EPR spectroscopy of iron- and nickel-doped [ZnAl]-layered double hydroxides: modeling active sites in heterogeneous water oxidation catalysts

Iron-doped nickel layered double hydroxides (LDHs) are among the most active heterogeneous water oxidation catalysts. Due to inter-spin interactions, however, the high density of magnetic centers results in line-broadening in magnetic resonance spectra. As a result, gaining atomic-level insight into the catalytic mechanism via electron paramagnetic resonance (EPR) is not generally possible. To circumvent spin-spin broadening, iron and nickel atoms were doped into non-magnetic [ZnAl]-LDH materials and the coordination environments of the isolated Fe(III) and Ni(II) sites were characterized. Multifrequency EPR spectroscopy identified two distinct Fe(III) sites (S = 5/2) in [Fe:ZnAl]-LDH. Changes in zero field splitting (ZFS) were induced by dehydration of the material, revealing that one of the Fe(III) sites is solvent-exposed (i.e. at an edge, corner, or defect site). These solvent-exposed sites feature an axial ZFS of 0.21 cm⁻¹ when hydrated. The ZFS increases dramatically upon dehydration (to -1.5 cm⁻¹), owing to lower symmetry and a decrease in the coordination number of iron. The ZFS of the other (“inert”) Fe(III) site maintains an axial ZFS of 0.19-0.20 cm⁻¹ under both hydrated and dehydrated conditions. We observed a similar effect in [Ni:ZnAl]-LDH materials; notably, Ni(II) (S = 1) atoms displayed a single, small ZFS (±0.30 cm⁻¹) in hydrated material, whereas two distinct Ni(II) ZFS values (±0.30 and ±1.1 cm⁻¹) were observed in the dehydrated samples. Although the magnetically-dilute materials were not active catalysts, the identification of model sites in which the coordination environments of iron and nickel were particularly labile (e.g. by simple vacuum drying) is an important step towards identifying sites in which the coordination number may drop spontaneously in water, a probable mechanism of water oxidation in functional materials

Overview of the Development and Applications of a Conceptual Framework for Analyzing Benefits and Costs of On-Farm Food Safety and Environmental Farm Plans

This series of six reports entitled: "On-Farm Food Safety and Environmental Farm Plans: Identifying and Classifying Benefits and Costs" was initiated soon after the launch of the Agricultural Policy Framework (APF) in 2002. The APF recognized the importance of food safety and environmental concerns for the future growth of the agriculture and Agri-food sector. For this reason, Agriculture and Agri-Food Canada (AAFC) commissioned this series of reports to develop a conceptual framework to strengthen our understanding of the potential benefit and cost implications of On-farm Food Safety (OFFS) and Environmental Farm Plans (EFP) that were key components of the APF. The reports were prepared by a group of academics with extensive knowledge of the agriculture and Agri-food sector and issues related to food safety, traceability and the environment. The first report presents a summary of the findings in the five main reports in the series. The second report presents the conceptual framework that was developed to help identify qualitatively the potential benefits and costs that the various players in the agriculture and agri-food supply chain would face in implementing OFFS and EFP programs. The third report applies this framework to pork, the fourth, to beef, the fifth, to grains and the sixth, to dairy. In general, benefits and costs are divided into both demand and supply side effects. In addition, both public and private costs and benefits are considered, especially since they help indicate where a role for government might be required and where markets are not working as well as they might. Based on these preliminary qualitative assessments, the beef and pork sector have more to gain from HACCP-based OFFS and EFP initiatives, due to their ability to gain market share from marketing their products internationally, while the grains sector already benefits internationally from its high quality reputation and the dairy sector is restricted to produce only for the domestic market. However, more work is required in these areas to validate and quantify costs and benefits.Agribusiness, Agricultural and Food Policy, Environmental Economics and Policy, Food Consumption/Nutrition/Food Safety, Production Economics, Resource /Energy Economics and Policy,

Infrared constraints on the dark mass concentration observed in the cluster Abell 1942

We present a deep H-band image of the region in the vicinity of the cluster Abell 1942 containing the puzzling dark matter concentration detected in an optical weak lensing study by Erben et al. (2000). We demonstrate that our limiting magnitude, H=22, would be sufficient to detect clusters of appropriate mass out to redshifts comparable with the mean redshift of the background sources. Despite this, our infrared image reveals no obvious overdensity of sources at the location of the lensing mass peak, nor an excess of sources in the I-H vs. H colour-magnitude diagram. We use this to further constrain the luminosity and mass-to-light ratio of the putative dark clump as a function of its redshift. We find that for spatially-flat cosmologies, background lensing clusters with reasonable mass-to-light ratios lying in the redshift range 0<z<1 are strongly excluded, leaving open the possibility that the mass concentration is a new type of truly dark object.Comment: 8 pages, 7 figures. MNRAS submitted (after referee revision

Dementia Prevalence Estimates in Sub-Saharan Africa: Comparison of two Diagnostic Criteria.

We have previously reported the prevalence of dementia in older adults living in the rural Hai district of Tanzania according to the Diagnostic and Statistical Manual of Mental Disorders, 4th edition (DSM-IV) criteria. The aim of this study was to compare prevalence rates using the DSM-IV criteria with those obtained using the 10/66 diagnostic criteria, which is specifically designed for use in low- and middle-income countries. In phase I, 1,198 people aged 70 and older were screened for dementia. A stratified sample of 296 was then clinically assessed for dementia according to the DSM-IV criteria. In addition, data were collected according to the protocol of the 10/66 Dementia Research Group, which allowed a separate diagnosis of dementia according to these criteria to be established. The age-standardised prevalence of clinical DSM-IV dementia was 6.4% (95% confidence interval [CI] 4.9-7.9%) and of '10/66 dementia' was 21.6% (95% CI 17.5-25.7%). Education was a significant predictor of '10/66 dementia', but not of DSM-IV dementia. There are large discrepancies in dementia prevalence rates depending on which diagnostic system is used. In rural sub-Saharan Africa, it is not clear whether the association between education and dementia using the 10/66 criteria is a genuine effect or the result of an educational bias within the diagnostic instrument. Despite its possible flaws, the DSM-IV criteria represent an international standard for dementia diagnosis. The 10/66 diagnostic criteria may be more appropriate when identification of early and mild cognitive impairment is required

Tuning hole mobility in InP nanowires

Transport properties of holes in InP nanowires were calculated considering electron-phonon interaction via deformation potentials, the effect of temperature and strain fields. Using molecular dynamics, we simulate nanowire structures, LO-phonon energy renormalization and lifetime. The valence band ground state changes between light- and heavy-hole character, as the strain fields and the nanowire size are changed. Drastic changes in the mobility arise with the onset of resonance between the LO-phonons and the separation between valence subbands.Comment: 4 pages, 4 figure

Field and Forage Crop Fertilization in the Rio Grande Plains.

4 p

Field and Forage Crop Fertilization in the Lower Rio Grande Valley.

4 p

EPR spectroscopy of iron- and nickel-doped [ZnAl]-layered double hydroxides: modeling active sites in heterogeneous water oxidation catalysts

Iron-doped nickel layered double hydroxides (LDHs) are among the most active heterogeneous water oxidation catalysts. Due to inter-spin interactions, however, the high density of magnetic centers results in line-broadening in magnetic resonance spectra. As a result, gaining atomic-level insight into the catalytic mechanism via electron paramagnetic resonance (EPR) is not generally possible. To circumvent spin-spin broadening, iron and nickel atoms were doped into non-magnetic [ZnAl]-LDH materials and the coordination environments of the isolated Fe(III) and Ni(II) sites were characterized. Multifrequency EPR spectroscopy identified two distinct Fe(III) sites (S = 5/2) in [Fe:ZnAl]-LDH. Changes in zero field splitting (ZFS) were induced by dehydration of the material, revealing that one of the Fe(III) sites is solvent-exposed (i.e. at an edge, corner, or defect site). These solvent-exposed sites feature an axial ZFS of 0.21 cm⁻¹ when hydrated. The ZFS increases dramatically upon dehydration (to -1.5 cm⁻¹), owing to lower symmetry and a decrease in the coordination number of iron. The ZFS of the other (“inert”) Fe(III) site maintains an axial ZFS of 0.19-0.20 cm⁻¹ under both hydrated and dehydrated conditions. We observed a similar effect in [Ni:ZnAl]-LDH materials; notably, Ni(II) (S = 1) atoms displayed a single, small ZFS (±0.30 cm⁻¹) in hydrated material, whereas two distinct Ni(II) ZFS values (±0.30 and ±1.1 cm⁻¹) were observed in the dehydrated samples. Although the magnetically-dilute materials were not active catalysts, the identification of model sites in which the coordination environments of iron and nickel were particularly labile (e.g. by simple vacuum drying) is an important step towards identifying sites in which the coordination number may drop spontaneously in water, a probable mechanism of water oxidation in functional materials