Tailoring Gold Nanoparticle Characteristics and the Impact on Aqueous-Phase Oxidation of Glycerol

Poly(vinyl alcohol) (PVA)-stabilized Au nanoparticles (NPs) were synthesized by colloidal methods in which temperature variations (−75 to 75 °C) and mixed H2O/EtOH solvent ratios (0, 50, and 100 vol/vol) were used. The resulting Au NPs were immobilized on TiO2 (P25), and their catalytic performance was investigated for the liquid phase oxidation of glycerol. For each unique solvent system, there was a systematic increase in the average Au particle diameter as the temperature of the colloidal preparation increased. Generation of the Au NPs in H2O at 1 °C resulted in a high observed activity compared with current Au/TiO2 catalysts (turnover frequency = 915 h–1). Interestingly, Au catalysts with similar average particle sizes but prepared under different conditions had contrasting catalytic performance. For the most active catalyst, aberration-corrected high angle annular dark field scanning transmission electron microscopy analysis identified the presence of isolated Au clusters (from 1 to 5 atoms) for the first time using a modified colloidal method, which was supported by experimental and computational CO adsorption studies. It is proposed that the variations in the populations of these species, in combination with other solvent/PVA effects, is responsible for the contrasting catalytic properties

Operando Spectroscopic Studies of Cu–SSZ-13 for NH3–SCR deNOx Investigates the Role of NH3 in Observed Cu(II) Reduction at High NO Conversions

The small pore zeolite chabazite (SSZ-13) in the copper exchanged form is a very efficient material for the selective catalytic reduction by ammonia (NH 3 ) of nitrogen oxides (NOx) from the exhaust of lean burn engines, typically diesel powered vehicles. The full mechanism occurring during the NH 3 –SCR process is currently debated with outstanding questions including the nature and role of the catalytically active sites. Time-resolved operando spectroscopic techniques have been used to provide new level of insights in to the mechanism of NH 3 –SCR, to show that the origin of stable Cu(I) species under SCR conditions is potentially caused by an interaction between NH 3 and the Cu cations located in eight ring sites of the bulk of the zeolite and is independent of the NH 3 –SCR of NOx occurring at Cu six ring sites within the zeolite

In-depth characterisation of metal-support compounds in spent Co/SiO2 Fischer-Tropsch model catalysts

Only little is known about the formation and morphology of metal-support compounds (MSCs) in heterogeneous catalysis. This fact can be mostly ascribed to the challenges in directly identifying these phases. In the present study, a series of Co/SiO2 model catalysts with different crystallite sizes was thoroughly characterised with focus on the identification of cobalt silicate, which is the expected metal-support compound for this particular catalyst system. The catalysts were exposed to simulated high conversion Fischer-Tropsch environment, i.e. water-rich conditions in the presence of hydrogen. The transformation of significant amounts of metallic cobalt to a hard-to-reduce phase has been observed. This particular MSC, Co2SiO4, was herein identified as needle- or platelet-type cobalt silicate structures by means of X-ray spectroscopy (XAS) and high-resolution scanning transmission electron microscopy (HRSTEM) in combination with elemental mapping. The metal-support compounds formed on top of fully SiO2-encapsulated nanoparticles, which are hypothesised to represent a prerequisite for the formation of cobalt silicate needles. Both, the encapsulation of cobalt nanoparticles by SiO2 via creeping, as well as the formation of these structures, were seemingly induced by high concentrations of water

Comparing Diet and Exercise Monitoring Using Smartphone App and Paper Diary: A Two-Phase Intervention Study

Background: There is increasing recognition that personalized approaches may be more effective in helping people establish healthier eating patterns and exercise more, and that this approach may be particularly effective in adolescents. Objective: The objective of this study was to investigate the use of a smartphone app (FoodWiz2) in supporting healthy lifestyle choices in adolescence. Methods: Participants (N=34: 11 male, 23 female) aged 16-19 years in full- or part-time education were recruited from sixth form colleges, schools, and other further education establishments in Norfolk and Suffolk, United Kingdom, between February and May 2015. Participants recorded food intake and exercise using a paper diary for 4-5 weeks and then used the app for the same duration. Initial nutrition education and general support were provided during the paper diary use, but the app included personalized messages sent in response to app activity. At the end of each study phase, participants completed an online questionnaire to describe their experience of using the paper diary and app. Results: Record completion declined throughout the study, possibly affected by examination pressure. Food intake data showed increased fruit consumption and significantly reduced consumption of chocolate snacks (P=.01) and fizzy drinks (P=.002) among participants using the app. Questionnaire responses indicated that the app was generally preferred to the paper diary, in particular, the app was seen as less boring to use (P=.03) and more acceptable in social settings (P<.001). Conclusions: This app-based approach has shown the potential for a more effective approach to improving adolescent diet and exercise levels

Electrochemical upgrading of biomass-derived 5-hydroxymethylfurfural and furfural over oxygen vacancy-rich NiCoMn-layered double hydroxides nanosheets

Rational design of low-cost and active electrocatalysts is crucial for upgrading of biomass-derived chemicals. Here, we report highly efficient catalysts ternary NiCoMn-layered double hydroxides (NiCoMn-LDHs) nanosheets which are oxygen vacancy-rich, produced under controllable conditions for the electrooxidation of both 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) and furfural to furoic acid (FurAc) under mild conditions, respectively. Electrochemical tests showed that the oxidation of HMF and furfural occurred prior to the oxidation of water at lower applied potentials with NiCoMn-LDHs catalysts. High yields of FDCA (91.7%) and FurAc (92.4%) were achieved in 2.5 h using 1.15 nm thick NiCoMn-LDHs nanosheets under the optimal conditions. The mechanism for the superior performance, high durability, and good faradaic efficiency has been elucidated by comprehensive characterization, which confirmed that ultrathin nanosheets expose more Co-NiOOH active sites with oxygen vacancies, facilitating the synergistic effect between HMF and furfural oxidation reaction on Co–Ni and Mn2+ states. The oxygen vacancy-rich NiCoMn-LDHs nanosheet catalysts present a novel and energy-efficient solution to obtain upgraded biochemicals

CD28 down-regulation on circulating CD4 T-cells is associated with poor prognoses of patients with idiopathic pulmonary fibrosis

Background: Although the etiology of idiopathic pulmonary fibrosis (IPF) remains perplexing, adaptive immune activation is evident among many afflicted patients. Repeated cycles of antigen-induced proliferation cause T-cells to lose surface expression of CD28, and we hypothesized this process might also occur in IPF. Methodology/Principal Findings: Peripheral blood CD4 T-cells from 89 IPF patients were analyzed by flow cytometry and cytokine multiplex assays, and correlated with clinical events. In comparison to autologous CD4 +CD28+cells, the unusual CD4+CD28 null lymphocytes seen in many IPF patients had discordant expressions of activation markers, more frequently produced cytotoxic mediators perforin (2.4±0.8% vs. 60.0±7.4%, p<0.0001) and granzyme B (4.5±2.8% vs.74.9±6.5%, p<0.0001), produced greater amounts of many pro-inflammatory cytokines, and less frequently expressed the regulatory T-cell marker FoxP3 (12.9±1.1% vs. 3.3±0.6% p<0.0001). Infiltration of CD4+CD28null T-cells in IPF lungs was confirmed by confocal microscopy. Interval changes of CD28 expression among subjects who had replicate studies were correlated with conterminous changes of their forced vital capacities (rs = 0.49, p = 0.012). Most importantly, one-year freedom from major adverse clinical events (either death or lung transplantation) was 56±6% among 78 IPF patients with CD4 +CD28+/CD4total≥82%, compared to 9±9% among those with more extensive CD28 down-regulation (CD4+CD28 +/CD4total<82%) (p = 0.0004). The odds ratio for major adverse events among those with the most extensive CD28 down-regulation was 13.0, with 95% confidence intervals 1.6-111.1. Conclusions/Significance: Marked down-regulation of CD28 on circulating CD4 T-cells, a result of repeated antigen-driven proliferations, is associated with poor outcomes in IPF patients. The CD4+CD28null cells of these patients have potentially enhanced pathogenic characteristics, including increased productions of cytotoxic mediators and pro-inflammatory cytokines. These findings show proliferative T-cell responses to antigen(s) resulting in CD28 down-regulation are associated with progression and manifestations of IPF, and suggest assays of circulating CD4 T-cells may identify patients at greatest risk for clinical deterioration. © 2010 Gilani et al

Investigation of MoOx/Al2O3 under Cyclic Operation for Oxidative and Non-Oxidative Dehydrogenation of Propane

A MoOx/Al2O3 catalyst was synthesised and tested for oxidative (ODP) and non-oxidative (DP) dehydrogenation of propane in a reaction cycle of ODP followed by DP and a second ODP run. Characterisation results show that the fresh catalyst contains highly dispersed Mo oxide species in the +6 oxidation state with tetrahedral coordination as [MoVIO4]2− moieties. In situ X-ray Absorption Spectroscopy (XAS) shows that [MoVIO4]2− is present during the first ODP run of the reaction cycle and is reduced to MoIVO2 in the following DP run. The reduced species are partly re-oxidised in the subsequent second ODP run of the reaction cycle. The partly re-oxidised species exhibit oxidation and coordination states that are lower than 6 but higher than 4 and are referred to as MoxOy. These species significantly improved propene formation (relatively 27% higher) in the second ODP run at similar propane conversion activity. Accordingly, the initial tetrahedral [MoVIO4]2− present during the first ODP run of the reaction cycle is active for propane conversion; however, it is unselective for propene. The reduced MoIVO2 species are relatively less active and selective for DP. It is suggested that the MoxOy species generated by the reaction cycle are active and selective for ODP. The vibrational spectroscopic data indicate that the retained surface species are amorphous carbon deposits with a higher proportion of aromatic/olefinic like species

Operando XAFS investigation on the effect of ash deposition on three-way catalyst used in gasoline particulate filters and the effect of the manufacturing process on the catalytic activity

Platinum group metals such as palladium and rhodium based catalysts are currently being implemented in gasoline particulate filter (GPF) autoexhaust after treatment systems. However, little is known about how the trapped particulate matter, such as the incombustible ash, interacts with the catalyst and so may affect its performance. This operando study follows the evolution of the Pd found in two different model GPF systems: one containing ash components extracted from a GPF and another from a catalyst washcoat prior to adhesion onto the GPF. We show that the catalytic activity of the two systems vary when compared with a 0 g ash containing GPF. Compared to the 0 g ash sample the 20 g ash containing sample had a higher CO light off temperature, in addition, an oscillation profile for CO, CO2 and O2 was observed, which is speculated to be a combination of CO oxidation, C deposition via a Boudouard reaction and further partial oxidation of the deposited species to CO. During the ageing procedure the washcoat sample reduces NO at a lower temperature than the 0 g ash sample. However, post ageing the 0 g ash sample recovers and both samples reduce NO at 310 °C. In comparison, the 20 g ash GPF sample maintains a higher NO reduction temperature of 410 °C post ageing, implying that the combination of high temperature ageing and presence of ash has an irreversible negative effect on catalyst performance

A transit timing analysis of seven RISE light curves of the exoplanet system HAT-P-3

We present seven light curves of the exoplanet system HAT-P-3, taken as part of a transit timing programme using the rapid imager to search for exoplanets instrument on the Liverpool Telescope. The light curves are analysed using a Markov chain Monte Carlo algorithm to update the parameters of the system. The inclination is found to be i= 86.75+0.22−0.21 °, the planet-star radius ratio to be Rp/R★= 0.1098+0.0010−0.0012 and the stellar radius to be R★= 0.834+0.018−0.026 R⊙, consistent with previous results but with a significant improvement in the precision. Central transit times and uncertainties for each light curve are also determined, and a residual permutation algorithm is used as an independent check on the errors. The transit times are found to be consistent with a linear ephemeris, and a new ephemeris is calculated as Tc(0) = 245 4856.701 18 ± 0.000 18 HJD and P= 2.899 738 ± 0.000 007 d. Model timing residuals are fitted to the measured timing residuals to place upper mass limits for a hypothetical perturbing planet as a function of the period ratio. These show that we have probed for planets with masses as low as 0.33 and 1.81 M⊕ in the interior and exterior 2:1 resonances, respectively, assuming the planets are initially in circular orbits