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Migration, desorption and voltage breakdown properties of cesium films on refractory electrodes, by pulse field emission microscopy
Desorption kinetics of multiple adsorbates - cesium with fluorine on molybdenum and tungsten with application to thermionic diodes
Alkali-ion desorption energies measured on polycrystalline refractory metals at low surface coverage by electron work function
Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.
Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K.
Preliminary modeling of hydrogen diffusion, desorption, and adsorption for YH based on experiments. The model developed in Bison will then be used in coupled multiphysics simulation to get preliminary results for a prototypical microreactor.
The many studies that have been conducted on water adsorption on zeolites were carried out in “adsorption” mode, from adsorption isotherms or single-point measurements, with the samples being first degassed at high temperature, and then exposed to water vapor at variable partial pressure. Here, we report Thermogravimetric Analysis (TGA) studies of HZSM-5 saturated with water at room temperature, thus studying water adsorption in “desorption” mode. In this work, TGA was used to ascertain the amount of water remaining as a function of the pretreatment temperature, and to identify the temperature at which one water molecule per framework Al atom persists. Solid-state 1H NMR spectroscopy, combined with molecular modeling, provided evidence for water molecules hydrogen bonded to Brønsted acid sites and formation of oxonium species for distinct water per framework Al atom. TGA is shown to be a simple and expeditious technique to measure the number of Brønsted acid sites in aluminosilicate zeolites, with advantages over the traditional methods of IR or TPD of dangerous adsorbed ammonia or pyridine. TGA of adsorbed water also provides information on the water clusters formed at the acid sites of HZSM-5, which are proportional to the number of acid sites.
Isotopic fractionation recorded in planetary materials provides insights into physical, chemical, and/or potential biological processes occurring on Solar System bodies. As we enter into the next decades of planetary exploration, the crucial information revealed by isotopic compositions of rocky and icy samples mandates that next generation spaceflight instrumentation possess the capability to measure isotope ratios in situ with sufficient precision/accuracy to distinguish between such processes. Here, in addition to identifying and fingerprinting complex organic materials with high accuracy and ultrahigh mass resolutions, laser desorption Orbitrap™ mass spectrometry (LD-O-MS) has the capability to determine the elemental and isotopic composition of solid planetary materials such as rock, regolith, organics, ice, etc. Here, we use a space-qualified LD-O-MS instrument comprising a 266 nm ultraviolet (UV) laser and Orbitrap mass analyzer ruggedized for planetary applications to investigate the stable isotopic composition of Ti and Zn metal plates. Based on the isotopic analyses, we constrain the performance of the CORALS instrument to sub per mille (‰) level accuracy and precision for Ti and at the per mille (‰) level for Zn. An LD-O-MS instrument is a versatile instrument capable of measuring isotopic composition of a variety of planetary samples and would constitute a critical instrument in the exploration of various planetary bodies including but not limited to Moon, Mars, Enceladus and other ocean or icy worlds, Ceres and other asteroids, and comets, thereby answering several high-priority questions pertaining to the formation and evolution of our Solar System.
The study of lipid molecular fossils by traditional biomarker analysis requires bulk sample crushing, followed by solvent extraction, and then the analysis of the extract by gas chromatography-mass spectrometry (GC–MS). This traditional analysis mixes all organic compounds in the sample regardless of their origins, with a loss of information on the spatial distribution of organic molecules within the sample. These shortcomings can be overcome using the chemical mapping of intact samples. Spectroscopic techniques such as UV fluorescence or Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are among those elemental and molecular mapping techniques. This study employed femtosecond (fs) laser ablation combined with single-photon ionization, a method called fs-laser desorption postionization mass spectrometry (fs-LDPI-MS). In this work, a pulsed ~75 fs, 800 nm laser was used to ablate the geological sample, which was then photoionized after a few microseconds by a pulsed 7.9 eV vacuum ultraviolet laser. An organic carbon-rich geological sample was used for this study to map hydrocarbon biomarkers in sediments that were previously studied by GC–MS. The petrography of this sample was examined by optical and fluorescence microscopy. It is demonstrated here that fs-LDPI-MS combined with petrography for multimodal imaging can expose buried compounds within the sample via in situ layer removal. When used in conjunction with traditional organic geochemical analysis, this method has the potential to determine the spatial distribution of organic biomarkers in geological material. Finally, fs-LDPI-MS imaging data are compared with ToF-SIMS imaging that is commonly used for such studies.
Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosols (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature programmed desorption - direct analysis in real time – high resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of a-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol -1 ) and saturated vapor mass concentrations (C T *, µg∙m -3 ) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, µg∙m -3 ). Further, the VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, enabling their categorization into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant total organic mass loadings (tOM) values of 1–100 µg∙m -3 . Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, C T *, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.
Probing the dynamics of molecular catalysts at electrode–electrolyte interfaces is essential for understanding catalytic mechanisms. Structure-specific spectroscopic methods are particularly powerful for examining electrocatalytic interfaces but are mostly used under steady-state conditions. Herein, we combined surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD) to investigate the dynamics of a molecular Ir-based water oxidation catalyst at the Au–electrolyte interface. We found that the amplitude of the absorbance of the catalyst is anticorrelated to that of interfacial water. This anticorrelation can be understood by the adsorption of the electrooxidized catalyst on the electrode and concurrent displacement of interfacial water. The infrared signals from the interface exhibit an increasing phase lag with respect to the electrode potential with an increasing scan rate of the potential. Kinetic modeling suggests that the potential-dependent adsorption–desorption kinetics of the molecular catalyst on the electrode gives rise to this phase lag. Furthermore, this study shows that PSD-SEIRAS is a powerful tool for investigating the interfacial dynamics of electrocatalytic systems.
Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) provides direct analytical readouts of small molecules that can be used to characterize the metabolic phenotypes of genetically engineered bacteria. In an effort to accelerate the time frame associated with the screening of mutant libraries, we have developed a high-throughput DESI-MSI analytical workflow implementing a single raster line-scan strategy that facilitates the collection of location-resolved molecular information from engineered strains on a subminute time scale. Evaluation of this “Fast-Pass” DESI-MSI phenotyping workflow on analytical standards demonstrated the capability of acquiring full metabolic profiling information with a throughput of ~40 s per sample. This Fast-Pass strategy was implemented in the analysis of genetically edited Escherichia coli strains that have been engineered to produce various free-fatty acids (FFAs) for applications relevant to biofuels. Due to the untargeted nature of DESI-MSI, the investigation of these strains yielded molecular information for both global metabolites and targeted detection of accumulated bioproducts, allowing simultaneous readouts of strain-specific chemical profiles and comparative measurements of FFA production levels.
Ambient ionization techniques enable mass spectrometry (MS) to expand into broader experimental contexts, although it is increasingly clear that results are influenced by the environmental conditions at the site of sampling. Desorption electrospray ionization (DESI), in particular, is affected by variations in relative humidity (RH) levels. Here we describe the design, development, and construction of an environmental control chassis that can actively modulate RH within ± 3% of user-defined set points across a broad humidity range (15%–70% RH). Preliminary characterization demonstrated differential analyte responses across a range of set points, with observed enhancement of leucine-enkephalin, sulfadimethoxine (negative mode), and maltose (positive mode) in response to increased humidity. The measurable differences in analyte signals across discrete humidity set points underscore the importance of environmental control in ambient ionization strategies. The humidity control system outlined here can be translated to other DESI platforms, with construction information provided herein.
Cold plasmas powered by the renewable electricity can facilitate CO 2 desorption for carbon capture materials (CaCO 3 ) at low temperatures.
Nanostructured surfaces enhance ion yields in matrix-assisted laser desorption–ionization mass spectrometry (MALDI-MS). The spike protein complex, S1, is one fingerprint signature of Sars-CoV-2 with a mass of 75 kDa. Here, we show that MALDI-MS yields of Sars-CoV-2 spike protein ions in the 100 kDa range are enhanced 50-fold when the matrix–analyte solution is placed on substrates that are coated with a dense forest of multi-walled carbon nanotubes, compared to yields from uncoated substrates. Nanostructured substrates can support the development of mass spectrometry techniques for sensitive pathogen detection and environmental monitoring.
Hydrogen, while being a potential energy solution, creates arguably the most important embrittlement problem in high-strength metals. However, the underlying hydrogen-defect interactions leading to embrittlement are challenging to unravel. Here, we investigate an intriguing hydrogen effect to shed more light on these interactions. By designing an in situ electron channeling contrast imaging experiment of samples under no external stresses, we show that dislocations (atomic-scale line defects) can move distances reaching 1.5 μm during hydrogen desorption. Combining molecular dynamics and grand canonical Monte Carlo simulations, we reveal that grain boundary hydrogen segregation can cause the required long-range resolved shear stresses, as well as short-range atomic stress fluctuations. Thus, such segregation effects should be considered widely in hydrogen research.
Possible collaborators are the intended audience for the review of thermal desorption spectroscopy activities at Los Alamos National Laboratory.
The $γ- LiAlO_2$ ceramics enriched with the $^6Li$ isotope are used in the form of annular pellets in tritium-producing burnable absorber rods (TPBARs). When irradiated in a pressurized water reactor (PWR), the $^6Li$ absorbs neutrons, simulating the nuclear characteristics of a burnable absorber rod, and produces tritium $(_{1}^{3}H, T)$. Once the $_{1}^{3}H$ is produced in the bulk of $γ- LiAlO_2$, it diffuses to its surface, forming different $_{1}^{3}H$ species (possibly $T, OT, T_2, or T_2O$). The $T_2O$ is expected to be generated from experiment, to avoid $_{1}^{3}H$ leakage. However, up to now, it is still not clear which $_{1}^{3}H$ species are formed on the $γ- LiAlO_2$ surface and travel to the getter. Besides, with the dramatic Li loss under irradiation, the secondary phase (possibly $LiAl_5O_8$) precipitates and participates into the $_{1}^{3}H$ diffusivity and $_{1}^{3}H$ species formation. Therefore, exploring $_{1}^{3}H$ species formation on and desorption from surfaces of $γ- LiAlO_2$ with related secondary phases becomes a very important task to provide a better understanding of $_{1}^{3}H$H species escaping from pellets.