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DOE OSTI2020

Facile Fabrication of Hierarchical MOF–Metal Nanoparticle Tandem Catalysts for the Synthesis of Bioactive Molecules

Multifunctional metal–organic frameworks (MOFs) that possess permanent porosity are promising catalysts in organic transformation. Herein, we report the construction of a hierarchical MOF functionalized with basic aliphatic amine groups and polyvinylpyrrolidone-capped platinum nanoparticles (Pt NPs). The postsynthetic covalent modification of organic ligands increases basic site density in the MOF and simultaneously introduces mesopores to create a hierarchically porous structure. The multifunctional MOF is capable of catalyzing a sequential Knoevenagel condensation–hydrogenation–intramolecular cyclization reaction. The unique selective reduction of the nitro group to intermediate hydroxylamine by Pt NPs supported on MOF followed by intramolecular cyclization with a cyano group affords an excellent yield (up to 92%) to the uncommon quinoline N-oxides over quinolines. The hierarchical MOF and polyvinylpyrrolidone capping agent on Pt NPs synergistically facilitate the enrichment of substrates and thus lead to high activity in the reduction–intramolecular cyclization reaction. The bioactivity assay indicates that the synthesized quinoline N-oxides evidently inhibit the proliferation of lung cancer cells. Finally, our findings demonstrate the feasibility of MOF-catalyzed direct synthesis of bioactive molecules from readily available compounds under mild conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Heterogeneous Diels–Alder tandem catalysis for converting cellulose and polyethylene into BTX

Producing biomass-derived aromatic hydrocarbons via controllable Diels–Alder reactions is a promising approach to recover energy and chemicals from waste streams. A tandem Diels–Alder catalysis consisting of SAPO-34 and Fe/HZSM-5 (stacked catalysis or mixed catalysis) was evaluated for thermochemical conversion of cellulose and polyethylene blends into benzene, toluene, and xylenes (BTX). Aromatization catalyst type significantly affected the activity of tandem catalysis, and the BTX obtained from the HZSM-5 stacked catalysis was ~2.3 times higher than that of the USY stacked one. An introduction of Fe active promoters into HZSM-5 increased the Lewis to Brønsted acid sites molar ratio (L/B) from 0.4 to 4.1. The comparison between Fe/HZSM-5 stacked catalysis and parent HZSM-5 single catalysis indicated that the former was more effective for BTX production, obtaining a nearly two-fold increase in yield with a high selectivity of 82.8%. A close proximity between Fe/HZSM-5 and SAPO-34 in the mixed catalysis increased the BTX enhancement to 1.8. A synergistic effect was provided by the coordination of Lewis and Brønsted acid sites in the Fe/HZSM-5 mixed catalysts for facilitating BTX generation, achieving a maximum of 25.9% at a Fe/HZSM-5 to SAPO-34 mass ratio of 1:1 with a theoretical L/B of 7.2. Finally, this work provides a sustainable strategy to produce biomass-derived aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

In-flight production of an isomeric beam of 16 N

In this work, an in-flight beam of 16 N was produced via the single-neutron adding ($\textit{d,p}$) reaction in inverse kinematics at the recently upgraded Argonne Tandem Linear Accelerator System (ATLAS) in-flight system. The amount of the 16 N beam which resided in its excited 0.120 MeV $J^\pi$ = 0 – isomeric state (T 1/2 ≈ 5 μs) was determined to be 40(5)% at a reaction energy of 7.9(3) MeV/$\textit{u}$, and 24(2)% at a reaction energy of 13.2(2) MeV/$\textit{u}$. The isomer measurements took place at an experimental station ≈ 30 m downstream of the production target and utilized an Al beam-stopping foil and a HPGe Clover detector. Composite 16 N beam rate determinations were made at the experimental station and the focal plane of the Argonne in-flight radioactive ion-beam separator (RAISOR) with Si ΔE-E telescopes. A Distorted Wave Born Approximation (DWBA) approach was coupled with the known spectroscopic information on 16 N in order to estimate the relative 16 N isomer yields and composite 16 N beam rates. In addition to the observed reaction-energy dependence of the isomer fraction, a large sensitivity to the angular acceptance of the recoils was also observed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2026

Coupling of high-resolution mass spectrometer and photosynthesis system for comprehensive leaf volatile metabolite profiling

Background Leaf-level biogenic volatile organic compounds (BVOCs) emissions represent a major source of organic gases in the atmosphere, influencing both climate and air quality. These emissions are strongly driven by environmental perturbations, which affect individual plant- to ecosystem-level processes. Uncovering all the BVOCs and understanding how their emissions respond to altered environmental conditions provide critical insights into vegetation-driven changes in atmospheric chemistry. We developed a tandem instrumentation setup that integrates a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) with parts-per-trillion detection limits and a photosynthetic infrared gas exchange system for the untargeted survey of all the BVOCs. This novel system enables simultaneous, real-time monitoring of BVOC emissions and photosynthetic parameters at the leaf level, offering new opportunities to disentangle the physiological and environmental drivers of VOC release. Furthermore, we established the VOC Analysis and Processing Optimization Resource (VAPOR), an open-access software tool designed for rapid data post-processing and the analysis of the variability of hundreds of BVOCs. We assessed the performance of the tandem system under varying background conditions, using standard gas mixtures and a range of environmental factors. Results Blank emissions were substantially lower for major BVOCs (e.g., isoprene) compared to those observed in plant emissions. Despite this, the observation of background-level VOCs highlights the importance of routinely acquiring and accounting for blank measurements in analyses using the coupled instrumentation. Introduction of known VOC concentrations to the system demonstrated a linear response across different compounds with varying molecular compositions, indicating minimal gas loss regardless of chemical moieties within the coupled instrumentation. We applied the optimized system to investigate the physiological mechanisms driving BVOC emissions across different genotypes of poplar and pennycress. The high mass resolution capabilities of the PTR-ToF-MS, coupled with comprehensive VAPOR-driven data analysis, enabled the identification of several important BVOCs, including methanol and methanethiol; these BVOCs displayed substantial variation across pennycress genotypes and showed concentrations ~ 100–350% higher than the blank. Moreover, isoprene emissions varied significantly among poplar genotypes grown in different potting media. Conclusions Tandem instrumentation offers a powerful tool for profiling volatile molecular markers and elucidating their genetic and environmental underpinnings. This approach enhances our ability to predict BVOC emissions in response to genotype by environmental interactions and contributes to a deeper understanding of vegetation responses to environmental changes.

Biogenic volatile organic compounds↗

DOE OSTI2024

High-throughput reaction discovery for Cs–Pb–Br nanocrystal synthesis

High-throughput reaction discovery is necessary to understand complex reaction spaces for inorganic nanocrystal synthesis. Here, we implemented a high-throughput continuous flow millifluidic reactor to perform reaction discovery for Cs–Pb–Br nanocrystal synthesis using a ligand assisted reprecipitation (LARP)-type approach. 3D-printed flow resistors enable the screening of up to 16 different mixing ratios within a single 90 s run, allowing for >270 different precursor concentration ratios to be quickly tested to explore the phase space that results in CsPbBr 3 , Cs 4 PbBr 6 , a biphasic mixture, or no product. To construct a full phase map from these high-throughput experiments, a neural network was trained and validated to predict the product composition (~500 000 points in precursor concentration space). The phase map predicts product composition/phase as a function of Cs–Pb–Br feed ratio. As a result, this approach demonstrates how high-throughput flow chemistry can be used in tandem with machine learning to rapidly explore nanocrystal reaction spaces in flow.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2006

Electron-Impact Ionization and Dissociative Ionization of Biomolecules

It is well recognized that secondary electrons play an important role in radiation damage to humans. Particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. Our study of electron-impact ionization of DNA fragments uses the improved binary-encounter dipole model and covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3(sup prime)- and C5 (sup prime)-deoxyribose-phospate cross sections, differing by less than 5%. Investigation of tandem double lesion initiated by electron-impact dissociative ionization of guanine, followed by proton reaction with the cytosine in the Watson-Crick pair, is currently being studied to see if tandem double lesion can be initiated by electron impact. Up to now only OH-induced tandem double lesion has been studied.

Huo, Winifred M.↗

DOE OSTI2022

Decay spectroscopy of the blocked fission product 130 $\mathrm{I}$

We report numerous applications rely on the identification and quantification of fission products with the activation technique, where γ-rays emitted in the decay are used to estimate the initial activity of the radionuclide of interest. 130 I is a so-called blocked fission product, which can be produced only directly through fission, a property that makes it particularly attractive for nuclear forensics. A source of 130 I was produced using a (p,n) reaction on enriched 130 Te at the Brookhaven Tandem Van de Graaff and its decay was studied with Gammasphere at Argonne National Laboratory. Two new levels were identified, and over 25 transitions were added, removed or re-placed in the level scheme, with intensity measurements made down to I γ = 0.00066 per 100 decays. The uncertainty on the intensities of the strongest transitions, those that are commonly used to quantify the activity of the radionuclide, was improved by a factor of 2 compared to the previous best assessment and discrepancies in the literature values were resolved. A detailed angular correlation analysis further permitted the determination of a number of spin assignments for excited levels and mixing ratios for γ-ray transitions

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2020

Synthesis of α,β‐ and β‐Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

Abstract We report a reaction platform for the synthesis of three different high‐value specialty chemical building blocks starting from bio‐ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde‐containing stream active for the production of C 4 aldehydes via base‐catalyzed aldol‐condensation. Then, the resulting C 4 adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β‐hydroxy acid (3‐hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β‐dihydroxy acid (2,3‐dihydroxybutanoic acid). Crotonic acid, 3‐hydroxybutanoic acid, and 2,3‐dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl‐co‐unsaturated acids resins, pharmaceutics, and bio‐degradable/ ‐compatible polymers, respectively.

Santhanaraj, Daniel↗

DOE OSTI2020

Synthesis of α,β‐ and β‐Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

Santhanaraj, Daniel↗

DOE OSTI2025

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Abstract Polyolefin waste is the largest polymer waste stream that could potentially serve as an advantageous hydrocarbon feedstock. Upcycling polyolefins poses significant challenges due to their inherent kinetic and thermodynamic stability. Traditional methods, such as thermal and catalytic cracking, are straightforward but require temperatures exceeding 400 °C for complete conversion because of thermodynamic constraints. We summarize and critically compare recent advances in upgrading spent polyolefins and model reactants via kinetic (and thermodynamic) coupling of the endothermic C─C bond cleavage of polyolefins with exothermic reactions including hydrogenation, hydrogenolysis, metathesis, cyclization, oxidation, and alkylation. These approaches enable complete conversion to desired products at low temperatures (<300 °C). The goal is to identify challenges and possible pathways for catalytic conversions that minimize energy and carbon footprints.

C-C cleavage↗

DOE OSTI2020

Search for the 1/2 + intruder state in 35 P

The excitation energy of deformed intruder states (specifically the 2p2h bandhead) as a function of proton number Z along N = 20 is of interest both in terms of better understanding the evolution of nuclear structure between spherical Ca 40 and the Island of Inversion nuclei, and for benchmarking theoretical descriptions in this region. At the center of the N = 20 Island of Inversion, the n p n h (where n = 2 , 4 , 6 ) neutron excitations across a diminished N = 20 gap result in deformed and collective ground states, as observed in Mg 32 . In heavier isotones, n p n h excitations do not dominate in the ground states but are present in the relatively low-lying level schemes. With the aim of identifying the expected 2 p 2 h x s 1 / 2 + state in P 35 , the only N = 20 isotone for which the neutron 2p2h excitation bandhead has not yet been identified, the S 36 ( d , He 3 ) P 35 reaction has been revisited in inverse kinematics with the HELical Orbit Spectrometer (HELIOS) at the Argonne Tandem Linac Accelerator System (ATLAS). While a candidate state has not been located, an upper limit for the transfer reaction cross section to populate such a configuration within a 2.5 to 3.6 MeV energy range provides a stringent constraint on the wave function compositions in both S 36 and P 35 .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2022

Activation of CO 2 by Actinide Cations (Th + , U + , Pu + , and Am + ) as Studied by Guided Ion Beam and Triple Quadrupole Mass Spectrometry

Reactions of CO 2 with Th+ have been studied using guided ion beam tandem mass spectrometry (GIBMS) and with An + (An + = Th + , U + , Pu + , and Am + ) using triple quadrupole inductively coupled plasma mass spectrometry (QQQ-ICP-MS). Additionally, the reactions ThO + + CO and ThO + + CO 2 were examined using GIBMS. Modeling the kinetic energy dependent GIBMS data allowed determination of bond dissociation energies (BDEs) for D o (Th + -O) and D o (OTh + -O) that are in reasonable agreement with previous GIBMS measurements. The QQQ-ICP-MS reactions were studied at higher pressures where multiple collisions between An + and the neutral CO 2 occur. As a consequence, both AnO + and AnO 2 + products were observed for all An + except Am + , where only AmO + was observed. Here, the relative abundances of the observed monoxides compared to the dioxides are consistent with previous reports of the AnO n + (n = 1, 2) BDEs. Comparison of the periodic trends of the group 4 transition metal, lanthanide (Ln), and actinide atomic cations in reactions with CO 2 (a formally spin-forbidden reaction for most M + ground states), and O 2 (a spin unrestricted reaction) indicate that spin conservation plays a minor role, if any, for the heavier An + metals. Further correlation of Ln + and An + + CO 2 reaction efficiencies with the promotion energy (E p ) to the first electronic state with two valence d-electrons (E p (5d 2 ) for Ln + and E p (6d 2 ) for An + ) indicates that the primary limitation in the activation of CO 2 is the energetic cost to promote from the electronic ground state of the atomic metal ion to a reactive state.

bond activation↗

DOE OSTI2026

The Cascade Effectiveness of 3-Terminal Tandem Photocathode Architectures as Applied to CO 2 Reduction

Cascade catalysis for photoelectrochemical CO 2 reduction (CO 2 R) decouples the overall reaction into sequential steps occurring on separately optimized catalysts (for example, Ag and Cu) between which an intermediate species such as CO is transferred. A 3-terminal tandem (3TT) photovoltaic architecture advantageously holds two different catalytic regions at different potentials under a single illumination source, but its overall efficiency is low. Using a stochastic reaction-diffusion model, we have examined 3TT photocathode design principles, focusing on the coupling of surface chemistry and transport of CO both inside the boundary layer and outward, into the bulk electrolyte. We find that ensuring that the lateral diffusion distance within the boundary layer is short compared to the boundary layer thickness and controlling bulk flow are key, with interdigitated designs showing an overall conversion efficiency improvement by 2 orders of magnitude compared to the side-by-side case without flow. These findings can be adapted for other cascaded architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Localized Heterogeneous Nucleation for Vapor‐Assisted Sequential Deposition of Metal Halide Perovskites

Vapor-assisted hybrid two-step deposition, which combines thermally evaporated inorganic layers with solution-processed organic halides to form halide perovskites, has emerged as a scalable and industry-compatible route for textured tandem photovoltaics. However, this process is often hindered by reaction-limited phase formation, particularly when compact, non-porous, and highly crystalline inorganic layers formed by thermal evaporation restrict subsequent conversion, resulting in incomplete reaction and pronounced depth-dependent heterogeneity. In this study, we introduce a strategy to regulate the inorganic precursor layer by incorporating localized heterogeneous nucleation sites. Sparsely distributed hydrophilic metal oxide species serve as effective nucleation centers during vapor deposition, enabling effective control over film morphology and crystal orientation from the early stages of growth. This tailored inorganic framework facilitates the subsequent incorporation of organic halides, alleviating reaction limitations and suppressing residual unreacted precursors. Consequently, the perovskite films exhibit improved stoichiometric uniformity and enhanced optoelectronic quality, enabling wide-bandgap perovskite solar cells with markedly improved performance and operational stability. This work provides important mechanistic insight into crystal growth engineering of vapor-deposited perovskite thin films.

nucleation↗

DOE OSTI2025

The balance of orbital overlap and orbital energy in the activation of methane by actinide cations: insights from inductively coupled plasma tandem mass spectrometry

The actinides present a unique challenge to chemical theory. The classical view of covalent bonding is driven by the extent of spatial overlap of valence orbitals. Modern theory has expanded assessments of covalency to include considerations of orbital energy degeneracy to assess orbital energy mixing between metal and ligand valence orbitals. Actinide–ligand (An–L) bonding has more recently been described as a balance between orbital overlap and orbital energy mixing, where 5f and L valence orbital overlap decreases while energy mixing between An 5f and L valence orbitals increases across the series. To test these existing views, we employed inductively coupled plasma tandem mass spectrometry to examine the kinetic energy dependences of reactions of actinide cations, Th + –Am + , with methane. Further, this is the first experimental report of the energy dependences of methane activation reactions involving the cations of Pa, Np, Pu, and Am and the first experimental determination of transuranic An + –D, An + –CD 2 , An + –CD 3 , and An + –CD bond dissociation energies. The correlation of the measured An + –CD 2 bond energies with E p (6d 2 ) indicates that An + 6d orbitals are the dominant contributors in the An + –CD 2 bonds. Close examination of the relative reactivities of An + offers additional support that the balance of classical and modern views of molecular bonding may lie between Np + and Pu + and that the increased reactivity of Th + –Np + may be attributed to the increased spatial extension of the 5f orbitals whereas covalent An + bond formation may be more driven by the decreasing energies of the 5f orbitals across the actinide series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Structure of the low-lying states in 99,101,103,105 Pd

In this work, the odd-mass 99-105 Pd nuclei were studied via 90-96 Zr( 12,13 C, xnγ) fusion/evaporation reactions. The beam was provided by the IFIN-HH Tandem accelerator at energies of approximately 50 MeV. Emitted gamma rays were detected by the hybrid multidetector system RoSphere. The structure of the low-lying excited states in 99-105 Pd and their gamma-decay pattern are discussed in the framework of the rigid triaxial rotor plus particle model, providing a reasonable description of the low-lying level energies, electromagnetic transition rates, and magnetic moments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1995

Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O

Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

Spectroscopy Deuterium Proton Ion Atmospheric Scie↗

DOE OSTI2022

Throughput Optimization of Molybdenum Carbide Nanoparticle Catalysts in a Continuous Flow Reactor Using Design of Experiments

Transition metal carbides (TMCs) have attracted significant attention because of their applications toward a wide range of catalytic transformations. However, the practicality of their synthesis is still limited because of the harsh conditions in which most TMCs are prepared. Recently, a solution-phase synthesis of phase-pure a-MoC1-x nanoparticles was presented. While this synthetic route yielded nanoparticles with exceptional catalytic performance, the reaction parameter space was not explored, and catalyst throughput was not optimized for scale-up. Continuous flow platforms coupled with statistical design of experiments (DoE) can provide a powerful method for understanding the reaction parameter space for optimizations. Here, we demonstrate the use of statistical DoE in tandem with response surface methodology for a parametric screening analysis to optimize the throughput of a MoC1-x nanoparticle synthesis utilizing a millifluidic flow reactor. A full factorial design was implemented to evaluate four input variables (reaction temperature, flow rate, solvent fraction of oleylamine, and precursor concentration) that carry statistically significant effects on three responses (throughput, residence time, and isolated yield). A Doehlert matrix was implemented to investigate each significant variable at a higher number of levels to optimize throughput. Our results give a nonintuitive set of experimental conditions that resulted in an optimized throughput of 2.2 g h-1. This translates to a 50-fold increase in throughput compared to the previously reported batch method. The catalytic performance of the MoC1-x nanoparticles produced under optimized throughput was demonstrated in the CO2 hydrogenation reaction. This DoE screening analysis and throughput optimization of MoC1-x synthesis open the door to an increased feasibility for scale-up.

design of experiments↗