Enhanced Catalytic Hydrogenation of Olefins in Sulfur-Rich Naphtha Using Molybdenum Carbide Supported on γ-Al2O3 Spheres under Steam Conditions: Simulating the Hot Separator Stream Process.

Spheres comprising 10 wt.% Mo2C/γ-Al2O3, synthesized through the sucrose route, exhibited unprecedented catalytic activity for olefin hydrogenation within an industrial naphtha feedstock that contained 23 wt.% olefins, as determined by supercritical fluid chromatography (SFC). The catalyst demonstrated resilience to sulfur, exhibiting no discernible deactivation signs over a tested 96 h operational period. The resultant hydrogenated naphtha from the catalytic process contained only 2.5 wt.% olefins when the reaction was conducted at 280 °C and 3.44 × 106 Pa H2, subsequently blended with Athabasca bitumen to meet pipeline specifications for oil transportation. Additionally, the carbide catalyst spheres effectively hydrogenated olefins under steam conditions without experiencing any notable hydrogenation in the aromatics. We propose the supported carbide catalyst as a viable alternative to noble metals, serving as a selective agent for olefin elimination from light petroleum distillates in the presence of steam and sulfur, mitigating the formation of gums and deposits during the transportation of diluted bitumen (dilbit) through pipelines.

Insights into the Characterization of the Self-Assembly of Different Types of Amphiphilic Molecules Using Dynamic Light Scattering.

The self-assembly of cetyltrimethylammonium bromide, sodium dodecylsulfate, Triton X-100, and sulfobetaine surfactants in aqueous solutions was examined by dynamic light scattering, both in the presence and absence of 0.1 M NaCl salt, across various temperatures. For each surfactant, critical parameters, such as concentration and phase transition temperatures, of micelles were determined by monitoring changes in the hydrodynamic diameter with concentration and temperature. Additionally, we explored the self-assembly behavior of these surfactants when they are introduced alongside polystyrene nanoparticles. Our findings enabled the elucidation of surfactant molecule adsorption mechanisms onto polystyrene nanoparticle surfaces. Furthermore, by analyzing variations in the z-average diameter and zeta potential, we were able to establish the Krafft point, a parameter that remains imperceptible when polystyrene nanoparticles are absent from the solution.

Solid-State NMR Spectroscopy: Towards Structural Insights into Starch-Based Materials in the Food Industry.

Solid-state NMR is a nondestructive and noninvasive technique used to study the chemical structure and dynamics of starch-based materials and to bridge the gap between structure-function relationships and industrial applications. The study of crystallinity, chemical modification, product blending, molecular packing, amylose-amylopectin ratio, end chain motion, and solvent-matrix interactions is essential for tailoring starch product properties to various applications. This article aims to provide a comprehensive and critical review of research characterizing starch-based materials using solid-state NMR, and to briefly introduce the most advanced and promising NMR strategies and hardware designs used to overcome the sensitivity and resolution issues involved in structure-function relationships.

Initiated Chemical Vapor Deposition (iCVD) of Bio-Based Poly(tulipalin A) Coatings: Structure and Material Properties.

A solvent-free route of initiated chemical vapor deposition (iCVD) was used to synthesize a bio-renewable poly(α-Methylene-γ-butyrolactone) (PMBL) polymer. α-MBL, also known as tulipalin A, is a bio-based monomer that can be a sustainable alternative to produce polymer coatings with interesting material properties. The produced polymers were deposited as thin films on three different types of substrates-polycarbonate (PC) sheets, microscopic glass, and silicon wafers-and characterized via an array of characterization techniques, including Fourier-transform infrared (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), ultraviolet visible spectroscopy (UV-vis), differential scanning calorimetry (DSC), size-exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Optically transparent thin films and coatings of PMBL were found to have high thermal stability up to 310 °C. The resulting PMBL films also displayed good optical characteristics, and a high glass transition temperature (Tg~164 °C), higher than the Tg of its structurally resembling fossil-based linear analogue-poly(methyl methacrylate). The effect of monomer partial pressure to monomer saturation vapor pressure (Pm/Psat) on the deposition rate was investigated in this study. Both the deposition rate and molar masses increased linearly with Pm/Psat following the normal iCVD mechanism and kinetics that have been reported in literature.

RAFT Polymerization of a Biorenewable/Sustainable Monomer via a Green Process.

A biorenewable polymer is synthesized via a green process using the RAFT principle for the first time in supercritical CO2 at 300 bar and 80 °C. α-Methylene-γ-butyrolactone polymers of various chain lengths and molecular weights are obtained. The molecular weights vary from 10 000 up to 20 000 with low polydispersity indexes (PDI <1.5). Furthermore, the monomer conversion in supercritical CO2 is substantially higher, respectively 85% for ScCO2 compared to ≈65% for polymerizations conducted in dimethyl formamide (DMF) solvent. Chain extensions are carried out to confirm the livingness of the formed polymers in ScCO2 . This opens up future possibilities of the formation of different polymer architectures in ScCO2 . The polymers synthesized in ScCO2 have glass transition temperature (Tg ) values ranging from 155 up to 190 °C. However, the presence of residual monomer encapsulated inside the formed polymer matrix affects the glass transition of the polymer that is lowered by increasing monomer concentrations. Hence, additional research is required to eliminate the remaining monomer concentration in the polymer matrix in order to arrive at the optimal Tg .

Solid State NMR a Powerful Technique for Investigating Sustainable/Renewable Cellulose-Based Materials.

Solid state nuclear magnetic resonance (ssNMR) is a powerful and attractive characterization method for obtaining insights into the chemical structure and dynamics of a wide range of materials. Current interest in cellulose-based materials, as sustainable and renewable natural polymer products, requires deep investigation and analysis of the chemical structure, molecular packing, end chain motion, functional modification, and solvent-matrix interactions, which strongly dictate the final product properties and tailor their end applications. In comparison to other spectroscopic techniques, on an atomic level, ssNMR is considered more advanced, especially in the structural analysis of cellulose-based materials; however, due to a dearth in the availability of a broad range of pulse sequences, and time consuming experiments, its capabilities are underestimated. This critical review article presents the comprehensive and up-to-date work done using ssNMR, including the most advanced NMR strategies used to overcome and resolve the structural difficulties present in different types of cellulose-based materials.

Solid State NMR Spectroscopy a Valuable Technique for Structural Insights of Advanced Thin Film Materials: A Review.

Solid-state NMR has proven to be a versatile technique for studying the chemical structure, 3D structure and dynamics of all sorts of chemical compounds. In nanotechnology and particularly in thin films, the study of chemical modification, molecular packing, end chain motion, distance determination and solvent-matrix interactions is essential for controlling the final product properties and applications. Despite its atomic-level research capabilities and recent technical advancements, solid-state NMR is still lacking behind other spectroscopic techniques in the field of thin films due to the underestimation of NMR capabilities, availability, great variety of nuclei and pulse sequences, lack of sensitivity for quadrupole nuclei and time-consuming experiments. This article will comprehensively and critically review the work done by solid-state NMR on different types of thin films and the most advanced NMR strategies, which are beyond conventional, and the hardware design used to overcome the technical issues in thin-film research.

Nanoparticles of well-defined 4-arm stars made using nanoreactors in water.

In this work, the use of a nanoreactor is demonstrated to rapidly prepare monodisperse polymer nanoparticles in water-based dispersion consisting of 4-arm star polymer via the R-group RAFT approach. It is shown that by heating a nanoparticle assembler above its lower critical solution temperature (LCST), stabilized nanoparticles are formed that act as a template for the 4-arm star RAFT-mediated polymerization of styrene. Monodisperse nanoparticles of size (between 40 and 90 nm) containing monodisperse polymer of desired molecular weight (30-95 k) are obtained with little star-star coupling due to compartmentalization. The nanoreactor technique allows independent control over the size and molecular weight with a 4-arm star topology.