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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Catalytic Approaches to C–O Activation in Biorenewable Feedstocks

The carbon present in biomass (the largest renewable source on the planet) continues to tempt us as a possible replacement for the carbon we currently obtain from fossil fuels. As we have recently reviewed, the challenges of extracting chemically useful feedstocks from biorenewables, and, especially, cellulosics, is largely under-developed relative to the maturity of the technologies for deriving industrially useful chemicals from petroleum. This ultimately boils down to problems in functionalization catalysis (for oil) versus defunctionalization (for cellulosics). The technology gap for achieving the selective defunctionalization of cellulosic feedstocks is much larger than it is for petroleum functionalization. This assessment suggests that the problem is not that bio-renewable feedstocks are fundamentally flawed from an economic and chemical sustainability perspective, but that we lack the technologies for deoxygenating cellulosic to more valuable chemicals. Bozell and Petersen have argued that integrated biorefineries will require a suite of products for viability (in analogy to an integrated petroleum refinery). These products will range from low-value high-volume energy related products (i.e. fuels) to high-value low-volume compounds focused on specialty markets and pharmaceuticals. The latter, although less impactful in terms of volume, is a critical economic component of the future integrated biorefinery. Our review was stimulated by their assessment of the state of the biorefinery and focused on the available chemistries for achieving low-volume high-value outcomes. To help fill this technology gap, we seek new catalytic technologies for synthesizing high-value chemicals from cellulosics and take the view that the inherent chirality of C 6 O 6 feedstocks will provide valuable materials for specialty and pharmaceutical applications, but only if one can achieve site-selective reactions that don’t denude the stereochemistry inherent to the sugars. Eliminative methods are less desirable as this deoxygenation scheme removes multiple stereocenters. The research plan outlined herein seeks methods for site-selective deoxygenation reactions that lead to high value specialty/pharma products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Production of carotenoids from aromatics and pretreated lignocellulosic biomass by Novosphingobium aromaticivorans

ABSTRACT Carotenoids are lipophilic compounds found in the membranes of various organisms. Individual carotenoids are also commodity chemicals, produced industrially for use as food additives, nutritional supplements, cosmetics, and pharmaceuticals. The alphaproteobacterium Novosphingobium aromaticivorans has previously been established as a potential platform microbe for converting aromatic compounds derived from lignocellulosic plant biomass into valuable extracellular products. Here, we show that N. aromaticivorans DSM 12444 cells naturally produce the carotenoid nostoxanthin, and we construct a set of gene deletion mutants that accumulate β-carotene, lycopene, or zeaxanthin, which are predicted intermediates in nostoxanthin biosynthesis as well as commodity chemicals. We also show that a mutant strain heterologously expressing a CrtW protein accumulates the carotenoid astaxanthin. When grown on vanillate as the carbon source, we find that the levels of carotenoids are not significantly affected by O 2 concentration in the tested range of 5% to 21% O 2 . We also show that these carotenoids are produced at comparable levels when strains are grown in liquor from alkaline pretreated sorghum biomass [sorghum alkaline pretreatment liquor (APL)], which contains a mixture of aromatics. Finally, we construct strains that produce zeaxanthin, β-carotene, or astaxanthin concurrently with 2-pyrone-4,6-dicarboxylic acid, a potential building block for biodegradable polymers, when grown in sorghum APL. Combined, our results show that N. aromaticivorans can simultaneously produce valuable intracellular and extracellular commodities when grown in the presence of either pure aromatics or pretreated lignocellulosic biomass. IMPORTANCE There is economic and environmental interest in generating commodity chemicals from renewable resources, such as lignocellulosic biomass, that can substitute for chemicals derived from fossil fuels. The bacterium Novosphingobium aromaticivorans is a promising microbial platform for producing commodity chemicals from lignocellulosic biomass because it can produce these from compounds in pretreated lignocellulosic biomass, which many industrial microbial catalysts cannot metabolize. Here, we show that N. aromaticivorans can be engineered to produce several valuable carotenoids. We also show that engineered N. aromaticivorans strains can produce these lipophilic chemicals concurrently with the extracellular commodity chemical 2-pyrone-4,6-dicarboxylic acid when grown in a complex liquor obtained from alkaline pretreated lignocellulosic biomass. Concurrent microbial production of valuable intra- and extracellular products can increase the economic value generated from the conversion of lignocellulosic biomass-derived compounds into commodity chemicals and facilitate the separation of water- and membrane-soluble products.

09 BIOMASS FUELS↗
DOE OSTI2023

Pickaxe: a Python library for the prediction of novel metabolic reactions

Abstract Background Biochemical reaction prediction tools leverage enzymatic promiscuity rules to generate reaction networks containing novel compounds and reactions. The resulting reaction networks can be used for multiple applications such as designing novel biosynthetic pathways and annotating untargeted metabolomics data. It is vital for these tools to provide a robust, user-friendly method to generate networks for a given application. However, existing tools lack the flexibility to easily generate networks that are tailor-fit for a user’s application due to lack of exhaustive reaction rules, restriction to pre-computed networks, and difficulty in using the software due to lack of documentation. Results Here we present Pickaxe, an open-source, flexible software that provides a user-friendly method to generate novel reaction networks. This software iteratively applies reaction rules to a set of metabolites to generate novel reactions. Users can select rules from the prepackaged JN1224min ruleset, derived from MetaCyc, or define their own custom rules. Additionally, filters are provided which allow for the pruning of a network on-the-fly based on compound and reaction properties. The filters include chemical similarity to target molecules, metabolomics, thermodynamics, and reaction feasibility filters. Example applications are given to highlight the capabilities of Pickaxe: the expansion of common biological databases with novel reactions, the generation of industrially useful chemicals from a yeast metabolome database, and the annotation of untargeted metabolomics peaks from an E. coli dataset. Conclusion Pickaxe predicts novel metabolic reactions and compounds, which can be used for a variety of applications. This software is open-source and available as part of the MINE Database python package ( https://pypi.org/project/minedatabase/ ) or on GitHub ( https://github.com/tyo-nu/MINE-Database ). Documentation and examples can be found on Read the Docs ( https://mine-database.readthedocs.io/en/latest/ ). Through its documentation, pre-packaged features, and customizable nature, Pickaxe allows users to generate novel reaction networks tailored to their application.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Light Hydrocarbon Separations Using Porous Organic Framework Materials

Light hydrocarbons (C 1 –C 3 ) are used as basic energy feedstocks and as commodity organic compounds for the production of many industrially necessary chemicals. Due to the nature of the raw materials and production processes, light hydrocarbons are generated as mixtures, but the high-purity single-component products are of vital importance to the petrochemical industry. Consequently, the separation of these C 1 –C 3 products is a crucial industrial procedure that comprises a significant share of the total global energy consumption per year. As a complement to traditional separation methods (distillation, partial hydrogenation, etc.), adsorptive separations using porous solids have received widespread attention due to their lower energy costs and higher efficiency. Extensive research has been devoted to the use of porous materials such as zeolites and metal-organic frameworks (MOFs) as solid adsorbents for these key separations, owing to the high porosity, tunable pore structures, and unsaturated metal sites present in these materials. Recently, porous organic framework (POF) materials composed of organic building blocks linked by covalent bonds have also shown excellent properties in light hydrocarbon adsorption and separation, sparking interest in the use of these materials as adsorbents in separation processes. In this Minireview we summarize the recent advances in the use of POFs for light hydrocarbon separations, including the separation of mixtures of methane/ethane, methane/propane, ethylene/ethane, acetylene/ethylene, and propylene/propane, while highlighting the relationships between the structural features of these materials and their separation performances. Finally, the difficulties, challenges, and opportunities associated with leveraging POFs for light hydrocarbon separations are discussed to conclude the review.

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

Nanoscale Examination of Chemical and Enzymatic Degradation of Plant Cell Walls

Lignocellulosic materials present the largest source of biomass for biotechnology and green energy. This study aimed at better understanding the cell wall disintegration mechanisms relevant for the biochemical conversion of biomass to carbohydrates. Herein, we examined nanoscale changes in cell wall structure and composition upon industrially relevant chemical and enzymatic treatments to achieve the desired level of breakdown. One treatment involved hydrogen peroxide and acetic acid to remove lignin. Another modification used the cellulase enzyme for cell wall degradation. Band excitation contact resonance atomic force microscopy was used to visualize and mechanically characterize cell wall layers. After cellulase treatments, we detected microcracks across the cell wall. Wet-chemical, Fourier-transform infrared and Raman spectroscopic analyses confirmed the removal of lignin and extractives through acid bleaching, while the enzymatic treatment minimally affected the biopolymer composition. Delignification resulted in cell wall delamination and reduced stiffness. In conclusion, X-ray diffraction revealed changes in cellulose structure and crystallinity.

Soini, Steven A. [Florida Atlantic Univ., Boca Rat↗
DOE OSTI2020

Manufacturing Process Design of a Micro-Scale Liquid-Liquid Extractor and Multi-phase Separator

Advances in process innovation within the chemical process industry are impeded by the cost of producing new innovative components. In this paper, various manufacturing process routes were evaluated for scaling up a micro-scale liquid-liquid extractor and multi-phase separator capable of separating immiscible phases that are used for the extraction of a chemical product into a lower boiling point solvent to make downstream distillation easier. A manufacturing process design methodology was used to evaluate both photochemical machining and binder jetting as a means for producing the micropost arrays within the separator. Cost curves show that for a 0.3 mm deep micropost array, photochemical machining was found to be much cheaper than binder jetting. However, because binder jetting processes enable microposts with over 13 times higher depth-to-width aspect ratios, binder jetting was found to decrease the overall costs of the extractor/separator by more than half for a 500 barrel per day plant, with breakeven as low as 15 barrels per day. These economics were confirmed by building extractor/separator plates and characterizing them dimensionally and functionally. The binder jet plates were found to perform better than photochemical plates leading to the complete separation of the organic phase from water. The utilization of slower sintering cycles combined with surface grinding provided acceptable dimensional tolerances for the binder jet plates. Using pressurized air during depowdering improved the economics for the binder jetting process.

42 ENGINEERING↗
DOE OSTI2024

Hazards and Probabilistic Risk Assessments of Advanced Nuclear Reactors Coupled with Industrial Facilities

This report provides a roadmap and tool kit for site specific risk assessments across a broad range of industrial customers co-located with advanced nuclear power plants (ANPP) that are not currently built and operating in the U.S. This report builds upon the body of work sponsored by the Department of Energy (DOE) Integrated Energy Systems Pathway that has produced industrial requirements studies and techno-economic assessments on the topics of feasibility of ANPP supported industrial processes. This report also leverages the DOE Light Water Reactor Sustainability (LWRS) program that has presented hazards assessment and generic probabilistic risk assessments (PRAs) for the addition of a heat extraction system (HES) to light-water reactors (LWRs) co-located with hydrogen production facilities. Many of the hazard assessments and risk assessments performed for the LWRS report are agnostic to whether the nuclear reactor is an ANPP or were adapted to the ANPP focus. The report performs hazards assessments to include industrial facilities: an oil refinery, a methanol plant, a synthetic fuel (synfuel) plant, the production of synthetic gas (syngas) as part of the methanol and synfuel plants, wood pulp and paper mills, and hydrogen production. Hydrogen production facilities are assessed in depth through prior reports in the LWRS program and the results are leveraged in this report. All these facilities are specified through industrial process and requirements research performed by national laboratories, universities, and interaction with industry. Many of the processes used in this report are pre-conceptual designs to use for decarbonization of the current technology facilities. A process of failure modes and effects analysis (what can go wrong) and accidentology (what has historically gone wrong) was used to determine the hazards presented to the nuclear power plant by the addition of the HES and the industrial customer. Chemical properties of feedstocks and products are summarized as part of the hazards assessment. Example analysis procedures are provided for each of the hazard types identified. These deterministic analyses can be used to assess adherence to licensing criteria. They can also be used to meet other safety goals like protection of the public, workers, or industrial facility equipment. A modular high temperature gas-cooled reactor (MHTGR) PRA only existing on paper was modeled and verified in modern PRA software. This will provide a tool for representative ANPP probabilistic analyses for future research.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Hazards and Probabilistic Risk Assessments of a Light-Water Reactor Coupled with Industrial Facilities

This report provides a roadmap and toolkit for site-specific risk assessments across a broad range of industrial customers co-located with nuclear power plants (NPPs). This report builds upon the body of work sponsored by the Department of Energy (DOE) Light-Water Reactor Sustainability (LWRS) Flexible Plant Operation and Generation Pathway that presented hazards assessment and generic probabilistic risk assessments (PRAs) for the addition of a heat extraction system (HES) to light-water reactors co-located with hydrogen production facilities. The report expands the hazards assessments to include other industrial facilities: an oil refinery, a methanol plant, a synthetic fuel (synfuel) plant, the production of synthetic gas (syngas) as part of the methanol and synfuel plants, and wood pulp and paper mills. All these facilities are specified through industrial process and requirements research performed by national laboratories, universities, and interaction with industry. Many of the processes used in this report are pre-conceptual designs to use for decarbonization of the current technology facilities. A process of failure modes and effects analysis (what can go wrong) and accidentology (what has historically gone wrong) was used to determine the hazards presented to the NPP by the addition of the HES and the industrial customer. Chemical properties of feedstocks and products are summarized as part of the hazards assessment. Example analysis procedures are provided for each of the hazard types identified. These deterministic analyses can be used to assess adherence to licensing criteria. They can also be used to meet other safety goals like protection of the public, workers, or industrial facility equipment. The probabilistic analysis consisted of three sizes of HESs modeled in a PRA to assess the impact on the initiating events (IE) and results of the PRA. The PRA results conclude that the resulting increases in IE frequencies are below the limits required for small changes to existing NPPs under 10 CFR 50.59.

08 HYDROGEN↗
DOE OSTI2023

Imprinting and Reproductive Health: A Toxicological Perspective

This overview discusses the role of imprinting in the development of an organism, and how exposure to environmental chemicals during fetal development leads to the physiological and biochemical changes that can have adverse lifelong effects on the health of the offspring. There has been a recent upsurge in the use of chemical products in everyday life. These chemicals include industrial byproducts, pesticides, dietary supplements, and pharmaceutical products. They mimic the natural estrogens and bind to estradiol receptors. Consequently, they reduce the number of receptors available for ligand binding. This leads to a faulty signaling in the neuroendocrine system during the critical developmental process of ‘imprinting’. Imprinting causes structural and organizational differentiation in male and female reproductive organs, sexual behavior, bone mineral density, and the metabolism of exogenous and endogenous chemical substances. Several studies conducted on animal models and epidemiological studies provide profound evidence that altered imprinting causes various developmental and reproductive abnormalities and other diseases in humans. Altered metabolism can be measured by various endpoints such as the profile of cytochrome P-450 enzymes (CYP450’s), xenobiotic metabolite levels, and DNA adducts. The importance of imprinting in the potentiation or attenuation of toxic chemicals is discussed.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Linker Vacancy Engineering of a Robust ftw–type Zr–MOF for Hexane Isomers Separation

Discrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or tailored pore surface functionality are crucial to achieve high-efficiency separation. Metal-organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw-type Zr-based MOF structure, HIAM-410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr 6 cluster and pyrene-1,3,6,8-tetracarboxylate (ptc 4– ). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X-ray diffraction data, aided by low-dose high-resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO-66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post-synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. As a result, the restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.

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

Results of an interlaboratory study on the working curve in vat photopolymerization II: Towards a standardized method

The working curve measurement in photopolymer additive manufacturing is a ubiquitous measure of the cure depth of a printing resin as a function of radiant exposure of light. The fit parameters from this measurement (the depth of light penetration D p and the critical exposure E c ) are used to evaluate and report a resin’s printability, optimize processing parameters, and inform print and resin quality control. Despite its widespread use, the working curve lacks a standard measurement method. Here, following up on our paper “Results of an Interlaboratory Study on the Working Curve in Vat Photopolymerization” from last year, an interlaboratory study on the working curve was performed using calibrated, reproducible, bandpass filtered light sources. With these light sources, the variability between labs in measured working curves was dramatically reduced from the initial interlaboratory study. Aggregate data from this experiment produced reliable D p and E c measurements at 385 nm of 39.2 ± 3.7 µm and 12.3 ± 3.0 mJ cm −2 , respectively. At 405 nm the values of D p and E c are 69.3 ± 3.8 µm and 17.9 ± 2.3 mJ cm −2 , respectively. The results are agnostic to the thickness measurement tool utilized by participants, ensuring broad applicability across laboratories. We also tested the generalizability of the proposed method of using a filtered light source by filtering a commercial 405 nm light source and obtaining a working curve in agreement with the aggregate data from the interlaboratory study. This interlaboratory study provides a basis for a documentary standard for the working curve, so that the entire photopolymer additive manufacturing industry can share reproducible and interoperable working curve data.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Gradient synthesis of carbon quantum dots and activated carbon from pulp black liquor for photocatalytic hydrogen evolution and supercapacitor

Black liquor (BL) is a by-product of the chemical pulping industry and is mainly used as a low-value fuel; however, its potential to produce high-value products has not been fully exploited. In this study, a green and simple strategy is reported for the gradient production of Na + -functionalized carbon quantum dots (Na + -CQDs) for the first time, N and S co-doped CQDs (N/S-CQDs), and N and S co-doped KOH-activated carbon (N/S-KAC) from BL by dialysis, hydrothermal carbonization and activation-carbonization, respectively. Due to the good electron trapping ability, photoluminescence and promising up-conversion luminescence of CQDs, the hydrogen evolution efficiency of Na + -CQDs/TiO 2 and N/S-CQDs/TiO 2 photocatalysts was improved by 2.45 and 1.46 times, respectively, compared with pure TiO 2 . N/S-KAC with a high specific surface area of 2294 m 2 g -1 provides an excellent specific capacitance of 253 F g -1 at 0.5 A g -1 and a promising energy density of 26.92 Wh kg -1 under a power density of 566 W kg -1 for the fabricated symmetrical supercapacitor. Moreover, the electrode material has good cycling stability with a capacitance retention of ~ 93.91% after 5000 cycles. In conclusion, this pathway provides a versatile and scalable approach for the construction and co-production of nanostructured materials, photocatalysts and energy storage devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Hybrid data-driven cement-stabilized soil design: An integration of machine learning, multi-objective optimization, and life cycle assessment

Soil stabilization is crucial in geotechnical engineering, yet conventional methods are often time-consuming, resource-intensive, and environmentally unsustainable. Despite growing interest in Machine Learning (ML) and optimization tools for mix design, few studies integrate these methods with decision-making techniques and environmental assessment to support practical implementation. This study proposes a hybrid data-driven framework for predicting strength, optimizing mix compositions, and evaluating environmental impacts via life cycle assessment of cement-stabilized soft soils. Six ML models were evaluated, and the top-performing eXtreme Gradient Boosting (XGB) model was further improved using the Grey Wolf Optimizer (GWO). The optimized XGB-GWO model, integrated with a polynomial cost function, served as the objective function in a multi-objective optimization problem solved via the Non-Dominated Sorting Genetic Algorithm II (NSGA-II), with final mix selection guided by the entropy-weighted TOPSIS method. Validation through a case study produced mix designs offering superior strength-cost trade-offs, with the optimal mix achieving 2243.2 kPa unconfined compressive strength and a 16.07 % reduction in carbon emissions compared to the highest-cost design. In conclusion, this study offers a sustainable, scalable approach to soil stabilization and supports informed decision-making in construction.

Life cycle assessment↗
DOE OSTI2022

Pore space partition of metal-organic frameworks for gas storage and separation

Pore space partition (PSP) concept is a synthetic design concept and can also serve as a structure analysis method useful for next-step synthetic planning and execution. PSP provides an integrated chemistry-topology-focused tool to design new materials platforms. While PSP is no less effective for making large-pore materials, the growing importance of small-molecule gas storage and separation for green-energy applications provides impetus for developing small-pore materials for which the PSP strategy is uniquely suited. Currently, the best embodiment of the PSP concept is the partitioned-acs (pacs) platform in which both fine or coarse adjustments to the building blocks have sparked a transformation of a prototype framework into a huge and continuously expanding family of chemically robust materials with controllable pore metrics and functionalities suitable for tailored applications. The pacs compositional diversity results from the platform’s intrinsic multi-module nature, geometric flexibility and tolerance towards individual module variations, and mutual structure-directing effects among various modules, all of which combine to enable the molecular-level uniform co-assemblies of chemical components rarely seen together elsewhere. Here, in this contribution, we present an overview of different pore space engineering methods and how different MOF materials have contributed to important advances in chemical stability, industrial gas storage and gas separation. In particular, we will focus on synthetic assembly of the pacs system, highlighting the differences of pacs materials from other MOF platforms and advantages of pacs materials in enhancing various MOF properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Characterization of aromatic acid/proton symporters in Pseudomonas putida KT2440 toward efficient microbial conversion of lignin-related aromatics

Pseudomonas putida KT2440 (hereafter KT2440) is a well-studied platform bacterium for the production of industrially valuable chemicals from heterogeneous mixtures of aromatic compounds obtained from lignin depolymerization. KT2440 can grow on lignin-related monomers, such as ferulate (FA), 4-coumarate (4CA), vanillate (VA), 4-hydroxybenzoate (4HBA), and protocatechuate (PCA). Genes associated with their catabolism are known, but knowledge about the uptake systems remains limited. In this work, we studied the KT2440 transporters of lignin-related monomers and their substrate selectivity. Based on the inhibition by protonophores, we focused on five genes encoding aromatic acid/H+ symporter family transporters categorized into major facilitator superfamily that uses the proton motive force. Furthermore, the mutants of PP_1376 (pcaK) and PP_3349 (hcnK) exhibited significantly reduced growth on PCA/4HBA and FA/4CA, respectively, while no change was observed on VA for any of the five gene mutants. At pH 9.0, the conversion of these compounds by hcnK mutant (FA/4CA) and vanK mutant (VA) was dramatically reduced, revealing that these transporters are crucial for the uptake of the anionic substrates at high pH. Uptake assays using 14 C-labeled substrates in Escherichia coli and biosensor-based assays confirmed that PcaK, HcnK, and VanK have ability to take up PCA, FA/4CA, and VA/PCA, respectively. Additionally, analyses of the predicted protein structures suggest that the size and hydropathic properties of the substrate-binding sites of these transporters determine their substrate preferences. Overall, this study reveals that at physiological pH, PcaK and HcnK have a major role in the uptake of PCA/4HBA and FA/4CA, respectively, and VanK is a VA/PCA transporter. This information can contribute to the engineering of strains for the efficient conversion of lignin-related monomers to value-added chemicals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Role of Silica Support in Phosphoric Acid Catalyzed Production of p -Xylene from 2,5-Dimethylfuran and Ethylene

p-Xylene is a commodity chemical of industrial importance for terephthalic acid production, for which renewable sourcing from naturally abundant lignocellulosic biomass is highly desired. Previous work demonstrated that phosphoric acid stabilized on siliceous zeolite supports (e.g., P-BEA, P-SPP) exhibits high selectivity toward p-xylene (>97%) from 2,5-dimethylfuran (DMF) and ethylene. However, the effect of the support and the contribution of heterogeneous versus homogeneous phosphoric acid on the observed catalytic behavior in the solvated reaction system have not been addressed. Here, we determine the phosphoric acid catalytic activity for DMF conversion and its selectivity to p-xylene when it is supported on a silica support as well as in the absence of a support. Specifically, phosphoric acid catalysis was studied in three different scenarios: (1) phosphoric acid was added in the liquid reaction mixture in the absence of any solid support, (2) phosphoric acid was added in the liquid reaction mixture along with inert silica support including siliceous zeolite (i.e., allowing for phosphoric acid–support assembly to proceed in the reaction mixture), and (3) phosphoric acid was first impregnated on the siliceous zeolite support and then the preassembled supported phosphoric acid catalyst was added in the liquid reaction mixture. We found that the reaction rate and selectivity to p-xylene are different in the above scenarios reflecting the effect of the solid support on the catalytic performance of phosphoric acid. In scenario 1, a low concentration of phosphoric acid (1.7 mM) in the absence of any solid support exhibited high selectivity to p-xylene (80% selectivity to p-xylene at 60% conversion of DMF), which decreased with increasing acid concentration. The selectivity to p-xylene and activity of phosphoric acid significantly increased by adding a silica support into the reaction system (scenario 2). Furthermore, this improvement was attributed to phosphoric acid partial association with the surface of the silica support under the reaction conditions (in situ catalyst assembly). Phosphoric acid predeposited on siliceous zeolite supports (e.g., P-BEA, P-SPP) synthesized via impregnation prior to the reaction (scenario 3) catalyzed the reaction heterogeneously without noticeable leaching and exhibited the highest activity and selectivity to p-xylene, suggesting an important role of the silica support and the need to ensure that phosphoric acid acts as a heterogeneous catalyst in order to accomplish selective conversion of DMF to p-xylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigating the Influence of Hexanuclear Clusters in Isostructural Metal–Organic Frameworks on Toxic Gas Adsorption

The efficient capture of toxic gases, such as ammonia (NH 3 ) and sulfur dioxide (SO 2 ), can protect the general population and mitigate widespread air pollution. Metal–organic frameworks (MOFs) comprise a tunable class of adsorbents with high surface areas that can meet this challenge by selectively capturing these gases at low concentrations. In this work, we explored how modifying the metal ions in the node of an isostructural MOF series from a transition metal to a lanthanide or actinide influences the electronic environment of the node-based active site. Next, we investigated the adsorption properties of each MOF toward the relatively basic NH 3 and relatively acidic SO 2 gases. Within the NU-907 family of MOFs, we found that Zr 6 -NU-907 exhibits the best uptake toward NH 3 at low pressures, while Th 6 -NU-907 demonstrates the best low-pressure performance for SO 2 adsorption. Here, tracking the infrared (IR) stretching frequency of the node-based μ 3 -OH groups provides insights into the electronegativity of the metal ion and suggests that the most electronegative metal ion (Zr) affords the node with the best NH 3 uptake at low pressures. In contrast, the Th 6 node contains additional coordinated water groups relative to the other M 6 nodes, which appears to yield the MOF with the greatest affinity for SO 2 uptake that occurs predominately through reversible physisorption interactions. Finally, in situ NH3 IR spectroscopic studies indicate that both NH 4 + and Lewis-bound NH 3 species form during adsorption. Combined, these results suggest that tuning the electronic properties and structure of the node-based active site in an MOF presents a viable strategy to change the affinity of an MOF toward toxic gases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗