An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates

The CO_{2} electro-reduction reaction (CORR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long known to be unique in their capabilities of catalyzing the conversion of CO_{2} to higher-order C1 and C2 fuels, such as hydrocarbons (CH_{4}, C_{2}H_{4} etc.) and alcohols (CH_{3}OH, C_{2}H_{5}OH), product selectivity remains a challenge. In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced infrared absorption spectroscopy (SEIRAS) and ambient-pressure X-ray photoelectron spectroscopy (APXPS), coupled to density-functional theory (DFT) calculations, to get insight into the reaction pathway for the CORR. We present a comprehensive reaction mechanism for the CORR, and show that the preferential reaction pathway can be rationalized in terms of metal-carbon (M-C) and metal-oxygen (M-O) affinity. We show that the final products are determined by the configuration of the initial intermediates, C-bound and O-bound, which can be obtained from CO_{2} and (H)CO_{3}, respectively. C1 hydrocarbons are produced via OCH_{3, ad} intermediates obtained from O-bound CO_{3, ad} and require a catalyst with relatively high affinity for O-bound intermediates. Additionally, C2 hydrocarbon formation is suggested to result from the C-C coupling between C-bound CO_{ad} and (H)CO_{ad}, which requires an optimal affinity for the C-bound species, so that (H)CO_{ad} can be further reduced without poisoning the catalyst surface. Our findings pave the way towards a design strategy for CORR catalysts with improved selectivity, based on this experimental/theoretical reaction mechanisms that have been identified

3-(1,3-Benzodioxol-5-yl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine

In the title compound, C25H19NO3, the oxazine ring displays a half-chair conformation. The fused benzene ring is nearly parallel to the naphthyl ring system, the dihedral angle between this benzene ring and the naphthyl system being 8.52 (11)°. The imino group is not involved in hydrogen bonding in the crystal structure

Non-covalent interactions in electrochemical reactions and implications in clean energy applications

Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provide new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion and storage devices. Here, we report systematic changes in the redox entropy of one-electron transfer reactions including [Fe(CN)6]3-/4-, [Fe(H2O)6]3+/2+and [Ag(H2O)4]+/0induced by the addition of redox inactive ions, where approximately twenty different known structure making/breaking ions were employed. The measured reaction entropy changes of these redox couples were found to increase linearly with higher concentration and greater structural entropy (having greater structure breaking tendency) for inactive ions with opposite charge to the redox centers. The trend could be attributed to the altered solvation shells of oxidized and reduced redox active species due to non-covalent interactions among redox centers, inactive ions and water molecules, which was supported by Raman spectroscopy. Not only were these non-covalent interactions shown to increase reaction entropy, but they were also found to systematically alter the redox kinetics, where increasing redox reaction energy changes associated with the presence of water structure breaking cations were correlated linearly with the greater exchange current density of [Fe(CN)6]3-/4-.United States. Department of Energy. Office of Basic Energy Science (Award Number DE-SC0001299/DE-FG02-09ER46577)Hong Kong (China). Innovation and Technology Commission (Project No. ITS/ 020/16FP)United States. Department of Energy (Contract No. DE-AC02-5CH11231

Orally administered low-molecular weight agaro-oligosaccharides are absorbed into the plasma of healthy humans

Agaro-oligosaccharides (AOSs) are known to have biological activities, such as anti-inflammatory, anti-tumor, and anti-obesity effects. Although existing evidence suggests the presence of AOSs in peripheral tissues after oral administration, whether AOSs permeate into the blood circulation remains unknown. Thus, we hypothesized that AOSs with low-molecular weight can permeate the human gastrointestinal tract. To test this hypothesis, the time course of absorption was examined by analyzing plasma samples before and 1, 2, and 4 h after ingestion. Analysis was performed using liquid chromatography/mass spectrometry after labeling with p-aminobenzoic ethyl ester. Our results showed that the plasma concentration of agarobiose (Abi) was higher than that of agarotetraose (Ate); however, agarohexaose was not detected. Additionally, plasma levels of Abi and Ate were proportional to the dose. These results suggest that permeation efficiency is dependent on the molecular weight and that the systemic absorption of Abi via the gastrointestinal tract is better than that of Ate. These findings will contribute to a better understanding of the bioactivity of orally administered AOSs in peripheral tissues

The change of plasma C-reactive protein and metabolite concentrations, and MPS sick degree score in Landrase selected for resistance to MPS, Large Yorkshire selected for immune performances and the crossbreed

Swine Mycoplasma Hyopneumoniea, hp, is known as a major factor to affect for the specific pneumonia (MPS). This damages is very serious because carrier rate of hp in piglets from 3 to 4 months of age is very high, the rate of piglets that the response of antibody to hp shows positive is 80 % over, and the rate that has very terrible tissue from MPS is 51% in Japanese pig farm. We bred a resistant strain to MPS by selection to decrease MPS pathogenic condition over 5 generations using Landrase (MPS strain), and a high immune performance strain by selection for peripheral phagocytosis, complement activity and antibody production against erysipelatous vaccine using Large Yorkshire (HI strain)

Localized states in 2D semiconductors doped with magnetic impurities in quantizing magnetic field

A theory of magnetic impurities in a 2D electron gas quantized by a strong magnetic field is formulated in terms of Friedel-Anderson theory of resonance impurity scattering. It is shown that this scattering results in an appearance of bound Landau states with zero angular moment between the Landau subbands. The resonance scattering is spin selective, and it results in a strong spin polarization of Landau states, as well as in a noticeable magnetic field dependence of the $g$ factor and the crystal field splitting of the impurity $d$ levels.Comment: 12 pages, 4 figures Submitted to Physical Review B This version is edited and updated in accordance with recent experimental dat