The catalytic nanodiode. Its role in catalytic reaction mechanisms in a historical perspective

Catalytic nanodiodes, Pt/TiO₂ or Pt/GaN produce continuous flow of hot electron current during carbon monoxide oxidation for hours in the 80–150 °C temperature range at pressures of 100 Torr of O₂ and 40 Torr of CO. These observations provide proof of the Schottky diode model of oxide supported metal catalysis of many reactions that have been proposed by Schwab, Solymosi and others since the 1960s. The flow of hot electrons should influence chemistry at oxide–metal interfaces and the metal particle size dependence of catalytic activity and selectivity.     

Dispersion of TiO2 Particles in PET/PP/TiO2 and PET/PP/PP‐g‐MA/TiO2 Composites Prepared with Different Blending Procedures

2 vol.‐% TiO₂ particles were incorporated into PET/PP blends with and without MA‐grafted PP compatibilizer. During extrusion of the PET/PP/TiO₂ composites the TiO₂ particles migrated from the PP matrix to the PET‐dispersed phase irrespective of the blending route. For the PET/PP/PP‐g‐MA/TiO₂ composites, however, the location of TiO₂ depended on the blending sequence. The preferred location of the TiO₂ nanoparticles was confirmed by SEM pictures taken from the chemically etched surface of the blends. The observed migration behavior was traced to differences in the interfacial tensions between TiO₂ and PET and TiO₂ and PP, and to TiO₂ encapsulation in one of the blend components during the related blending procedure.

     

Compensation Effect of Benzene Hydrogenation on Pt(111) and Pt(100) Analyzed by the Selective Energy Transfer Model

Kinetic measurements at low temperatures (310–360 K) using gas chromatography (GC) for benzene hydrogenation on Pt(100) and Pt(111) single crystal surfaces have been carried out at Torr pressures. These kinetic measurements demonstrated a linear compensation effect for the production of cyclohexane. A detailed application of the model of selective energy transfer to the experimentally obtained results yields the vibrational frequency of the adsorbate leading to reaction. This frequency is attributed to ring distortion modes. The vibrational frequency of the heat bath, or catalyst, is ascribed to a Pt-H mode. An approximate heat of adsorption of the reacting molecule is also calculated from the model.     

Metallic Nanoparticles in Heterogeneous Catalysis

Catalysis Letters - Heterogeneous catalysis is a chemical process achieved at solid–gas or solid–liquid interfaces. Many factors including the particle size, shape and metal-support...     

Mechanisms of heat transfer between a surface and a gas-fluidized bed for combustor application

There is currently considerable interest in the development of fluidized-bed boilers for efficient and environmentally clean combustion of coal. Fluidized beds have the advantages of high heat transfer rates and intimate mixing of additives such as limestone or dolomite for sulfur dioxide absorption produced as a result of combustion of coal containing sulfur. However, design for optimum heat transfer remains uncertain and essentially empirical. The mechanisms of heat transfer are complicated because of the many variables in a commercial combustion operation such as particle size distribution, particle shape, particle and gas thermal properties, reactor geometry and boiler tube design.An understanding of the mechanisms of bed to tube heat transfer is essential to sound design and interpretation of empirically derived correlations. Here we will review and criticize the major mechanisms of heat transfer that have been proposed. These mechanisms are proposed and developed from two schools of thought: (a) The principal resistance to heat transfer is a fluid film, and the moving fluidized particles scour the film to reduce the resistance to heat transfer; (b) Heat is absorbed by the fluidized particles and the rate of heat transfer depends on the rate of heat absorption.Radiant heat transfer is also discussed in this review in detail. Heat transfer by radiation is an important consideration in combustors but has received limited attention. The results of theoretical calculations are given which have been recently reported on the basis of the alternate-slab model of Gabor.The review will predominantly deal with the mechanistic models of heat transfer and various correlations developed over years will not be covered as this topic is dealt with in another review article by Saxena, Grewal, Gabor, Zabrodsky and Galershtein.     

Assessment of edema using STIR+ via 3D cardiovascular magnetic resonance imaging in patients with suspected myocarditis

Objective

To evaluate three-dimensional T2-weighted fast spin echo triple inversion recovery sequences (STIR+) for the diagnosis of myocardial edema in patients with suspected early myocarditis after respiratory or gastrointestinal tract viral infection and at follow-up.

Materials and methods

We prospectively examined 28 patients with suspected myocarditis and 37 controls matched for gender and age. An ECG-triggered STIR+ was used to cover the entire left ventricle in short-axis images with 10-mm slice thickness and no interslice gap. The global signal intensity ratio (heart muscle in relation to skeletal muscle) was calculated (global STIR+ ratio) to evaluate edema. All patients had repeat examinations at follow-up (mean interval 4.9 months, 1–12 months).

Results

The mean global STIR+ ratio was 2.15 ± 0.4 in the initial examination of patients as compared to 1.78 ± 0.3 in controls (p < 0.0001) and 1.89 ± 0.3 in patients at follow-up (p = 0.0001 vs. first visit). Left ventricular ejection fraction did not differ between patients and controls at baseline and at follow-up.

Conclusion

We could identify a significantly higher global STIR+ ratio in patients with suspected myocarditis compared to controls, and a dynamic change during follow-up. The global STIR+ ratio may, therefore, be useful for the diagnosis of myocarditis and should be further explored.

     

Effect of moisture and filler content on the structural,thermal and dielectric properties of polyamide‐6/boehmite alumina nanocomposites

Polyamide‐6 (PA‐6)/boehmite alumina (BA) nanocomposites were prepared via direct melt compounding. Structural, thermal and dielectric properties of ‘as‐received’ (including moisture) and ‘dried’ (thermally treated) specimens were examined. The BA nanofiller was homogeneously dispersed in the PA‐6 matrix. XRD and FTIR revealed that crystallization of PA‐6 in the γ phase was favoured over α phase with increasing BA content. The crystallinity index (CI) and the percentage of α and γ phases were also evaluated. Dried specimens exhibited a lower CI than as‐received specimens while the CI decreased with the addition of filler. Broadband dielectric spectroscopy revealed the presence of γ, β and α relaxations, the Maxwell–Wagner–Sillars effect and the contribution of conductivity relaxation in the as‐received samples. The drying procedure unmasked a double feature of both β and α modes. The results of the complementary techniques were analysed and the effects of moisture and/or the incorporation of BA nanofiller on the microstructure of the PA‐6 matrix are disclosed. © 2019 Society of Chemical Industry     

Shape memory crosslinked polyurethanes containing thermoreversible Diels‐Alder couplings

Crosslinked polyurethanes (PUs) containing irreversible (allophanate) and reversible Diels‐Alder chemical bonds were synthesized using various diisocyanates (methylene diphenyl diisocyanate MDI, 1,6‐hexamethylenediisocyanate HDI) and poly(?‐caprolactone) ((PCL) with different molecular weights (M_n = 10 kg/mol, 25 kg/mol, 50 kg/mol) as diol component. The melting/crystallization of PCL and the reversible DA bonds acted as temperature‐activated switches for shape memory performances, while allophanate network provided the permanent crosslinks for these PUs. The reversible DA bonds were obtained by the reaction of diisocyanate‐ended prepolymers with furfurylamine (FA) followed by the addition of bismaleimide (BMI). The permanent crosslinks between the linear chains containing DA bonds were achieved using additional amounts of diisocyanates (MDI or HDI). The above reaction path was supported by infrared spectroscopic results and swelling experiments. Tensile mechanical and shape memory properties in tension of the PUs were determined and discussed as a function of composition and crosslink densities deduced from swelling and dynamic mechanical analysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44145.