First-principles-informed energy span and microkinetic analysis of ethanol catalytic conversion to 1,3-butadiene on MgO

Kinetic modeling of single-step catalytic conversion of ethanol to 1,3-butadiene is necessary to inform accurate process design. This paper uses first-principles-informed energy span and microkinetic analysis to explore the reaction free energy landscapes and kinetic limitations of competing reaction pathways on a MgO (100) step-edge. Previous studies suggested mechanisms proceeding via both dehydrogenation and dehydration of ethanol, and highlighted sensitivity to conditions and catalyst composition. Here, we use the energy span concept to characterize the theoretical maximum turnover and degree of turnover frequency control for states in each reaction pathway, finding the dehydration route to be less active for 1,3-butadiene, and suggesting rate-determining states in the dehydrogenation, dehydration, and condensation steps. The influence of temperature on the relative rate contribution of each state is quantified and explained through the varying temperature sensitivity of the free energy landscape. A microkinetic model is developed to explore competition between pathways, interaction with gas-phase species, and surface coverage limitations. This suggests that the turnover may be significantly lower than predicted solely based on energetics. Turnover frequency determining states found to have high surface coverage include adsorbed ethanol and two longer, oxygenated hydrocarbons. The combined energy span and microkinetic analysis permits investigation of a complex system from two perspectives and helps elucidate conflicting observations of rate determining steps and product distribution by considering both energetic and kinetic limitations. The impact of uncertainty in the energy landscape is quantified using a correlated error model. While the range of predictions is large, the average performance and trends are similar

Surface Analysis Insight Note: Observations relating to photoemission peak shapes, oxidation state, and chemistry of titanium oxide films

It is common practice to describe the coordination of metal atoms in a binding configuration with their nearest neighbors in terms of oxidation state, a measure by which the number of electrons redistributed between atoms forming chemical bonds. In XPS terms, change to an oxidation state is commonly inferred by correlating photoemission signal with binding energy. The assumption, when classifying photoemission signals into distinct spectral shapes, is that a distribution of intensities shifted to lower binding energy is evidence of a reduction in oxidation state. In this Insight note, we raise the prospect that changes in photoemission peak shape may occur without obvious changes, determined by XPS in stoichiometry for a material. It is well known that TiO2 measured by XPS yields reproducible Ti 2p photoemission peaks. However, on exposing TiO2 to ion beams, Ti 2p photoemission evolves to complex distributions in intensity, which are particularly difficult to analyze by traditional fitting of bell‐shaped curves to these data. For these reasons, in this Insight note, a thin film of TiO2 deposited on a silicon substrate is chosen for analysis by XPS and linear algebraic techniques. Alterations in spectral shapes created from modified TiO2, which might be interpreted as the change in oxidation state, are assessed in terms of relative proportions of titanium to oxygen. It is found through detailed analysis of spectra that quantification by XPS, using procedures routinely used in practice, is not in accord with the typical interpretations of photoemission shapes. The data processing methods used and results presented in this work are of particular relevance to elucidating fundamental phenomena governing the surface evolution of materials‐enabled energy processes where cyclic/non‐steady usage changes the nature of bonding, especially in the presence of contaminants

Definition of a new (Doniach-Sunjic-Shirley) peak shape for fitting asymmetric signals applied to reduced graphene oxide/graphene oxide XPS spectra

The existence of asymmetry in X-ray photoelectron spectroscopy (XPS) photoemission lines is widely accepted, but line shapes designed to accommodate asymmetry are generally lacking in theoretical justification. In this work, we present a new line shape for describing asymmetry in XPS signals that is based on two facts. First, the most widely known line shape for fitting asymmetric XPS signals that has a theoretical basis, referred to as the Doniach-Sunjic (DS) line shape, suffers from a mathematical inconvenience, which is that for asymmetric shapes the area beneath the curve (above the x-axis) is infinite. Second, it is common practice in XPS to remove the inelastically scattered background response of a peak in question with the Shirley algorithm. The new line shape described herein attempts to retain the theoretical virtues of the DS line shape, while allowing the use of a Shirley background, with the consequence that the resulting line shape has a finite area. To illustrate the use of this Doniach-Sunjic-Shirley (DSS) line shape, a set of spectra obtained from varying amounts of graphene oxide (GO) and reduced GO on a patterned, heterogeneous surface are fit and discussed

Effects of Eyjafjallajökull volcanic ash on innate immune system responses and bacterial growth in vitro.

To access publisher's full text version of this article click on the hyperlink at the bottom of the pageOn 20 March 2010, the Icelandic volcano Eyjafjallajökull erupted for the first time in 190 years. Despite many epidemiological reports showing effects of volcanic ash on the respiratory system, there are limited data evaluating cellular mechanisms involved in the response to ash. Epidemiological studies have observed an increase in respiratory infections in subjects and populations exposed to volcanic eruptions.We physicochemically characterized volcanic ash, finding various sizes of particles, as well as the presence of several transition metals, including iron. We examined the effect of Eyjafjallajökull ash on primary rat alveolar epithelial cells and human airway epithelial cells (20-100 µg/cm(2)), primary rat and human alveolar macrophages (5-20 µg/cm(2)), and Pseudomonas aeruginosa (PAO1) growth (3 µg/104 bacteria).Volcanic ash had minimal effect on alveolar and airway epithelial cell integrity. In alveolar macrophages, volcanic ash disrupted pathogen-killing and inflammatory responses. In in vitro bacterial growth models, volcanic ash increased bacterial replication and decreased bacterial killing by antimicrobial peptides.These results provide potential biological plausibility for epidemiological data that show an association between air pollution exposure and the development of respiratory infections. These data suggest that volcanic ash exposure, while not seriously compromising lung cell function, may be able to impair innate immunity responses in exposed individuals.National Institutes of Health (NIH) R01 HL079901 NIH RO1 HL096625 R21HL109589 National Science Foundation NSF-EAR0821615 National Institute of Environmental Health Sciences (NIEHS) through the University of Iowa Environmental Health Sciences Research Center NIEHS/NIH P30 ES005605 National Center for Research Resources, NI

Synthesis and properties of polyamide–Ag2S composite based solar energy absorber surfaces

Silver sulfide (Ag2S), an efficient solar light absorber, was synthesized using a modified chemical bath deposition (CBD) method and polyamide 6 (PA) as a host material via solution phase reaction between AgNO3 and Na2S2O3. X-ray diffraction (XRD) data showed a single, α-Ag2S (acanthite), crystalline phase present while surface and bulk chemical analyses, performed using X-ray photoelectron (XPS) and energy dispersive (EDS) spectroscopies, showed 2:1 Ag:S ratio. Direct and indirect bandgaps obtained from Tauc plots were 1.3 and 2.3 eV, respectively. Detailed surface chemical analysis showed the presence of three distinct sulfur species with majority component due to the Ag2S chemical bonds and minority components due to two types of oxygen–sulfur bonds. Conductivity of the resulting composite material was shown to change with the reaction time thus enabling to obtain controlled conductivity composite material. The synthesis method presented is based on the low solubility of Ag2S and is potentially green, no by-product producing, as all Ag2S nucleated outside the host material can be recycled into the process via dissolving it in HNO3

Structural, Chemical and Optical Properties of the Polyethylene–copper Sulfide Composite Thin Films Synthesized Using Polythionic Acid as Sulfur Source

Synthesis and properties of thin copper sulfide films deposited on polyethylene were explored for the development of low cost hybrid organic–inorganic photovoltaic materials. Polyethylene was used as a model organic host material for thin copper sulfide film formation. Adsorption–diffusion method was used which utilized consecutive exposure of polyethylene to polythionic acid followed by aqueous Cu(II/I) solution. Several crystalline copper sulfide phases were obtained in synthesized samples and elucidated using X-ray diffraction. Surface chemical composition determined using X-ray photoelectron spectroscopy showed the presence of copper sulfides in combination with copper hydroxide. Thickness of the composite material films ranged from several microns to ∼18 μm and depended on the Cu(II/I) exposure time. Bandgap of the materials obtained was measured and ranged from 1.88 to 1.17 eV. Importantly, heating these complex copper sulfide crystalline phase containing films at 100 °C in inert atmosphere invariably resulted in a single copper sulfide, anilite (Cu1.75S), phase. Anilite possesses a bandgap of 1.36 eV and has demonstrated excellent photovoltaic properties. Thus, the method described in this work can be used for a low cost large scale composite thin film photovoltaic material deposition based on anilite as photoactive material