio-based aromatic compounds in nature, and its valorization is essential to the sustainability of lignocellulosic biorefining. Characterizing lignin-derived compounds remains challenging due to the heterogeneity of this biopolymer. Tandem mass spectrometry is a promising tool for lignin structural analytics, as fragmentation patterns of model compounds can be extrapolated to identify characteristic moieties in complex samples. This work extends previous resonance excitation type collision-induced dissociation (CID) methods that identified lignin oligomers containing β-Ο-4, β-5, and β-β bonds, to also identify characteristics of 5-5, β-1, and 4-Ο-5 dimers, enabled by quadrupole time-of-flight (QTOF) CID with energy-resolved mass spectrometry (ERMS). Overall, beam type ERMS offers in-depth structural information and could ultimately contribute to tools for high-throughput lignin dimer identification.

09 BIOMASS FUELS↗

DOE OSTI2026

Electrocatalytic Hydrotreatment of Bio-Oil: Exploring Interactions Between Functional Groups

Electrocatalytic hydrotreatment (ECH) is being explored as a sustainable route for upgrading bio-oil to renewable fuels and chemicals. Bio-oil, produced by the fast pyrolysis of lignocellulosic biomass, is a complex mixture of compounds with various oxygen-containing functional groups, such as anhydrosugars, carboxylic acids, ketones, aldehydes, furans, phenols and alcohols. The ECH of several bio-oil model compound binary mixtures was conducted to investigate the interactions between these functional groups. Notably, phenolic compound reduction was significantly inhibited in the presence of aldehydes, particularly furfural. A strategy involving the reagent-based reduction of the aldehyde to an alcohol prior to ECH was shown to partially mitigate this inhibitory effect. Additionally, qualitative studies on the ECH of catalytic fast pyrolysis (CFP) oil with low aldehyde content showed promising results. These studies achieved the conversion of cyclopentenones and phenolic compounds present in the CFP oil to cyclopentanols and cyclohexanols, respectively.

09 BIOMASS FUELS↗

DOE OSTI2023

Interaction of Anisole on Alumina-Supported Ni and Mo Oxide Hydrodeoxygenation Catalysts

The conversion of biomass to transportation fuels and value-added chemicals is a promising method to reduce reliance on fossil fuels. Mo-based catalysts have been shown to be highly active in the hydrodeoxygenation of biomass-derived phenolic compounds. The catalyst active phase, surface species, and the effect of adding additional metals is not comprehensively understood. Here we compare the temperature-dependent adsorption behavior of the model compound anisole 2 on an alumina-supported mixed nickel molybdenum oxide catalyst with two reference catalysts of molybdenum oxide and nickel oxide. Raman spectroscopy showed that the catalysts contain significant amounts of molybdates and molybdoaluminates, in addition to NiMoO 4 in the nickel molybdenum catalyst and MoO 3 in the molybdenum-only catalyst. Using transmission infrared spectroscopy under a controlled environment, we find that anisole chemisorbed largely through the oxygen in the methoxy group to form surface-bound phenoxy and methoxy species on all the catalysts. Ambient pressure X-ray photoelectrons spectroscopy measurements of the catalysts in anisole vapor showed reduced Mo atoms are the binding sites. The surface interaction and removal temperature of these species varied with the metal composition. The MoO x component dominated the adsorption behavior in both MoO x and NiMoO x catalysts. The formation of new aromatics, including methylated rings, depended on Ni composition. Upon adding hydrogen to induce the hydrodeoxygenation of anisole, undesirable polynuclear aromatic species were quickly formed on the Mo-based catalysts. In conclusion, these results suggest that the molybdenum oxide controls the adsorption and reactivity of the surface species, with a cooperative effect by Ni.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

High-Throughput Microbial Community Analyses to Establish a Natural Fungal and Bacterial Consortium from Sewage Sludge Enriched with Three Pharmaceutical Compounds

Emerging and unregulated contaminants end up in soils via stabilized/composted sewage sludges, paired with possible risks associated with the development of microbial resistance to antimicrobial agents or an imbalance in the microbial communities. An enrichment experiment was performed, fortifying the sewage sludge with carbamazepine, ketoprofen and diclofenac as model compounds, with the aim to obtain strains with the capability to transform these pollutants. Culturable microorganisms were obtained at the end of the experiment. Among fungi, Cladosporium cladosporioides, Alternaria alternata and Penicillium raistrickii showed remarkable degradation rates. Population shifts in bacterial and fungal communities were also studied during the selective pressure using Illumina MiSeq. These analyses showed a predominance of Ascomycota (Dothideomycetes and Aspergillaceae) and Actinobacteria and Proteobacteria, suggesting the possibility of selecting native microorganisms to carry out bioremediation processes using tailored techniques.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Understanding the influence of solvents on the Pt-catalyzed hydrodeoxygenation of guaiacol

Bio-oil derived from fast pyrolysis of lignocellulosic biomass needs to be deoxygenated to become a substitute for petroleum fuels. Here, we study the hydrodeoxygenation mechanism of guaiacol, a bio-oil model compound derived from the lignin fraction of biomass, on Pt(1 1 1) terrace sites in the presence of water, diethyl ether, 1-butanol, and n-hexane as solvent. Using first-principles periodic density functional theory (DFT) calculations and mean-field microkinetic reactor modeling, a detailed reaction mechanism is investigated targeting various products such as catechol, phenol, anisole, benzene, cyclohexanone, and cyclohexanol. Solvent phase DFT outcomes are mostly similar to that of the vapor phase; however, microkinetic modeling results suggest that rate controlling species and transition states differ somewhat in the various reaction environments. Catechol was found to be the major aromatic product across all reaction environments. Over Pt(1 1 1), unsaturated monooxygenate production from catechol is unlikely.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Elucidating Biomass-Derived Pyrolytic Lignin Structures from Demethylation Reactions through Density Functional Theory Calculations

Pyrolytic lignin is a fraction of pyrolysis oil that contains a wide range of phenolic compounds that can be used as intermediates to produce fuels and chemicals. However, the characteristics of the raw lignin structure make it difficult to establish a pyrolysis mechanism and determine pyrolytic lignin structures. Herein this study proposes dimer, trimer, and tetramer structures based on their relative thermodynamic stability for a hardwood lignin model in pyrolysis. Different configurations of oligomers were evaluated by varying the positions of the guaiacyl (G) and syringyl (S) units and the bonds βO4 and β5 in the hardwood model lignin through electronic structure calculations. The homolytic cleavage of βO4 bonds is assumed to occur and generate two free radical fragments. These can stabilize by taking hydrogen radicals that may be in solution during the intermediate liquid (pathway 1) formation before the thermal ejection. An alternative pathway (pathway 2) could occur when the radicals use intramolecular hydrogen, turning themselves into stable products. Subsequently, a demethylation reaction can take place, thus generating a methane molecule and new oligomeric lignin-derived molecules. The most probable resulting structures were studied. We used FTIR and NMR spectra of selected model compounds to evaluate our calculation approach. Thermophysical properties were calculated using group contribution methods. The results give insights into the lignin oligomer structures and how these molecules are formed. They also provide helpful information for the design of pyrolysis oil separation and upgrading equipment.

09 BIOMASS FUELS↗

DOE OSTI2022

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

DOE OSTI2025

Effect of Solvents on Lignin–Surface Interactions via Molecular Dynamics Simulations

Lignin, an essential building block of lignocellulosic biomass, is a potential abundant source of aromatic monomers for the polymer and chemical industry. Reductive catalytic fractionation (RCF) is one promising process that can produce high yields of phenolic monomers and oligomers from lignin under different catalytic conditions. An important choice in optimizing RCF is the selection of solvent; however, detailed insights into solvent effects on lignin behaviors and interactions remain limited. Here, in this work, we perform all-atom molecular dynamics simulations to study the solvation of lignin, solvent-mediated conformational changes, and the interaction of solvated lignin oligomers with model surfaces. We focus on the behavior of an oligomeric lignin model compound in methanol, ethanol, a binary mixture of ethanol and water, and water at both the RCF reaction temperature (473 K) and room temperature. Analysis of structural features of lignin suggests that these three organic solvent systems favorably solvate lignin, resulting in a more extended conformation suitable for catalytic conversion to valuable chemicals. We further introduce model palladium (Pd) and carbon (C) surfaces to understand how solvent choice impacts adsorption onto a representative catalytic surface and support, and to quantify the competition among the reactant and solvent molecules for the surface. Unbiased simulations suggest strong adsorption of lignin on both Pd and C surfaces at 473 K, with notable solvent-mediated differences in adsorption energies. Additionally, our findings indicate that lignin adsorption is promoted by the entropy change resulting from the displacement of solvent molecules from the surface. This study provides a molecular perspective of adsorption of lignin onto varying surfaces, which is a step towards understanding and optimizing the catalytic conversion of lignin into valuable chemicals.

adsorption↗

DOE OSTI2025

Cleavage of C-O and C-C Bonds in Lignin-Derived Compounds to Produce Aromatics Using Molybdenum-Containing MFI Zeolites

Lignin, the most abundant source of renewable arenes, is a viable feedstock for the production of aromatic compounds. However, the prevalence of resilient C-C bonded oligomeric fragments in lignin-derived streams can compromise monomer yields during reductive catalytic fractionation (RCF). To address this issue, we developed a bifunctional molybdenum-containing MFI (Mo/H-MFI) zeolite catalyst capable of cleaving both C-O and C-C bonds in lignin-derived molecules to produce aromatic monomers. Using propylguaiacol as a model compound, we demonstrated the importance of proximity between metallic molybdenum carbide sites and the Bronsted acid sites in the zeolite in achieving high carbon yields (~80%) of benzene, toluene, propylbenzene, and phenol while maintaining catalyst stability (>98% stable conversion for 20 h). A reaction network involving both C-O and C-C bond cleavage pathways was proposed based on kinetic studies using key intermediates as feeds. Finally, we successfully depolymerized partially deoxygenated lignin oil obtained from the RCF of poplar using a continuous, two-pass catalytic process. This work highlights the potential of the bifunctional Mo/H-MFI catalyst in upgrading complex lignin feedstocks and provides a methodological approach for converting lignin-derived compounds into platform aromatic chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Assessing the Role of the Support in Acetic Acid Hydrodeoxygenation Selectivity on Pt/TiO2

To produce drop-in quality biofuels following the thermochemical conversion of biomass via catalytic fast pyrolysis (CFP), hydrodeoxygenation (HDO) reactions can be performed to remove excess oxygen and create a more stable bio-oil product. HDO reactions involve co-feeding the CFP vapor-phase product and H2 gas over bi-functional catalysts, such as noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2). Recent model-compound studies, focusing on important classes of species in the CFP vapor mixture, have sought to determine the role of the various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in producing the observed desired deoxygenation and undesired decarboxylation/decarbonylation products. One important class of compounds in the CFP vapor-phase product is carboxylic acids (e.g., acetic acid). Prior experimental work on acetic acid HDO (AA-HDO) found that Pt/C and Pt/TiO2 catalysts favored the formation of undesired C-C and desired C-O bond-dissociation products; however, the fundamental surface chemistry driving this shift in selectivity has not been established. This presentation employs atomic-scale modeling to determine, through comparisons of adsorption and reaction energetics, how Pt-metal, Pt-TiO2-interface, and interfacial-vacancy sites catalyze the competing reaction pathways for AA-HDO. Our analysis indicates that hydroxyl vacancies at the Pt-TiO2 interface are critical for lowering barriers for C-O bond-cleavage steps, such that they become favorable/competitive with respect to C-C bond-dissociation steps.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

DOE OSTI2026

Coordination-Induced Weakening of N–H Bonds Driven by Bimetallic Cooperativity in Zr/Co Compounds

The bond dissociation free energy (BDFE) of the element-hydrogen bonds of protic substrates have been found to decrease upon metal coordination. Herein, an early/late heterobimetallic complex is used to examine the impact on the BDFE N−H when the substrate binding site and the redox-active site are two different metals that are spatially separated. A tris- (phosphinoamide) framework is used to link a d 0 ZrIV center with an accessible substrate binding site to a coordinatively saturated redox-active Co center, which serves as an appended electron reservoir. A series of aniline, amido, and imido Zr/Co model compounds were synthesized starting from the Zr IV /Co −I aniline adduct PhH 2 N−Zr(MesNP i Pr 2 ) 3 CoCN t Bu (2). 2,4,6-tristert- butylphenoxyl radical ( t Bu 3 ArO • ) was used to abstract one or two H atoms and produce the amido and imido complexes PhHNZr( MesNP i Pr 2 ) 3 CoCN t Bu (3) and PhN≡Zr(MesNP i Pr 2 ) 3 CoCNtBu (4), respectively. Using open-circuit potential measurements, the BDFE N−H within 2 and 3 were determined to be 37 kcal/mol (2) and 55 kcal/mol (3). Cyclic voltammetry measurements were conducted to determine the Co I/0 and Co 0/−I redox potentials. The pK a s were then estimated using the Bordwell equation to provide further insight into the thermochemical aspects of the observed proton coupled electron transfer (PCET) reactions.

Bond dissociation free energy↗

DOE OSTI2023

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more-stable bio-oil product. HDO reactions are performed by co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2) are active and selective toward these HDO reactions. Griffin and co-workers showed that Pt/TiO2 catalysts promote the desired deoxygenation steps for m-cresol HDO while mitigating undesired C-C bond-breaking steps that reduce the overall value/energy density of the biofuel. Such model-compound studies to inform the design of improved catalysts for HDO chemistry are necessary to improve the overall process economics/efficiencies for biofuels production. One important class of bio-derived compounds that has not been studied extensively with respect to HDO chemistry, particularly at the atomic level, is carboxylic acids. Past experimental work indicates that Pt/C and Pt/TiO2 catalysts are selective toward C-C and C-O bond-dissociation products for acetic acid HDO, respectively. To understand the role of Pt/TiO2 active sites in this observed change in selectivity and guide catalyst development, the work in this presentation focuses on modeling the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in acetic acid HDO. Density functional theory (DFT) calculations were performed using the Vienna Ab initio Simulation Package (VASP). The exchange-correlation functional was approximated by the Perdew-Burke-Ernzerhof functional. Dispersion interactions were captured using the D3 method. Projector augmented-wave potentials described electron-ion interactions, and electron wavefunctions were expanded via a planewave basis with an energy cutoff of 500 eV. Activation barriers were calculated using the climbing image nudged elastic band method. Results and Discussion: To discern the role of Pt-metal and Pt-TiO2 interface sites in promoting acetic acid HDO chemistry, Pt(111) slab and anatase TiO2(101)-supported Pt-nanowire (PtNW/OH-TiO2) surface models were constructed, respectively. Because H2 is co-fed in HDO reactions, the anatase support was terminated with OH groups. Interfacial vacancies have been shown to facilitate Ru/TiO2-catalyzed phenol HDO; thus, an interfacial model with an OH vacancy was also considered (PtNW/OHv-TiO2). Pt-TiO2-interface sites stabilize adsorption of all studied acetic acid HDO surface intermediates relative to terrace Pt-metal sites, particularly when an interfacial-OH vacancy is present. Oxygenated species prefer to bind at the OH vacancy through the O atom, suggesting a preference for C-O over C-C bond cleavage at these sites. This hypothesis is supported by net-negative and net-positive average shifts in the reaction energy and activation energy barriers for C-O and C-C bond-breaking steps, respectively, at Pt-TiO2-interface sites relative to Pt-metal sites. Using the calculated energetics, the predicted minimum-energy pathway was determined for each surface. Pt(111) is predicted to follow decarboxylation, producing undesired methane and carbon dioxide. Conversely, PtNW/OH-TiO2 and PtNW/OHv-TiO2 are both predicted to produce desired acetaldehyde and ethane. The interfacial vacancy may also play a key role in facilitating the first C-O bond-breaking step in acetic acid HDO, lowering the barrier by 0.6 eV relative to the defect-free interface model. These results demonstrate the critical role of the Pt-TiO2 interface in the shift in acetic acid HDO selectivity experimentally observed on Pt/C and Pt/TiO2 catalysts. The results herein demonstrate the important role of the Pt-TiO2 interface and interfacial oxygen vacancies in improving the carbon efficiency for HDO reactions in CFP upgrading.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

DOE OSTI2023

Biomimetic oxidative copolymerization of hydroxystilbenes and monolignols

Hydroxystilbenes are a class of polyphenolic compounds that behave as lignin monomers participating in radical coupling reactions during the lignification. Here, we report the synthesis and characterization of various artificial copolymers of monolignols and hydroxystilbenes, as well as low-molecular-mass compounds, to obtain the mechanistic insights into their incorporation into the lignin polymer. Integrating the hydroxystilbenes, resveratrol and piceatannol, into monolignol polymerization in vitro, using horseradish peroxidase to generate phenolic radicals, produced synthetic lignins [dehydrogenation polymers (DHPs)]. Copolymerization of hydroxystilbenes with monolignols, especially sinapyl alcohol, by in vitro peroxidases notably improved the reactivity of monolignols and resulted in substantial yields of synthetic lignin polymers. The resulting DHPs were analyzed using two-dimensional NMR and 19 synthesized model compounds to confirm the presence of hydroxystilbene structures in the lignin polymer. The cross-coupled DHPs confirmed both resveratrol and piceatannol as authentic monomers participating in the oxidative radical coupling reactions during polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Role Evaluation of Active Groups in Lignin on UV-Shielding Performance

The contribution of the active groups in lignin to ultraviolet (UV)-shielding performance still remains unclear. In this study, we employed 16 lignin model compounds and theoretical calculations to ascertain the contribution of different functional groups to UV-shielding performance. These results showed that the order of UV-shielding performance on functional groups was -C=C–CHO > -C=C–COOH > -C=C–CH 2 OH > --C=C > quinone > -COOH > -OCH 3 ≈ -OH. Moreover, the synergism between the para-substituted electron-donating group -OH and the electron-withdrawing group allyl on the aromatic ring played a major role in UV-shielding performance of lignin models, whereas the additive effect of meta/ortho-substituted -OCH 3 played a secondary role. Furthermore, we found that the hydrophile–lipophile balance (HLB) value of lignin models also greatly affected the sunscreen protection factor (SPF) of lignin model-based sunscreens. A closer HLB value of lignin to 8.89 corresponded with a higher SPF of the lignin model-based sunscreen. The commercial photoprotective ingredient ethylhexyl methoxycinnamate (EHMC) and lignin models had a synergistic effect on UV-shielding performance caused by the π–π stacking interaction between the parallel-displaced stacked aromatic rings of lignin models and EHMC. Additionally, the UV irradiation test showed that these sunscreens prepared using lignin models and EHMC exhibited good photostability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Interfacial Electrochemistry of Catalyst-Coordinated Graphene Nanoribbons

The immobilization of molecular electrocatalysts on conductive electrodes is an appealing strategy for enhancing their overall activity relative to those of analogous molecular compounds. Here, in this study, we report on the interfacial electrochemistry of self-assembled two-dimensional nanosheets of graphene nanoribbons (GNR-2DNS) and analogs containing a Rh-based hydrogen evolution reaction (HER) catalyst (RhGNR-2DNS) immobilized on conductive electrodes. Proton-coupled electron transfer (PCET) taking place at N-centers of the nanoribbons was utilized as an indirect reporter of the interfacial electric fields experienced by the monolayer nanosheet located within the electric double layer. The experimental Pourbaix diagrams were compared with a theoretical model, which derives the experimental Pourbaix slopes as a function of parameter f, a fraction of the interfacial potential drop experienced by the redox-active group. Interestingly, our study revealed that GNR-2DNS was strongly coupled to glassy carbon electrodes (f = 1), while RhGNR-2DNS was not (f = 0.15). We further investigated the HER mechanism by RhGNR-2DNS using electrochemical and X-ray absorption spectroelectrochemical methods and compared it to homogeneous molecular model compounds. RhGNR-2DNS was found to be an active HER electrocatalyst over a broader set of aqueous pH conditions than its molecular analogs. We find that the improved HER performance in the immobilized catalyst arises due to two factors. First, redox-active bipyrimidine-based ligands were shown to dramatically alter the activity of Rh sites by increasing the electron density at the active Rh center and providing RhGNR-2DNS with improved catalysis. Second, catalyst immobilization was found to prevent catalyst aggregation that was found to occur for the molecular analog in the basic pH. Overall, this study provides valuable insights into the mechanism by which catalyst immobilization can affect the overall electrocatalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Elucidating the Effects of Temperature on Nonaqueous Redox Flow Cell Cycling Performance

The impact of cell temperature is a relatively underexplored area within the burgeoning field of nonaqueous redox flow batteries (NAqRFBs). Here, we investigate the effect of elevated temperature on the performance of nonaqueous redox electrolytes and associated flow cells. Using a model compound, N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT), in a propylene-carbonate-based electrolyte, we experimentally measure the temperature dependence of relevant physicochemical properties (i.e., electrolyte conductivity, viscosity, diffusivity) and electrochemical characteristics (i.e., chemical and electrochemical reversibility) across a temperature range of 30 °C to 70 °C. We then perform flow cell studies, finding that while ohmic and mass transport resistances decrease significantly with increases in temperature for the MEEPT/MEEPT +· redox couple, accessible electrolyte capacity gradually reduces at temperatures > 50 °C. Ex-situ, post-test characterization using microelectrode voltammetry suggests that this capacity fade is due to instability of the MEEPT radical cation. Finally, using MEEPT as a posolyte and a model viologen negolyte (bis(2-(2-methoxyethoxy)ethyl)viologen), we assemble a full cell and perform polarization analyses, observing a 2× increase in the peak power density when the operating temperature is increased from 30 °C to 70 °C. Broadly, this work highlights opportunities for systematic engineering of nonaqueous electrolytes and flow cells for higher power operation at elevated temperatures.

Electrochemistry↗

DOE OSTI2024

Structural Trends and Vibrational Analysis of N,N,N′,N′−Tetramethylmalonamide Complexes Across the Lanthanide Series

Fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining chemical behavior of rare-earth metals in complex liquid-liquid extraction processes, which in turn affects the distribution ratios and efficacy of separations as a whole. In this work, we explore the structural trends between the lanthanides and a neutral N,N,N',N'-tetramethylmalonamide (TMMA) ligand within four isolated families of solid-state compounds: Ln(trans-TMMA) 2 (NO 3 ) 3 Ln=La-Nd, Sm; Ln(cis-TMMA) 2 (NO 3 ) 3 Ln=Eu-Tb, Er; [Ln(TMMA) 3 (NO 3 ) 2 ][Ln(TMMA)(NO 3 ) 4 ] Ln=Dy-Tm; Ln(Κ 2 -TMMA)(iPrOH)(NO 3 ) 3 and Ln(Κ 1 -TMMA)(Κ 2 -TMMA)(NO 3 ) 3 Ln=Yb, Lu. Moving across the lanthanide series, we note the formation of both discrete charge-neutral complexes, as well as charged molecular anion-cation pairs, with variations in spatial ligand arrangement, coordination numbers, and ligand denticities. IR and Raman spectroscopy paired with DFT frequency calculations were used for an in-depth investigation of vibrational modes unique to each structural family. The collection of isolated model compounds was also discussed in the context of liquid-liquid separations based on reported distribution ratios from malonamide extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

An In Situ , Automated High-Explosives Aging Method Utilizing Two-Dimensional Gas Chromatography–Mass Spectrometry

Understanding chemical changes that occur in high explosives as they age is of great importance to the safe employment and storage of these compounds. Traditional methods of aging high explosives even under accelerated aging conditions are time intensive with durations on the order of months to years. The nature of traditional aging analyses reduces each sample to a snapshot data point often separated widely in time, requiring many assumptions as to how the degradation products develop. Further complicating matters, several analytical techniques are typically employed for each sample analysis in order to ascertain an entire picture of the decomposition pathways. To address these shortcomings with existing methods, a new method of accelerated aging of high explosives utilizing comprehensive two-dimensional gas chromatography coupled to high-resolution mass spectrometry (GC × GC-HRMS) was developed using 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) as a model compound for method development. This in situ automated method reduces the time scale of aging to a matter of hours using the inlet of the GC × GC as the aging vessel. GC × GC in combination with HRMS allowed for the collection of both evolved gases and other decomposition products produced during the entire aging process in real time with HRMS providing far greater certainty in identification of explosives aging products. Additionally, this method allowed for a higher throughput of samples with greatly simplified sample preparation. Chemometric analysis of the GC × GC-HRMS data set via the alteration analysis (ALA) enabled discovery of statistically significant chemical changes providing insight into the variation of decomposition pathways with varying aging temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗