Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Progress in the development of mesoporous solid acid and base catalysts for converting carbohydrates into platform chemicals

This chapter provides a general overview of recent studies on catalytic conversion of fructose, glucose, and cellulose to platform chemicals over porous solid acid and base catalysts, including zeolites, ion-exchange resins, heteropoly acids, as well as structured carbon, silica, and metal oxide materials. Attention is focused on the dehydration of glucose and fructose to HMF, isomerization of glucose to fructose, hydrolysis of cellulose to sugar, and glycosidation of cellulose to alkyl glucosides. The correlation of porous structure, surface properties, and the strength or types of acid or base with the catalyst activity in these reactions is discussed in detail in this chapter.

Optical communication based on the periodic nonlinear Fourier transform signal processing

In this work we introduce the periodic nonlinear Fourier transform (PNFT) and propose a proof-of-concept communication system based on it by using a simple waveform with known nonlinear spectrum (NS). We study the performance (addressing the bit-error-rate (BER), as a function of the propagation distance) of the transmission system based on the use of the PNFT processing method and show the benefits of the latter approach. By analysing our simulation results for the system with lumped amplification, we demonstrate the decent potential of the new processing method.

Synthesis of highly efficient and recyclable visible-light responsive mesoporous g-C3N4 photocatalyst via facile template-free sonochemical route

Herein we demonstrate a facile template-free sonochemical strategy to synthesize mesoporous g-C3N4 with a high surface area and enhanced photocatalytic activity. The TEM and nitrogen adsorption–desorption studies confirm mesoporous structure in g-C3N4 body. The photocatalytic activity of mesoporous g-C3N4 is almost 5.5 times higher than that of bulk g-C3N4 under visible-light irradiation. The high photocatalytic performance of the mesoporous g-C3N4 was attributed to the much higher specific surface area, efficient adsorption ability and the unique interfacial mesoporous structure which can favour the absorption of light and separation of photoinduced electron–hole pairs more effectively. A possible photocatalytic mechanism was discussed by the radicals and holes trapping experiments. Interestingly, the synthesized mesoporous g-C3N4 possesses high reusability. Hence the mesoporous g-C3N4 can be a promising photocatalytic material for practical applications in water splitting as well as environmental remediation.

Protocol optimization for the mild detemplation of mesoporous silica nanoparticles resulting in enhanced texture and colloidal stability

Porosity development of mesostructured colloidal silica nanoparticles is related to the removal of the organic templates and co-templates which is often carried out by calcination at high temperatures, 500-600 °C. In this study a mild detemplation method based on the oxidative Fenton chemistry has been investigated. The Fenton reaction involves the generation of OH radicals following a redox Fe3+/Fe2+ cycle that is used as catalyst and H2O2 as oxidant source. Improved material properties are anticipated since the Fenton chemistry comprises milder conditions than calcination. However, the general application of this methodology is not straightforward due to limitations in the hydrothermal stability of the particular system under study. The objective of this work is three-fold: 1) reducing the residual Fe in the resulting solid as this can be detrimental for the application of the material, 2) shortening the reaction time by optimizing the reaction temperature to minimize possible particle agglomeration, and finally 3) investigating the structural and textural properties of the resulting material in comparison to the calcined counterparts. It appears that the Fenton detemplation can be optimized by shortening the reaction time significantly at low Fe concentration. The milder conditions of detemplation give rise to enhanced properties in terms of surface area, pore volume, structural preservation, low Fe residue and high degree of surface hydroxylation; the colloidal particles are stable during storage. A relative particle size increase, expressed as 0.11%·h-1, has been determined.

Silica promoted self-assembled mesoporous aluminas. Impact of the silica precursor on the structural, textural and acidic properties

This paper investigates the effect of silica addition on the structural, textural and acidic properties of an evaporation induced self-assembled (EISA) mesoporous alumina. Two silica addition protocols were applied while maintaining the EISA synthesis route. The first route is based on the addition of a Na-free colloidal silica suspension (Ludox®), and the second method consists of the co-hydrolysis of tetraethyl orthosilicate (TEOS) with aluminium tri-sec-butoxide, to favour a more intimate mixing of the Al- and Si-hydrolysed species. The properties of the so derived materials were compared to the SiO2-free counterpart. The SiO2 addition was always beneficial from a structural and textural standpoint. TEOS appears to have a truly promoting effect; the ordering, surface area and pore volume are all improved. For Ludox®, the enhancement comes from the formation of smaller pores by a densification of the structure. The crystallization of γ-alumina depends on the interaction between the Al- and Si-species in the mesophase. Ludox®-based materials achieved crystallization at 750 °C but the intimate mixing in the TEOS-based mesophases shows a suppression of the phase transformation by 50-100 °C, with respect to the SiO2-free counterpart. This reduces the textural features substantially. For all SiO2-modified materials, the enhancement in the surface area is not accompanied by a concomitant improvement of total acidity, and the formation of weak Lewis acid sites was promoted. These effects were ascribed to SiO2 migration to the surface that blocks part of the acidity.

Detemplation of soft mesoporous silica nanoparticles with structural preservation

A mild protocol that allows the template removal of soft un-aged silica nanoparticles was investigated. After oxidizing the organic template by Fenton chemistry, a good structural preservation is only achieved when the material is equilibrated and dried in a low-surface tension solvent. This avoids excessive capillary stress induced by the high surface tension of water, a major component in the Fenton reaction medium. The Fenton reaction should be carried out under mild conditions as well; otherwise the sample deteriorates by extensive hydrolysis, and capillary stress, and the structural ordering diminishes severely. We propose employing 10 ppm Fe concentration at 70 °C for 24 h for the cetyltrimethylammonium bromide template. The proposed protocol involves 2 steps resulting in an overall significantly higher pore volume attributed to the wider pores and limited particle agglomeration, while the calcined counterpart evidences aggregation and loss of the hexagonal ordering. n-BuOH exchange is unnecessary when the mesophase is stabilized by ageing, as the structure resists the water capillary stress. © The Royal Society of Chemistry 2013.

Thermal counterflow in a periodic channel with solid boundaries

We perform numerical simulations of finite temperature quantum turbulence produced through thermal counterflow in superfluid 4He, using the vortex filament model. We investigate the effects of solid boundaries along one of the Cartesian directions, assuming a laminar normal fluid with a Poiseuille velocity profile, whilst varying the temperature and the normal fluid velocity. We analyze the distribution of the quantized vortices, reconnection rates, and quantized vorticity production as a function of the wall-normal direction. We find that the quantized vortex lines tend to concentrate close to the solid boundaries with their position depending only on temperature and not on the counterflow velocity. We offer an explanation of this phenomenon by considering the balance of two competing effects, namely the rate of turbulent diffusion of an isotropic tangle near the boundaries and the rate of quantized vorticity production at the center. Moreover, this yields the observed scaling of the position of the peak vortex line density with the mutual friction parameter. Finally, we provide evidence that upon the transition from laminar to turbulent normal fluid flow, there is a dramatic increase in the homogeneity of the tangle, which could be used as an indirect measure of the transition to turbulence in the normal fluid component for experiments.

Periodic polymer photonic bandgap structures for on-chip optical cavities

Integrated on-chip optical platforms enable high performance in applications of high-speed all-optical or electro-optical switching, wide-range multi-wavelength on-chip lasing for communication, and lab-on-chip optical sensing. Integrated optical resonators with high quality factor are a fundamental component in these applications. Periodic photonic structures (photonic crystals) exhibit a photonic band gap, which can be used to manipulate photons in a way similar to the control of electrons in semiconductor circuits. This makes it possible to create structures with radically improved optical properties. Compared to silicon, polymers offer a potentially inexpensive material platform with ease of fabrication at low temperatures and a wide range of material properties when doped with nanocrystals and other molecules. In this research work, several polymer periodic photonic structures are proposed and investigated to improve optical confinement and optical sensing. We developed a fast numerical method for calculating the quality factor of a photonic crystal slab (PhCS) cavity. The calculation is implemented via a 2D-FDTD method followed by a post-process for cavity surface energy radiation loss. Computational time is saved and good accuracy is demonstrated compared to other published methods. Also, we proposed a novel concept of slot-PhCS which enhanced the energy density 20 times compared to traditional PhCS. It combines both advantages of the slot waveguide and photonic crystal to localize the high energy density in the low index material. This property could increase the interaction between light and material embedded with nanoparticles like quantum dots for active device development. We also demonstrated a wide range bandgap based on a one dimensional waveguide distributed Bragg reflector with high coupling to optical waveguides enabling it to be easily integrated with other optical components on the chip. A flexible polymer (SU8) grating waveguide is proposed as a force sensor. The proposed sensor can monitor nN range forces through its spectral shift. Finally, quantum dot - doped SU8 polymer structures are demonstrated by optimizing spin coating and UV exposure. Clear patterns with high emission spectra proved the compatibility of the fabrication process for applications in optical amplification and lasing.

Síntese e caracterização de materiais mesoporosos para a captura de CO2: influência do óxido de níquel

Several materials are currently under study for the CO2 capture process, like the metal oxides and mixed metal oxides, zeolites, carbonaceous materials, metal-organic frameworks (MOF's) organosilica and modified silica surfaces. In this work, evaluated the adsorption capacity of CO2 in mesoporous materials of different structures, such as MCM-48 and SBA- 15 without impregnating and impregnated with nickel in the proportions 5 %, 10 % and 20 % (m/m), known as 5Ni-MCM-48, 10Ni-MCM-48, 20Ni-MCM-48 and 5Ni-SBA-15, 10NiSBA-15, 20Ni-SBA-15. The materials were characterized by means of X-ray diffraction (XRD), thermal analysis (TG and DTG), Fourier transform infrared spectroscopy (FT-IR), N2 adsorption and desorption (BET) and scanning electron microscopy (SEM) with EDS. The adsorption process was performed varying the pressure of 100 - 4000 kPa and keeping the temperature constant and equal to 298 K. At a pressure of 100 kPa, higher concentrations of adsorption occurred for the materials 5Ni-MCM-48 (0.795 mmol g-1 ) and SBA-15 (0.914 mmol g-1 ) is not impregnated, and at a pressure of 4000 kPa for MCM-48 materials (14.89 mmol g-1) and SBA-15 (9.97 mmol g-1) not impregnated. The results showed that the adsorption capacity varies positively with the specific area, however, has a direct dependency on the type and geometry of the porous structure of channels. The data were fitted using the Langmuir and Freundlich models and were evaluated thermodynamic parameters Gibbs free energy and entropy of the adsorption system

Study of Periodic and Quasi-Periodic Structures in Silicon-on-Insulator

In this thesis, a numerical design approach has been proposed and developed based on the transmission matrix method in order to characterize periodic and quasi-periodic photonic structures in silicon-on-insulator. The approach and its performance have been extensively tested with specific structures in 2D and its validity has been verified in 3D.

Dispersion and energy relations in periodic chains and grids

In this study wave propagation, dispersion relations, and energy relations for linear elastic periodic systems are analyzed. In particular, the dispersion relations for monoatomic chain of infinite dimension are obtained analytically by writing the Block-type wave equation for a unit cell in order to capture the dynamic behavior for chains under prescribed vibration. By comparing the discretized model (mass-spring chain) with the solid bar system, the nonlinearity of the dispersion relation for chain indicates that the periodic lattice is dispersive in contrast to the continuous rod, which is non dispersive. Further investigations have been performed considering one-dimensional diatomic linear elastic mass-spring chain. The dispersion relations, energy velocity, and group velocity have been derived. At certain range of frequencies harmonic plane waves do not propagate in contrast with monoatomic chain. Also, since the diatomic chain considered is a linear elastic chain, both of the energy velocity and the group velocity are identical. As long as the linear elastic condition is considered the results show zero flux condition without residual energy. In addition, this paper shows that the diatomic chain dispersion relations are independent on the unit cell scheme. Finally, an extension for the study covers the dispersion and energy relations for 2D- grid system. The 2x2 grid system show a periodicity of the dispersion surface in the wavenumber domain. In addition, the symmetry of the surface can be exploited to identify an Irreducible Brillouin Zone (IBZ). Compact representations of the dispersion properties of multidimensional periodic systems are obtained by plotting frequency as the wave vector’s components vary along the boundary of the IBZ, which leads to a widely accepted and effective visualization of bandgaps and overall dispersion properties.

Direct synthesis of methanol by partial oxidation of methane with oxygen over cobalt modified mesoporous H-ZSM-5 catalyst

Peer reviewed

A generalised formulation for computing the microbuckling load in periodic layered materials

Acknowledgments The financial support of the part of this research by The Royal Society, The Royal Academy of Engineering and The Carnegie Trust for the Universities of Scotland is gratefully acknowledged.

A generalised formulation for computing the microbuckling load in periodic layered materials

Acknowledgments The financial support of the part of this research by The Royal Society, The Royal Academy of Engineering and The Carnegie Trust for the Universities of Scotland is gratefully acknowledged.