Publications by authors named "Kenneth J Livi"

Multimetallic nanoalloy catalysts have attracted considerable interest for enhancing the efficiency and selectivity of many electrochemically driven chemical processes. However, the preparation of homogeneous bimetallic alloy nanoparticles remains a challenge. Here, we present a room-temperature and scalable, host-guest approach for synthesis of dilute Cu in Ag alloy nanoparticles.

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The local structure and geometry of catalytic interfaces can influence the selectivity of chemical reactions. Selectivity is often critical for the practical realization of reactions such as the electroreduction of carbon dioxide (CO). Previously developed strategies to manipulate the structure and geometry of catalysts for electroreduction of CO involve complex processes or fail to efficiently alter the selectivity.

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Layered manganese (Mn) oxides, such as birnessite, are versatile materials in industrial applications and common minerals mediating elemental cycling in natural environment. Many of birnessite properties are controlled by Mn(III) concentration and particle sizes. Thus, it is important to synthesize birnessite nanoparticles with controlled Mn(III) concentrations and sizes so that one can tune its properties for many applications.

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Electrochemical reduction of CO2, an artificial way of carbon recycling, represents one promising solution for energy and environmental sustainability. However, it is challenged by the lack of active and selective catalysts. Here, we report a two-step synthesis of highly dense Cu nanowires as advanced electrocatalysts for CO2 reduction.

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Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII.

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Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals.

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High-temperature superconductivity has a range of applications from sensors to energy distribution. Recent reports of this phenomenon in compounds containing electronically active BiS2 layers have the potential to open a new chapter in the field of superconductivity. Here we report the identification and basic properties of two new ternary Bi-O-S compounds, Bi2OS2 and Bi3O2S3.

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To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.

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Manganese (Mn) oxides are among the strongest mineral oxidants in the environment and impose significant influence on mobility and bioavailability of redox-active substances, such as arsenic, chromium, and pharmaceutical products, through oxidation processes. Oxidizing potentials of Mn oxides are determined by Mn valence states (2+, 3+, 4+). In this study, the effects of beam damage during electron energy-loss spectroscopy (EELS) in the transmission electron microscope have been investigated to determine the "safe dose" of electrons.

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Increasing evidence suggests that the physicochemical properties of inhaled nanoparticles influence the resulting toxicokinetics and toxicodynamics. This report presents a method using scanning transmission electron microscopy (STEM) to measure the Mn content throughout the primary particle size distribution of welding fume particle samples collected on filters for application in exposure and health research. Dark field images were collected to assess the primary particle size distribution and energy-dispersive X-ray and electron energy loss spectroscopy were performed for measurement of Mn composition as a function of primary particle size.

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Arsenite (As(III)) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (As(V)). As(III) oxidation by Mn(IV)-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During As(III) oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attributed to Mn-oxide surface passivation.

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Teeth have provided insights into many topics including primate diet, paleobiology, and evolution, due to the fact that they are largely composed of inorganic materials and may remain intact long after an animal is deceased. Previous studies have reported that the mechanical properties, chemistry, and microstructure of human enamel vary with location. This study uses nanoindentation to map out the mechanical properties of Alouatta palliata molar enamel on an axial cross-section of an unworn permanent third molar, a worn permanent first molar, and a worn deciduous first molar.

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The nature of Ni-hydroxide precipitates on pyrophyllite were reexamined by analytical electron microscopy (AEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), powder X-ray diffraction (PXRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy. Chemical analysis of precipitates showed that the precipitate contains about 20% Al. HRTEM imaging showed that the precipitate was amorphous and PXRD failed to find any crystalline peaks associated with cnrystalline Ni-Al layered double-hydroxide (LDH) or alpha-Ni(OH)2.

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We demonstrate a new strategy to bond nanowires (NWs) using diffusion bonding of gold (Au). The strategy was used to form very large scale, electrically interconnected 3D NW networks composed of both homogeneous and heterogeneous (multisegmented) NWs. The size of the networks ranged from tens of micrometers to millimeters.

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Bimetallic reductants are frequently more reactive toward organohalides than unamended iron and can also alter product distributions, yet a molecular-level explanation for these phenomena remains elusive. In this study, surface characterization of six iron-based bimetallic reductants (Au/Fe, Co/Fe, Cu/Fe, Ni/Fe, Pd/Fe, and Pt/Fe) revealed that displacement plating produced a non-uniform overlayer of metallic additive on iron. Batch studies demonstrated that not all additives enhanced rates of 1,1,1-trichloroethane (1,1,1-TCA) reduction nor was there any clear periodic trend in the observed reactivity (Ni/Fe approximately Pd/Fe > Cu/Fe > Co/ Fe > Au/Fe approximately Fe > Pt/Fe).

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Permeable reactive barriers employing iron as a reactive surface have received extensive attention. A remaining issue, however, relates to their longevity. As an integral part of a long-term column study conducted to examine the influence of inorganic cosolutes on iron reactivity toward chlorinated solvents and nitroaromatic compounds, Master Builder iron grains were characterized via scanning and transmission electron microscopy, electron energy loss spectroscopy (EELS), micro-Raman spectroscopy, and X-ray diffraction.

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