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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

BODIPY and dipyrrin as unexpected robust anchoring groups on TiO 2 nanoparticles

Covalent attachment of molecules to metal oxide surfaces typically demands the presence of an anchoring group that in turn requires synthetic steps to introduce. BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) chromophores have long been used in dye-sensitized solar cells, but carboxylic acid groups typically had to be installed to act as surface anchors. We now find that even without the introduction of such anchors, the unmodified BODIPY can bind to TiO 2 surfaces via its BF 2 group through boron–oxygen surface bonds. Dipyrrin, the parent molecule of BODIPY, is also capable of binding directly to TiO 2 surfaces, likely through its chelating nitrogen atoms. These binding modes prove to be even more robust than that of an installed carboxylate and offer a new way to attach molecular complexes to surfaces for (photo)catalytic applications since, once bound, we show that surface bound BODIPY and dipyrrin derivatives exhibit ultrafast photoinjection of electrons into the conduction band of TiO 2 .

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

Polytypism in semi-disordered lizardite and amesite by low-dose HAADF-STEM

Serpentine minerals exert important controls on the physical properties of ultramafic rocks and have the potential to influence deformation phenomena in fault zones and to control the release of water in subducted slabs. Sheet serpentine generally, and lizardite and amesite specifically, can adopt alternative crystallographic stacking arrangements called polytypes. Polytypism has been extensively studied in fully ordered crystals, but it remains largely enigmatic in the more common semi-disordered crystals that in long-range analyses such as X-ray diffraction only exhibit random combinations of 0b and ±1/3b interlayer shifts. To date, atomic-resolution imaging to identify locally ordered polytypes has been precluded by the beam-sensitive nature of this hydrous magnesium silicate mineral. Here, in this study, we employed low-dose high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to study the polytypic structure of semi-disordered lizardite and amesite. Because the electron dose was as low as ~6000 e–/Å 2 , it was possible to directly resolve oxygen atomic columns and all the cations with a resolution of ~1 Å and reveal the short-range order. For lizardite, we identified long-period non-standard polytypes, including examples with 3, 4, 8, and 9 layers stemming from the ordering of the octahedral tilt along the a-axis. For amesite, we found short-range ordered polytypes with periodicities of up to 42 Å stemming from the ordering of interlayer shifts along the b-axis. The resolution was sufficient to determine the relative abundance of 6R 2 , 6R 1 , 2H 1 , and 2H 2 polytypes in amesite to be 46.1, 29.6, 7.7, and 1.9%, respectively. This is contrary to the expectation that the most common form of amesite is the 2H 2 polytype, which may be more likely to form macroscopic crystals suitable for conventional X-ray diffraction-based studies. We conclude that HAADF-STEM methods open the way for the characterization of beam-sensitive minerals and to resolve the structural details of less well-ordered (but possibly more abundant) minerals at a unit-cell scale.

58 GEOSCIENCES↗
DOE OSTI2025

Sensitivity of nEXO to 136 Xe charged-current interactions: Background-free searches for solar neutrinos and fermionic dark matter

We study the sensitivity of nEXO to solar neutrino charged-current interactions, 𝜈 𝑒 + 136 Xe → 136 Cs*+𝑒 − , as well as analogous interactions predicted by models of fermionic dark matter. Due to the recently observed low-lying isomeric states of 136 Cs, these interactions will create a time-delayed coincident signal observable in the scintillation channel. Here we develop a detailed Monte Carlo simulation of scintillation emission, propagation, and detection in the nEXO detector to model these signals under different assumptions about the timing resolution of the photosensor readout. We show this correlated signal can be used to achieve background discrimination on the order of 10 −9 , enabling nEXO to make background-free measurements of solar neutrinos above the reaction threshold of 0.668 MeV. We project that nEXO could measure the flux of neutrinos from the carbon-nitrogen-oxygen cycle with a statistical uncertainty of 25%, thus contributing a novel and competitive measurement toward addressing the solar metallicity problem. Additionally, nEXO could measure the mean energy of the 7 Be neutrinos with a precision of 𝜎 ≤ 1.5 keV and could determine the survival probability of 7 Be and pep solar 𝜈𝑒 with precision comparable to the state of the art. These quantities are sensitive to the Sun’s core temperature and to nonstandard neutrino interactions, respectively. Here, the strong background suppression would allow nEXO to search for charged-current interactions of fermionic dark matter in the mass range 𝑚 𝜒 = 0.668–7 MeV with a sensitivity up to three orders of magnitude better than current limits.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

NanoSIP: NanoSIMS Applications for Microbial Biology

High-resolution imaging with secondary ion mass spectrometry (nanoSIMS) has become a standard method in systems biology and environmental biogeochemistry and is broadly used to decipher ecophysiological traits of environmental microorganisms, metabolic processes in plant and animal tissues, and cross-kingdom symbioses. When combined with stable isotope-labeling—an approach we refer to as nanoSIP—nanoSIMS imaging offers a distinctive means to quantify net assimilation rates and stoichiometry of individual cell-sized particles in both low- and high-complexity environments. While the majority of nanoSIP studies in environmental and microbial biology have focused on nitrogen and carbon metabolism (using 15 N and 13 C tracers), multiple advances have pushed the capabilities of this approach in the past decade. The development of a high-brightness oxygen ion source has enabled high-resolution metal analyses that are easier to perform, allowing quantification of metal distribution in cells and environmental particles. New preparation methods, tools for automated data extraction from large data sets, and analytical approaches that push the limits of sensitivity and spatial resolution have allowed for more robust characterization of populations ranging from marine archaea to fungi and viruses. Further, NanoSIMS studies continue to be enhanced by correlation with orthogonal imaging and ‘omics approaches; when linked to molecular visualization methods, such as in situ hybridization and antibody labeling, these techniques enable in situ function to be linked to microbial identity and gene expression. Here we present an updated description of the primary materials, methods, and calculations used for nanoSIP, with an emphasis on recent advances in nanoSIMS applications, key methodological steps, and potential pitfalls.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2026

Modeling Radiolysis and Chemical Reactions during Dry Storage of Aluminum-clad Spent Nuclear Fuel

After aluminum-clad spent nuclear fuel (ASNF) is removed from the reactor, it is initially stored in spent fuel pools, which are specially designed water-filled basins that provide temporary cooling to reduce the temperature of the fuel assemblies and provide radiation shielding. ASNF continues to generate heat due to the radioactive decay of elements within the fuel, which persists for many years post-shutdown as the residual radioactive products decay into more stable elements. During the wet storage period, an oxyhydroxide layer composed of boehmite/bayerite forms on the surfaces of the aluminum cladding from exposure to water in the pools. Road-ready packaging for long-term disposition of the ASNF involves dry storage in helium backfilled DOE standard canisters (DSCs). When the ASNF is removed from water storage and dried, most of the water is removed, but some physisorbed and chemisorbed water remains in the oxyhydroxide layers. This residual water can produce hydrogen when exposed to radiation from the ASNF during dry storage. Predicting hydrogen accumulation over time in the DSCs is critical for long-term storage considerations. Previous modeling efforts have developed coupled computational fluid dynamics (CFD)-chemical models to simulate temperature, pressure, and gas phase concentrations within the DSCs. These models use the thermal field predicted by CFD as input to a radiolysis model for the gas phase and the surface oxyhydroxide layer chemistry. Given the long storage period of the DSCs and the impracticality of long-term experiments, a simulation-based approach is necessary to assess chemical evolution within the canisters. This study advances the development of a modeling framework designed to simulate the chemical evolution of spent fuel canisters. Both thermal and radiation-driven reactions are considered, with radiation kinetics quantified using G-values. Sensitivity analysis identifies key parameters influencing species composition. Reaction pathway diagrams offer insight into dominant species formation routes, enabling more effective comparisons between model predictions and experimental observations, particularly regarding the production of hydrogen. Results show that the model predicts significant hydrogen gas production with minimal oxygen generation, primarily due to hydrogen formation via boehmite pathways. These findings underscore the importance of accurately characterizing surface-bound species and radiolysis kinetics. A deeper understanding of these mechanisms is critical for evaluating the long-term safety of nuclear waste storage.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗
DOE OSTI2025

A heat and mass transfer model for evaluation of damaged cesium chloride radiological sources

Radiological sources are vital to many applications, and typically contain byproducts from waste streams which decay over time to form complex mixtures of elements. Daughter products resulting from these decay processes can introduce complicating factors to the integrity and safety of the vessel that contains the radiological material. Sources containing cesium 137 ( 137 Cs) are of particular interest, because the decay of this isotope produces barium metal which reacts readily and exothermically with oxygen. This work employs physics-based numerical tools to examine the thermal response of a radiological source containing a mixture of cesium and barium in the event that vessel walls are damaged and atmospheric gases contact source material. A parametric study was conducted to determine the sensitivity of the response to various factors, including vessel geometry, source material age, the degree of vessel damage, and other parameters. Here, it was found that the peak temperatures that occurred within the source material strongly depend on these parameters, particularly vessel geometry and age, which determine whether a breach would be a relatively minor accident or a catastrophic incident. Finally, the model’s sensitivity to uncertain thermophysical properties is discussed.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Redox regulation of m 6 A methyltransferase METTL3 in β-cells controls the innate immune response in type 1 diabetes

Type 1 Diabetes (T1D) is characterized by the destruction of pancreatic ß-cells. Several observations have renewed the interest in ß-cell RNA sensors and editors. Here, in this study, we report that N 6 -methyladenosine (m 6 A) is an adaptive ß-cell safeguard mechanism that controls the amplitude and duration of the antiviral innate immune response at T1D onset. m 6 A writer methyltransferase 3 (METTL3) levels increase drastically in ß-cells at T1D onset but rapidly decline with disease progression. m 6 A-sequencing revealed the m 6 A hypermethylation of several key innate immune mediators including OAS1, OAS2, OAS3, and ADAR1 in human islets and EndoC-ßH1 cells at T1D onset. METTL3 silencing enhanced OAS levels by increasing its mRNA stability. Consistently, in vivo gene therapy, to prolong Mettl3 overexpression specifically in ß-cells, delayed diabetes progression in the non-obese diabetic (NOD) mouse model of T1D. Mechanistically, the accumulation of reactive oxygen species blocked upregulation of METTL3 in response to cytokines, while physiological levels of nitric oxide enhanced its expression. Furthermore, for the first time to our knowledge, we report that the cysteines in position C276 and C326 in the zinc finger domains of the METTL3 protein are sensitive to S-nitrosylation (SNO) and are significant for the METTL3-mediated regulation of OAS mRNA stability in human ß-cells. Collectively, we report that m 6 A regulates ß-cells to control the innate immune response during the onset of T1D in humans.

2'-5'-oligoadenylate synthetase↗
DOE OSTI2020

Suppression of voltage-decay in Li 2 MnO 3 cathode via reconstruction of layered-spinel coexisting phases

Voltage decay, i.e., the voltage decrease during electrochemical cycling, has been a decade-long challenge for lithium-ion batteries. This issue not only leads to a substantial loss of energy density, but also raises challenges for the battery management system, hindering the commercial application of high capacity lithium-rich oxide. Here, we show that through a combination of electrochemical conditioning and thermal treatment, Li 2 MnO 3 , the parent compound of lithium-rich oxide, which typically displays severe voltage and capacity decay, could be converted into a new phase that essentially suppresses the voltage decay with improved capacity retention and rate performance. Furthermore, by combining atomic-sensitive nuclear magnetic resonance, differential electrochemical mass spectrometry and synchrotron-based resonant inelastic X-ray scattering, we disclose that treatment triggers the formation of three-coexisting phases, i.e., the lithium-rich layered, spinel and defect spinel phases, which enables improved reversibility of the oxygen redox activity and enhanced manganese redox reactions in the initial cycle. Our findings suggest the key role of the local structure in the voltage decay problem and provide insights for material optimizations towards lithium- and manganese-rich cathodes without the voltage decay.

25 ENERGY STORAGE↗
DOE OSTI2022

Observation of site-selective chemical bond changes via ultrafast chemical shifts

The concomitant motion of electrons and nuclei on the femtosecond time scale marks the fate of chemical and biological processes. Here we demonstrate the ability to initiate and track the ultrafast electron rearrangement and chemical bond breaking site-specifically in real time for the carbon monoxide diatomic molecule. We employ a local resonant x-ray pump at the oxygen atom and probe the chemical shifts of the carbon core-electron binding energy. We observe charge redistribution accompanying core-excitation followed by Auger decay, eventually leading to dissociation and hole trapping at one site of the molecule. The presented technique is general in nature with sensitivity to chemical environment changes including transient electronic excited state dynamics. This work provides a route to investigate energy and charge transport processes in more complex systems by tracking selective chemical bond changes on their natural timescale.

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

Uncertainty Quantification of a Light Water Pulsed-Neutron Die-Away Experiment to Thermal Neutron Scattering Laws

Thermal neutron scattering laws are important nuclear data for many nuclear science and engineering applications. Validation helps to ensure that a thermal neutron scattering law has a high quality and often employs critical benchmarks as integral experiments. Recently, pulsed-neutron die-away benchmarks have been used as an experiment to validate thermal neutron scattering laws. Herein, we evidence how this alternative integral experiment has a high sensitivity to these nuclear data by performing an uncertainty quantification analysis. The analysis randomly sampled the nuclear model parameters associated with hydrogen bound in light water thermal neutron scattering law and sampled other nuclear data that influenced the experiment’s integral parameter (e.g., elastic scattering, absorption in hydrogen and oxygen) from their respective covariance matrices. The thermal neutron scattering law caused an uncertainty in the integral parameter that reached 2.67%, which exceeds by an order of magnitude the uncertainties induced in commonly used thermal solution critical benchmarks. The validation performed here, although limited due to a poor description of the historical experiment, indicated that the ENDF/B-VIII.0 thermal neutron scattering law well predicted the integral parameter. These results motivate further benchmark and validation efforts using pulsed-neutron die-away experiments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Submicrometer spectromicroscopy of UO 2 aged under high humidity conditions

We report the oxidation of uranium dioxide is a complicated process, depending on factors including humidity, temperature, and microstructure. To further determine the characteristics of this process, UO 2 particles were allowed to age and agglomerate under 98% relative humidity at room temperature for 378 days. A focused ion beam (FIB) section of this agglomeration was then measured at the O K-edge, U N 5 -edge, and C K-edge using the scanning transmission x-ray microscope (STXM) at the Advanced Light Source. O K-edge and U N 5 -edge x-ray absorption measurements allowed for the elemental and chemical species mapping of the agglomerates and indicated the formation of schoepite at the submicrometer scale in specific locations. Non-negative matrix factorization was employed to elucidate the main components at the O K-edge, which were uranyl (schoepite) formed primarily at the interface of the sample with controlled atmosphere, a UO 2 -like bulk component present in the majority of the sample, and an oxygen species present at the surface of the FIB section, which is likely adsorbed water. STXM spectromicroscopy measurements at the U N 5 -edge measurements also confirmed the location of oxidized uranium. This analysis is a valuable insight into the formation of schoepite on UO 2 and shows the sensitivity to and utility of STXM spectromicroscopy for uranium speciation.

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

Role of Surface Termination in the Metal–Insulator Transition of V 2 O 3 (0001) Ultrathin Films

Surface termination is known to play an important role in determining the physical properties of materials. It is crucial to know how surface termination affects the metal–insulator transition (MIT) of V 2 O 3 films for both fundamental understanding and its applications. By changing growth parameters, we achieved a variety of surface terminations in V 2 O 3 films that are characterized by low-energy electron diffraction (LEED) and photoemission spectroscopy techniques. Depending upon the terminations, our results show that MIT can be partially or fully suppressed near the surface region due to the different fillings of the electrons at the surface and subsurface layers and the change of screening length compared to the bulk. Across MIT, a strong redistribution of spectral weight and its transfer from a high-to-low-binding energy regime is observed in a wide energy scale. Our results show that the total spectral weight in the low-energy regime is not conserved across MIT, indicating a breakdown of the “sum rules of spectral weight”, signature of a strongly correlated system. Such a change in spectral weight is possibly linked to the change in hybridization, lattice volume (i.e., effective carrier density), and the spin degree of freedom in the system that occurs across MIT. We find that MIT in this system is strongly correlation-driven, where the electron–electron interactions play a pivotal role. Furthermore, our results provide better insight into the understanding of the electronic structure of strongly correlated systems and highlight the importance of accounting for surface effects during interpretation of the physical property data mainly using surface-sensitive probes, such as surface resistivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Tacky Elastomers to Enable Tear-Resistant and Autonomous Self-Healing Semiconductor Composites

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus (<1 MPa) and ultrahigh deformability with fracture strain above 800%. More importantly, failure behavior is not sensitive to precut notches under deformation. Autonomous self-healing at room temperature, both mechanical and electronic, is demonstrated through the physical contact of two separate films. The composite film also shows device stability in the ambient environment over 5 months due to much-improved barrier property to both oxygen and water. Butyl rubber is broadly applicable to various p-type and n-type semiconducting polymers for fabricating self-healable electronics to provide new resilient electronics that mimic the tear resistance and healable property of human skin.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Caffeic acid attenuates irradiation-induced hematopoietic stem cell apoptosis through inhibiting mitochondrial damage

Highlights: • IR-induced mitochondrial damage accelerates HSC apoptosis. • CA attenuates mitochondrial damage and apoptosis of HSCs induced by IR. • CA protects against BM hematopoietic failure in mice after IR exposure. Hematopoietic stem cells (HSCs) are sensitive to ionizing radiation (IR) damage, and its injury is the primary cause of bone marrow (BM) hematopoietic failure and even death after exposure to a certain dose of IR. However, the underlying mechanisms remain incompletely understood. Here we show that mitochondrial oxidative damage, which is characterized by mitochondrial reactive oxygen species overproduction, mitochondrial membrane potential reduction and mitochondrial permeability transition pore opening, is rapidly induced in both human and mouse HSCs and directly accelerates HSC apoptosis after IR exposure. Mechanistically, 5-lipoxygenase (5-LOX) is induced by IR exposure and contributes to IR-induced mitochondrial oxidative damage through inducing lipid peroxidation. Intriguingly, a natural antioxidant, caffeic acid (CA), can attenuate IR-induced HSC apoptosis through suppressing 5-LOX-mediated mitochondrial oxidative damage, thus protecting against BM hematopoietic failure after IR exposure. These findings uncover a critical role for mitochondria in IR-induced HSC injury and highlight the therapeutic potential of CA in BM hematopoietic failure induced by IR.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Integrated Effects of Site Hydrology and Vegetation on Exchange Fluxes and Nutrient Cycling at a Coastal Terrestrial‐Aquatic Interface

Abstract The complex interactions among soil, vegetation, and site hydrologic conditions driven by precipitation and tidal cycles control the biogeochemical transformations and bi‐directional exchange of carbon and nutrients across the terrestrial–aquatic interfaces (TAIs) in coastal regions. This study uses a highly mechanistic model, Advanced Terrestrial Simulator (ATS)‐PFLOTRAN, to explore how these interactions affect exchanges of materials and carbon and nitrogen cycling. We used a transect in the Chesapeake Bay region that spans zones of open water, coastal wetland, transition, and upland forest. We designed several simulation scenarios to parse the effects of the individual controlling factors and the sensitivity of carbon cycling to reaction rate parameters derived from laboratory experiments. Our simulations reveal an active zone for carbon cycling under the transition zones between the wetland and the upland. Evapotranspiration is found to enhance the exchange fluxes between the surface and subsurface domains, resulting in a higher dissolved oxygen concentration in the TAIs. The transport of organic carbon derived from plant leaves and roots provide an additional source of organic carbon needed for the aerobic respiration and denitrification processes in the TAIs. The variability in reaction rate parameters associated with microbial activities is also found to play a dominant role in controlling the heterogeneity and dynamics of the simulated redox conditions. This modeling‐focused exploratory study enabled us to better understand the complex interactions among soil, water and microbes that govern the hydro‐biogeochemical processes at the TAIs, which is an important step toward representing coastal ecosystems in larger‐scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Data and Scripts associated with “Lambda-PFLOTRAN: Workflow for Incorporating Organic Matter Chemistry Informed by Ultra High Resolution Mass Spectrometry into Biogeochemical Modeling.”

This data package is associated with the publication “Lambda-PFLOTRAN: Workflow for Incorporating Organic Matter Chemistry Informed by Ultra High Resolution Mass Spectrometry into Biogeochemical Modeling” submitted to Geoscientific Model Development (Muller et al., 2024). In this manuscript, organic matter chemistry and thermodynamics are directly connected to reactive transport simulators through the newly developed Lambda-PFLOTRAN (Parallel Reactive Flow and Transport model) workflow tool that succinctly incorporates organic matter chemistry data generated from Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) into reaction networks to simulate aerobic respiration of the organic matter and the resulting biogeochemistry. Lambda-PFLOTRAN is a python-based workflow, executed through a Jupyter Notebook interface, that digests raw FTICR-MS data, develops a representative reaction network based on substrate-explicit thermodynamic modeling (also termed lambda modeling due to its key thermodynamic parameter λ used therein), and completes a biogeochemical simulation with the open source, reactive flow, and transport code PFLOTRAN. This data package contains Jupyter Notebook based workflows for two test cases for running biogeochemical simulations of organic matter oxidation identified by FTICR-MS. It contains four primary folders (workflow, data, src, and analysis), a file-level metadata file (Muller_2024_Lambda_PFLOTRAN_Manuscript_Data_Package_flmd.csv) that lists all the files contained in this data package with a short description of each, and a data dictionary (Muller_2024_Lambda_PFLOTRAN_Manuscript_Data_Package_dd.csv) file that describes the tabular column headers. The ‘workflow’ folder contains the Jupyter Notebook based workflows for running the lambda analysis, PFLOTRAN simulation, sensitivity analysis and parameter estimation. The ‘data’ folder contains the FTICR-MS data, initial conditions, and incubation data for test cases 1 and 2 in folders titled ‘WHONDRS’ and ‘Colloids’, respectively. The data folder also has a ‘Database’ folder containing a reaction network for bulk organic matter (assumed to be CH2O) and a general database for PFLOTRAN (hanford_rxn_network). The CH2O reaction network defines bulk organic matter oxidation. Biogeochemical simulations are completed for both the lambda binned organic matter and bulk organic matter reaction networks. The ‘hanford_rxn_network’ database includes information required for PFLTORAN simulations including ion size, molar mass, and charge of the aqueous species, gases, and minerals phases. The ‘src’ folder contains python source codes for performing lambda analysis, PFLOTRAN simulation, sensitivity analysis and parameter estimation. The ‘analysis’ folder contains outputs from the test cases 1 and 2 including lambda analysis, PFLOTRAN runs and the calibration results.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Effects of the method of active site characterization for determining structure-sensitivity in Ag-catalyzed ethylene epoxidation

We report catalysts have been prepared on a low surface area α-Al 2 O 3 support used commercially for previous generation olefin epoxidation catalysts. Prescreening of the low surface area alumina (0.73 m 2 /g) indicated the absence of acid catalyzed isomerization of EO at an evaluation temperature of 210 °C. A 0.1 wt% Ag base material synthesized by incipient wetness impregnation of AgNO 3 was used as a base material for electroless deposition (ED) of additional Ag to increase particle sizes by controlled reduction of Ag + directly onto the preexisting Ag surface to form weight loadings between 0.3 and 5.0 wt% metal. A 12 wt% Ag/α-Al 2 O 3 using Ag 2 C 2 O 4 as the Ag precursor was also prepared to compare performance of the ED samples with a catalyst more typical of industrial formulations. Characterization by SEM, STEM, and hydrogen titration of oxygen precovered Ag characterized before and after catalytic evaluation indicated that microscopy is required to accurately represent distributions of Ag particle sizes, but H 2 titration of O-precovered Ag gives the best representation of active sites since it directly counts the number of Ag surface sites. Larger particles >100 nm are resistant to both Ag sintering and carbon foulant; TOF values were relatively insensitive to particle size with only a 2.2 × difference between the best and worst performing samples. Selectivity, which is not a function of TOF, shows the most significant structure sensitivity effect where particle sizes follow the trend 67 nm ≈ 92 nm (58% EO) < 157 nm (67% EO) < 211–542 nm (73% EO). The lower EO selectivities were also correlated with increased fouling for the smaller Ag sizes, suggesting that more strongly bound EO precursor(s) leads to combustion and CO 2 /H 2 O formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗