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At least 145 records · Page 8

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

deLaRee, Ana B.↗

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

DeLaRee, Ana B.↗

Advances in catalytic production processes of biomass-derived vinyl monomers

Plastic industries currently source the majority of monomers from crude oil substances. Although we have witnessed a significant interest of companies in the utilization of sustainable feedstock materials for bio-based compound synthesis in the past decade, the transition to photosynthetic or chemosynthetic plant-based production in a circular carbon economy is largely slow due to complex biomass processing, costs and related reaction factors. The upgrade of the separated platform chemicals with a deeper supporting understanding of processes, models and a root–cause analysis about the underlying distribution challenges of engineered transformation mechanisms, catalyzed conversion pathways and selectivity would be beneficial to advance applied scientific development, bio-refining and manufacturing output amount. This review provides a summary, assessment and perspective for three important polymer-forming vinyl molecules, i.e. acrylic acid, methacrylic acid and styrene. These provide a backbone to produce acrylates, polystyrene, resins, rubbers, protective surface coatings, adhesives, textiles and other obtained copolymers. A succinct analytical overview on the thermo-catalytic intermediate routes for property-wise drop-in alternatives is presented. Sugars, acrolein, allyl alcohol, ethylbenzene, glycerol, 3-hydroxypropionic acid, isobutene, itaconic acid and lactic acid are considered as the main starting reactants. Catalysts span mixed metal oxides, silicates, native or impregnated zeolite frameworks (HBEA, HZSM, and MFI) and hetero-poly acids as well as homogeneous base hydroxides or platinum group metals, supported on carbon, alumina and sulfates. Finally, the article concludes with a brief state sum-up of the results, topics and opportunities for systematic future research or scaling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

A Donor–Acceptor [2]Catenane for Visible Light Photocatalysis

Colored charge-transfer complexes can be formed by the association between electron-rich donor and electron-deficient acceptor molecules, bringing about the narrowing of HOMO–LUMO energy gaps so that they become capable of harnessing visible light. In an effort to facilitate the use of these widespread, but nonetheless weak, interactions for visible light photocatalysis, it is important to render the interactions strong and robust. Furthermore, we employ a well-known donor–acceptor [2]catenane—formed by the mechanical interlocking of cyclobis(paraquat-p-phenylene) and 1,5-dinaphtho[38]crown-10—in which the charge-transfer interactions between two 4,4'-bipyridinium and two 1,5-dioxynaphthalene units are enhanced by mechanical bonding, leading to increased absorption of visible light, even at low concentrations in solution. As a result, since this [2]catenane can generate persistent bipyridinium radical cations under continuous visible-light irradiation without the need for additional photosensitizers, it can display good catalytic activity in both photo-reductions and -oxidations, as demonstrated by hydrogen production—in the presence of platinum nanoparticles—and aerobic oxidation of organic sulfides, such as l-methionine, respectively. This research, which highlights the usefulness of nanoconfinement present in mechanically interlocked molecules for the reinforcement of weak interactions, can not only expand the potential of charge-transfer interactions in solar energy conversion and synthetic photocatalysis but also open up new possibilities for the development of active artificial molecular shuttles, switches, and machines.

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NASA Tech Briefs, September 2007

Topics covered include; Rapid Fabrication of Carbide Matrix/Carbon Fiber Composites; Coating Thermoelectric Devices To Suppress Sublimation; Ultrahigh-Temperature Ceramics; Improved C/SiC Ceramic Composites Made Using PIP; Coating Carbon Fibers With Platinum; Two-Band, Low-Loss Microwave Window; MCM Polarimetric Radiometers for Planar Arrays; Aperture-Coupled Thin-Membrane L-Band Antenna; WGM-Based Photonic Local Oscillators and Modulators; Focal-Plane Arrays of Quantum-Dot Infrared Photodetectors; Laser Range and Bearing Finder With No Moving Parts; Microrectenna: A Terahertz Antenna and Rectifier on a Chip; Miniature L-Band Radar Transceiver; Robotic Vision-Based Localization in an Urban Environment; Programs for Testing an SSME-Monitoring System; Cathodoluminescent Source of Intense White Light; Displaying and Analyzing Antenna Radiation Patterns; Payload Operations Support Team Tools; Space-Shuttle Emulator Software; Soft Real-Time PID Control on a VME Computer; Analyzing Radio-Frequency Coverage for the ISS; Nanorod-Based Fast-Response Pressure-Sensitive Paints; Capacitors Would Help Protect Against Hypervelocity Impacts; Diaphragm Pump With Resonant Piezoelectric Drive; Improved Quick-Release Pin Mechanism; Designing Rolling-Element Bearings; Reverse-Tangent Injection in a Centrifugal Compressor; Inertial Measurements for Aero-assisted Navigation (IMAN); Analysis of Complex Valve and Feed Systems; Improved Path Planning Onboard the Mars Exploration Rovers; Robust, Flexible Motion Control for the Mars Explorer Rovers; Solar Sail Spaceflight Simulation; Fluorine-Based DRIE of Fused Silica; Mechanical Alloying for Making Thermoelectric Compounds; Process for High-Rate Fabrication of Alumina Nanotemplates; Electroform/Plasma-Spray Laminates for X-Ray Optics; An Automated Flying-Insect Detection System; Calligraphic Poling of Ferroelectric Material; Blackbody Cavity for Calibrations at 200 to 273 K; KML Super Overlay to WMS Translator; High-Performance Tiled WMS and KML Web Server; Modeling of Radiative Transfer in Protostellar Disks; Composite Pulse Tube; Photometric Calibration of Consumer Video Cameras; Criterion for Identifying Vortices in High- Pressure Flows; Amplified Thermionic Cooling Using Arrays of Nanowires; Delamination-Indicating Thermal Barrier Coatings; Preventing Raman Lasing in High-Q WGM Resonators; Procedures for Tuning a Multiresonator Photonic Filter; Robust Mapping of Incoherent Fiber-Optic Bundles; Extended-Range Ultrarefractive 1D Photonic Crystal Prisms; Rapid Analysis of Mass Distribution of Radiation Shielding; Modeling Magnetic Properties in EZTB; Deep Space Network Antenna Logic Controller; Modeling Carbon and Hydrocarbon Molecular Structures in EZTB; BigView Image Viewing on Tiled Displays; and Imaging Sensor Flight and Test Equipment Software.

Source record↗

N-Doped Graphene (N-G)/MOF(ZIF-8)-Based/Derived Materials for Electrochemical Energy Applications: Synthesis, Characteristics, and Functionality

In recent years, graphene-type materials originating from metal–organic frameworks (MOFs) or integrated with MOFs have exhibited notable performances across various applications. However, a comprehensive understanding of these complex materials and their functionalities remains obscure. While some studies have reviewed graphene/MOF composites from different perspectives, due to their structural–functional intricacies, it is crucial to conduct more in-depth reviews focusing on specific sets of graphene/MOF composites designed for particular applications. In this review, we thoroughly investigate the syntheses, characteristics, and performances of N-G/MOF(ZIF-8)-based/derived materials employed in electrochemical energy conversion and storage systems. Special attention is given to realizing their fundamental functionalities. The discussions are divided into three segments based on the application of N-G/ZIF-8-based/derived materials as electrode materials for batteries, electrodes for electrochemical capacitors, and electrocatalysts. As electrodes for batteries, N-G/MOF(ZIF-8) materials can mitigate issues like an electrode volume expansion for Li-ion batteries and the ‘shuttle effect’ for Li-S batteries. As electrodes for electrochemical capacitors, these materials can considerably improve the ion transfer rate and electronic conductivity, thereby enhancing the specific capacitance while maintaining the structural stability. Also, it was observed that these materials could occasionally outperform standard platinum-based catalysts for the electrochemical oxygen reduction reaction (ORR). The reported electrochemical performances and structural parameters of these materials were carefully tabulated in uniform units and scales. Through a critical analysis of the present synthesis trends, characteristics, and functionalities of these materials, specific aspects were identified that required further exploration to fully utilize their inherent capabilities.

Electrochemistry↗

Density Functional Tight Binding Insights into Plasmonic Silver–Platinum Nanoparticles and Alloys for Enhanced Photocatalysis

Developing accurate and efficient Slater-Koster (SK) tight-binding parameter sets is essential for quantum plasmonic studies of alloyed metal nanoparticles, as conventional time dependent density functional theory (TD-DFT) calculations are computationally prohibitive for larger clusters. In this work, we develop and validate density functional tight binding (DFTB) parameter sets for both ground state (GS-SK) and excited state (ES-SK) calculations to study the structural, electronic, and optical properties of silver (Ag), platinum (Pt), and Ag–Pt nanoalloys. Our investigation of the ground state properties demonstrates that the GS-SK parameters enable DFTB to closely reproduce the electronic structures of platinum clusters with diverse sizes and geometries – showing qualitative agreement with DFT for density of states (DOS) profiles and energy levels. The ES-SK parameters accurately describe excited-state properties compared to TD-DFT reference calculations, including the broad, featureless absorption profiles of Pt that are dominated by interband transitions. Using the ES-SK parameters within a real-time TD-DFTB framework, we compute size-dependent optical absorption spectra of Ag, Pt and Ag-Pt nanocubes containing up to 1099 atoms (size ∼4.18 nm). A detailed study of Ag–Pt and Pt-Ag core–shell nanoparticles shows quenching of the Ag plasmon resonance even at monolayer coverage for Ag-Pt, but not for Pt-Ag. We also show how to define submonolayer Ag-core Pt-shell cubic structures that have similar optical properties to those generated experimentally for much larger particles, which offers potential for describing plasmon-enhanced photocatalysis. Collectively, the GS-SK and ES-SK parameter sets provide an accurate, computationally efficient approach for modeling the complex optical and electronic behavior of noble–transition metal nanostructures and their alloys.

SPR↗

Invariant Molecular Representations for Heterogeneous Catalysis

Catalyst screening is a critical step in the discovery and development of heterogeneous catalysts, which are vital for a wide range of chemical processes. In recent years, computational catalyst screening, primarily through density functional theory (DFT), has gained significant attention as a method for identifying promising catalysts. However, the computation of adsorption energies for all likely chemical intermediates present in complex surface chemistries is computationally intensive and costly due to the expensive nature of these calculations and the intrinsic idiosyncrasies of the methods or data sets used. This study introduces a novel machine learning (ML) method to learn adsorption energies from multiple DFT functionals by using invariant molecular representations (IMRs). To do this, we first extract molecular fingerprints for the reaction intermediates and later use a Siamese-neural-network-based training strategy to learn invariant molecular representations or the IMR across all available functionals. Our Siamese network-based representations demonstrate superior performance in predicting adsorption energies compared with other molecular representations. Notably, when considering mean absolute values of adsorption energies as 0.43 eV (PBE-D3), 0.46 eV (BEEF-vdW), 0.81 eV (RPBE), and 0.37 eV (scan+rVV10), our IMR method has achieved the lowest mean absolute errors (MAEs) of 0.18 0.10, 0.16, and 0.18 eV, respectively. These results emphasize the superior predictive capacity of our Siamese network-based representations. The empirical findings in this study illuminate the efficacy, robustness, and dependability of our proposed ML paradigm in predicting adsorption energies, specifically for propane dehydrogenation on a platinum catalyst surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Adsorbate-Induced Structural Evolution of Iron Carbide Nanoparticles

Iron carbide (Fe x C y ) nanoparticles (NPs) are promising candidates for replacing platinum group metals in industrial applications, such as high-temperature Fischer–Tropsch synthesis. However, due to their amorphous nature, characterization of the active sites has been challenging experimentally and computationally. Here, using a combined density functional theory (DFT), neural network interatomic potential-assisted global optimization, and ensemble learning study, we evaluate dynamic surface changes associated with syngas (H and CO) interactions. For this purpose, we have developed a general procedure that we use to model an experimentally relevant 270-atom Fe 182 C 88 NP using the neural network-assisted stochastic surface walk global optimization algorithm (SSW-NN). Once generated, the Fe 182 C 88 NP active sites and particle morphology are thoroughly characterized before the effects of syngas adsorbate interactions are explored by using DFT and molecular dynamics simulations. Lastly, we explore correlations between geometric and electronic features of the active sites and the adsorption of H (H ads ), using a regularized random forest machine learning algorithm. In doing so, we identified the Fe–C coordination number and p orbital occupancy as the most important descriptors affecting H ads . Furthermore, using a combined ML and quantum chemistry approach, our work demonstrates a general and efficient procedure for generating and probing complex surface phenomena on binary nanoparticles.

Adsorption↗

Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties

A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)-ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis- (terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4!-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump–probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T 1 ) excited states of these chromophores feature absorption manifolds that span the 800–1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T 1 → T n ) > 4 × 10 4 M –1 cm –1 ]. Dynamic hyperpolarizability (β λ ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800–1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large βHRS values over the 1200–1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large βHRS values over the 850–1200 nm region. Generalized Thomas–Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent β λ values, including two- and three-level contributions for both β zzz and β xzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. Furthermore, these analyses qualitatively rationalize how the βzzz and βxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined βHRS values as a function of irradiation wavelength that derive from substantial singlet–triplet mixing, and complex interactions among multiple different β tensor components that modulate the long wavelength regime of the nonlinear optical response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aqueous Interfaces in Chemical Separations

Chemical separations play a vital role in refinery and reprocessing of critical materials, such as platinum group metals, rare earths, and actinides. The choice of separation system─whether it is liquid–liquid extraction (LLE), sorbents, or membranes─depends on specific needs and applications. In almost all separation processes, the desired metal ions adsorb or transfer across an aqueous interface, such as the solid/liquid interface in sorbents or oil/water interfaces in LLE. Despite these separation technologies being extensively used for decades, our understanding of the molecular-scale mechanisms governing ion adsorption and transport at interfaces remains limited. This knowledge gap presents a significant challenge in meeting the increasing demands for these critical materials due to their growing use in advanced technologies. Fortunately, recent advancements in surface-specific experimental and computational techniques offer promising avenues to bridge this gap and facilitate the development of next-generation separation systems. Interestingly, unanswered questions regarding interfacial phenomena in chemical separations hold great relevance to various fields, including energy storage, geochemistry, and atmospheric chemistry. Therefore, the model interfacial systems developed for studying chemical separations, such as amphiphilic molecules assembled at a solid/water, air/water, or oil/water interface, may have far-reaching implications, extending beyond separations and opening doors to addressing a wide range of scientific inquiries. This perspective discusses recent interfacial studies elucidating amphiphile–ion interactions in chemical separations of metal ions. Finally, these studies provide direct, molecular-scale information about solute and solvent behavior at aqueous interfaces, including multivalent and complex ions in highly concentrated solutions, which play key roles in LLE of critical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genesis of Nanogalvanic Corrosion Revealed in Pearlitic Steel

Nanoscale, localized corrosion underpins billions of dollars in damage and material costs each year; however, the processes responsible have remained elusive due to the complexity of studying degradative material behavior at nanoscale liquid–solid interfaces. Recent improvements to liquid cell scanning/transmission electron microscopy and associated techniques enable this first look at the nanogalvanic corrosion processes underlying this widespread damage. Nanogalvanic corrosion is observed to initiate at the near-surface ferrite/cementite phase interfaces that typify carbon steel. In minutes, the corrosion front delves deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally, converting the ferrite to corrosion product normal to each buried cementite grain. Over the following few minutes, the corrosion product that lines each cementite grain undergoes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure.

36 MATERIALS SCIENCE↗

A DFT Comparison of C–C Reductive Coupling from Terminal Cyanido and Cyaphido Complexes of Nickel

The density functional theory study of the thermal C–C reductive coupling from terminal cyanido and hypothetical cyaphido complexes of [Ni(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) revealed the key reaction intermediate in the reductive C–CP coupling being a σ-CC complex unlike an η 2 -aryl complex in the Ni C–CN system, as already observed in our previous studies. The reaction in THF is endothermic by 4.9 kcal/mol for cyanido with a 32.0 kcal/mol activation barrier and exothermic by 28.5 kcal/mol for cyaphido with an 11.3 kcal/mol activation barrier. To compare our results with the existing experimental data, we chose mesityl as the aryl group and also studied the CP reaction with [Pt(dmpe)] and [Pt(dmpm)] (dmpe = 1,2-bis(dimethylphosphino)methane) fragments. Our findings are consistent with the thermodynamically uphill photolytic C–CP bond activation in phosphaalkynes with Pt and a faster thermal back-reaction with [Pt(dmpe)] compared to that of [Pt(dmpm)]. Furthermore, based on the natural population analysis, when the polarity of the C–C bond is inverted, the sign of ΔG° is also inverted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fischer-Tropsch synthesis: Direct cobalt nitrate reduction of promoted Co/Al 2 O 3 catalysts

Direct reduction of cobalt nitrate versus conventional calcination/reduction treatment was conducted using alumina with identical methodology as previously applied to SiO 2 and TiO 2 . Similar BET surface areas, pore volumes and pore size distributions were obtained for the activated calcined and uncalcined catalysts indicating no significant difference on morphological properties. However, the reducibility slightly increases and Co crystallite size is smaller for activated uncalcined samples. Reduction phenomena were analyzed by TPR-MS and TPR-EXAFS/XANES. Combining these techniques allows an explanation of the complex phenomena occurring during the direct reduction of cobalt nitrate, as both nitrate decomposition and cobalt oxide reduction are involved. Cobalt nitrate species are converted to CoO x intermediates. These species are oxidized by NO X (from nitrate decomposition) to Co 3 O 4 spinel, which is converted to CoO prior to Co 0 formation. Noble metals (Pt, Re, Ru and Ag) improve cobalt oxide reducibility, especially for the final reduction step (i.e., CoO to Co 0 ). The effect of direct nitrate reduction on FT activity was investigated using a 1 L CSTR. Activated unpromoted and Pt-promoted uncalcined catalysts achieved higher initial and steady-state CO conversions in comparison to the corresponding calcined catalysts. The best performance was achieved with direct reduction of uncalcined 0.5%Pt-25%Co/Al 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Agentic framework for programmatic crystal structure generation using a fine-tuned worker–supervisor large language model

Platinum group metals (PGMs) underpin many catalytic technologies but face severe supply constraints, motivating the search for alternative materials and computational methods to accelerate discovery. While atomistic simulation tools such as Pymatgen and ASE have streamlined structure manipulation, they require detailed inputs, limiting accessibility for experimentalists and slowing early-stage exploration. Here, in this study, we present an AI-driven agentic framework that orchestrates worker–supervisor large language models (LLMs). The worker translates natural-language prompts of varying abstraction into valid crystallographic structures using a compact LLM fine-tuned with low-rank adaptation on a curated text–code–CIF dataset, emphasizing energy-efficient training. Benchmarking against the baseline CodeGen-350M-mono model shows that fine-tuning reduces hallucination rates from 100% to as low as 5% and improves structural match accuracy to up to 82% for fully specified inputs. Accuracy declines with decreasing prompt detail but remains nontrivial even when only stoichiometry and space group are provided, underscoring the LLM’s capacity for crystallographic inference. The supervisor Claude LLM evaluates the outputs and triggers iterative refinement through the worker’s built-in structure manipulation capabilities (e.g., supercell scaling, strain, vacancy, and substitution operations). We further demonstrate use cases for technologically relevant catalysts, including IrO 2 , pyrochlore Pb 2 Ir 2 O 7 , Ni 2 FeO 4 , and Ni 3 Mo, where the framework generates physically consistent structures that can be refined via geometry optimization. This work introduces a low-energy, language-driven pathway for integrating human and machine intelligence in materials design, paving the way for AI-assisted synthesis planning and high-throughput screening of complex oxides.

AI agent↗

Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure regulator (BPR). After soaking the parts to be cleaned in the clean vessel for a period, the CO2 with contaminants is flushed out of the cleaning vessel using fresh CO2 in a first-in-first-out (FIFO) method. The contaminants are either precipitating out in the boil-off container or being trapped in a filter subsystem. The parts to be cleaned are secured in a basket inside and can be rotated up to 1,400 rpm by a magnetic drive. The fluid flows within the vessel generate tangential forces on the parts surfaces, enhancing the cleaning effectiveness and shortening the soaking time. During the FIFO flushing, the pump subsystem pushes fresh CO2 into the cleaning vessel at a constant flow rate between 0.01 and 200 mL/min, while the BPR regulates the pressure in the cleaning vessel to within 0.1 bar by controlling the needle position in an outlet valve. The fresh CO2 gas flows through the heat exchanger at a given temperature before entering the cleaning vessel. A platinum resistance thermometer (PRT) reads the cleaning vessel interior temperature that can be controlled to within 0.1 K. As a result, cleaning vessel temperature remains constant during the FIFO flushing. There is no change in solvent power during FIFO flushing since both temperature and pressure inside the cleaning vessel remain unchanged, thus minimizing contaminants left behind. During decompression, both temperature and pressure are strictly controlled to prevent bubbles from generating in the cleaning vessel that could stir up the contaminants that sank to the bottom by gravity.

Lin, Ying↗

Electronic Rearrangement in Steps of Reductive Elimination of Polar Electrophiles Leads to Refinement of Redox Events

The oxidative addition/reductive elimination of polar molecules such as methyl iodide at late metal centers has a strongly supported $S_{N^2}$ mechanism for many key organometallic complexes, including important industrial catalysts. In the reductive elimination direction, it is proposed that a ligand initially dissociates, typically a halide, followed by subsequent nucleophilic attack at the ligand trans to the now vacant site. The prevailing view is the metal reduction occurs upon transferring the electrophile in the $S_{N^2}$ step. Herein, we report the use of an ensemble of computational techniques to characterize the electronic structure of the reactants and intermediates along this reductive elimination pathway. These calculations demonstrate, unexpectedly, that the initiating loss of an anionic ligand from the octahedral highly oxidized structure leads to an electronic rearrangement that shifts electron density from the apical ligand back toward the metal resulting in an inversion of the electron flow between the metal and apical ligand. The anisotropic shift in electron density to the metal disproportionately affects the apical position, which is best described as a Pt → Me dative bond. With this Pt → Me bonding description, our interpretation of the IUPAC oxidation state formalism would assign the intermediate as Pt ΙΙ . Although counterintuitive, the formal and functional reduction of the metal thus occurs upon halide dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗