Origin of the polychromatic photoluminescence of zeolite confined Ag clusters: temperature- and co-cation-dependent luminescence

Zeolite confined silver clusters (AgCLs) have attracted extensive attention due to their remarkable luminescent properties, but the elucidation of the underlying photophysical processes and especially the excited-state dynamics remains a challenge. Herein, we investigate the bright photoluminescence of AgCLs confined in Linde Type A zeolites (LTA) by systematically varying the temperature (298–77 K) and co-cation composition (Li/Na) and examining their respective influence on the steady-state and time-resolved photoluminescence. The observed polychromatic emission of the tetrahedral Ag₄(H₂O)_n²⁺ clusters ranges from orange to violet and three distinct emitting species are identified, corresponding to three long-lived triplet states populated consecutively and separated by a small energy barrier. These long-lived species are at the origin of the polychromatic luminescence with high photoluminescence quantum yields. Furthermore, the Li-content dependence of decay times points to the importance of guest–host–guest interactions in tuning the luminescent properties with a 43% decrease of the dominating decay time by increasing Li content. Based on our findings, a simplified model for the photophysical kinetics is proposed that identifies the excited-state processes. The results outlined here pave the way for a rational design of confined metal clusters in various frames and inspire the specified applications of Ag-zeolites.

The temperature- and co-cation-dependent photoluminescence of zeolite confined Ag clusters was systematically investigated. Bright polychromatic emission and intriguing excited-state dynamics were observed and a kinetic model was proposed.     

Blowup of solutions of the unsteady Prandtl's equation

We prove that for certain classes of compactly supported C^∞ initial data, smooth solutions of the unsteady Prandtl's equation blow up in finite time. © 1997 John Wiley & Sons, Inc.     

Direct electro-deposition of graphene from aqueous suspensions

We describe the direct electro-chemical reduction of graphene oxide to graphene from aqueous suspension by applying reduction voltages exceeding -1.0 to -1.2 V. The conductivity of the deposition medium is of crucial importance and only values between 4-25 mS cm(-1) result in deposition. Above 25 mS cm(-1) the suspension de-stabilises while conductivities below 4 mS cm(-1) do not show a measurable deposition rate. Furthermore, we show that deposition can be carried out over a wide pH region ranging from 1.5 to 12.5. The electro-deposition process is characterised in terms of electro-chemical methods including cyclic voltammetry, quartz crystal microbalance, impedance spectroscopy, constant amperometry and potentiometric titrations, while the deposits are analysed via Raman spectroscopy, infra-red spectroscopy, X-ray photoelectron spectroscopy and X-ray diffractometry. The determined oxygen contents are similar to those of chemically reduced graphene oxide, and the conductivity of the deposits was found to be ～20 S cm(-1).     

Catalytic asymmetric synthesis of mycocerosic acid

The first catalytic asymmetric total synthesis of mycocerosic acid was achieved via the application of iterative enantioselective 1,4-addition reactions and allows for the efficient construction of 1,3-polymethyl arrays with full stereocontrol; further exemplified by the synthesis of tetramethyl-decanoic acid, a component of the preen-gland wax of the graylag goose, Anser anser.     

Note on Solutions of the Strominger System from Unitary Representations of Cocompact Lattices of {SL(2,\mathbb{C})}

This note is motivated by a recently published paper (Biswas and Mukherjee in Commun Math Phys 322(2):373–384, 2013). We prove a no-go result for the existence of suitable solutions of the Strominger system in a compact complex parallelizable manifold \({M = G/\Gamma}\) . For this, we assume G to be non-abelian, the Hermitian metric to be induced from a right invariant metric on G, the Bianchi identity to be satisfied using the Chern connection and furthermore the gauge field to be flat. In Biswas and Mukherjee (Commun Math Phys 322(2):373–384, 2013) it is claimed that one such solution exists on \({SL(2, \mathbb{C})/\Gamma}\) . Our result contradicts the main result in Biswas and Mukherjee (Commun Math Phys 322(2):373–384, 2013).     

Multiscale approach to CO2 hydrate formation in aqueous solution: phase field theory and molecular dynamics. Nucleation and growth

A phase field theory with model parameters evaluated from atomistic simulations/experiments is applied to predict the nucleation and growth rates of solid CO(2) hydrate in aqueous solutions under conditions typical to underwater natural gas hydrate reservoirs. It is shown that under practical conditions a homogeneous nucleation of the hydrate phase can be ruled out. The growth rate of CO(2) hydrate dendrites has been determined from phase field simulations as a function of composition while using a physical interface thickness (0.85+/-0.07 nm) evaluated from molecular dynamics simulations. The growth rate extrapolated to realistic supersaturations is about three orders of magnitude larger than the respective experimental observation. A possible origin of the discrepancy is discussed. It is suggested that a kinetic barrier reflecting the difficulties in building the complex crystal structure is the most probable source of the deviations.     

A simple equilibrium model for shallow-cumulus-topped mixed layers

A new equilibrium model for shallow-cumulus-topped mixed layers is presented. A variant on the w _* closure for the shallow-cumulus mass flux is applied that retains the convective area-fraction in its formulation. As opposed to being constant, the fraction is explicitly modeled using a statistical closure as a function of the saturation deficit and humidity variance at cloud base. As a consequence, important new interactions are introduced between the convective transport, humidity, and depth of the mixed layer. This mechanism, which we call the mass-flux humidity feedback, helps determine the character of the equilibrium state such that the mixed-layer top is maintained close to the cloud-base height. Due to the strong sensitivity of the mass flux to the area fraction, the latter thus acts as a regulator or valve mechanism on moist convective transport. As a consequence, the mixed-layer model is able to explain the robustness of many aspects of the shallow-cumulus boundary layer that is typically found in observations and large-eddy simulations (LESs). The model is evaluated for a single-LES case as well as for global climatology obtained from a 40-year reanalysis of meteorological data by the European Centre for Medium-range Weather Forecasts (ECMWF). LES characteristics of convective mass flux, cloud fraction, humidity variance, cloud-base height, and surface fluxes of heat and humidity are reproduced. The solution on reanalysis fields reproduces the spatial structure of mixed-layer temperature and humidity and their associated surface fluxes in the subtropical Atlantic and Pacific trade wind regions. Furthermore, the spatial structure of the convective area-fraction matches that of synoptic surface observations of frequency of occurrence of shallow cumulus. Particularly striking is the smooth onset of the convective area-fraction and mass flux along the trade-wind trajectory that is reproduced, from zero to typical trade-wind values. The cumulus onset represents the necessity for shallow-cumulus mass flux to occur in order to close the mixed-layer budgets of heat, moisture, and mass, as a response to the changing magnitude of large-scale subsidence and free tropospheric humidity along the trajectory. Finally, the mass flux model is implemented in an intermediate-complexity tropical climate model to study its behavior when fully interactive with the larger-scale flow. A climate run then shows that the model is stable, due to the mass-flux humidity feedback acting to keep the shallow-cumulus boundary layer close to its equilibrium state for long, climatological timescales.     

Selective catalytic oxidation of organosulfur compounds with tert-butyl hydroperoxide

Rates and selectivities for the oxidation of various organosulfur compounds with tert-butyl hydroperoxide were measured on CoAPO-5 (APO = aluminophosphate; Co/P = 0.05), Co/H-Y (Co/Al = 0.15), and MoO(x)/Al2O3 (15 % wt MoO3). Rates increased with increasing electron density at the sulfur atom (methyl phenyl sulfide>diphenyl sulfide>4-methyldibenzothiophene>2,5-dimethyl thiophene). Rates (per metal atom) were significantly higher on CoAPO-5 than on Co/H-Y, MoO(x)/Al2O3, or homogeneous Co acetate catalysts. Small amounts of sulfoxides (1-oxide) were detected on all catalysts at low reactant conversions, together with their corresponding sulfones; at higher conversions, only sulfones (1,1-dioxide) were detected, indicating that the oxidation of sulfoxides is much faster than for organosulfur reactants in the sequential oxidation pathways prevalent on these catalysts. Framework Co cations were not leached from CoAPO-5 during the oxidation of 4-methyldibenzothiophene, but most exchanged Co cations in H-Y and >20 % of Mo cations in MoO(x)/Al2O3 were extracted during these reactions. The fraction of redox-active Co cations in CoAPO-5 and Co/H-Y was measured by reduction-oxidation cycles using H2 and O2 and by UV-visible spectroscopy. This fraction was much larger in CoAPO-5 (0.35) than in Co/H-Y (0.01), consistent with the higher oxidation rates measured on CoAPO-5 and with the involvement of redox-active species in kinetically-relevant steps in catalytic oxidation sequences. Redox-active Co cations at framework positions within accessible channels are required for catalytic activity and structural stability during oxidative desulfurization, whether hydroperoxides are used as reactants or as intermediates (when O2 is used as the oxidant).