Preparation and Characterisation of Polyurethane Acrylate-Based Titanium Dioxide Pigment for Blue Light-Curable Ink.

Herein, a polyurethane acrylate-based TiO2 (PU-TiO2) was fabricated using a two-step method. First, a polyurethane prepolymer was prepared. Second, PU-TiO2 was prepared using amino-modified TiO2 (A-TiO2). The best synthesis process of the polyurethane prepolymer was when the reaction temperature was 80 °C, the reaction time was 3 h and the R-value of the polyurethane acrylate was 2. Next, the influence of the A-TiO2 content on the structure and performance of PU-TiO2 was examined. The analysis of the rheological properties of the PU-TiO2 ink indicated that its viscosity gradually increased as the A-TiO2 content increased. The tensile performance of film improved because of the presence of A-TiO2. The photo-polymerisation and photo-rheological performance indicated that the PU-TiO2 structure changed from a hyperbranched structure with TiO2 as the core to a segmented structure, as the A-TiO2 content was 3%.

In Situ Blue-Light-Induced Photocurable and Weavable Hydrogel Filament.

A self-lubricating hydrogel filament was achieved by establishing an in situ photocuring system and using camphorquinone/diphenyl iodonium hexafluorophosphate (CQ/DPI) as the blue-light photoinitiators, acrylamide (AM) and N,N-dimethylacrylamide (DMAA) as the monomers, polyethylene glycol diacrylate (PEGDA) as the cross-linker, and lecithin as the lipid lubricant. The blue-light photopolymerization efficiency and the photorheological properties of the hydrogel precursor were investigated by photodifferential scanning calorimetry and a photorheological system. With the increase of DMAA, the photopolymerization efficiency of the precursor improved, while the elasticity of poly(DMAA/AM) decreased accordingly. The physical cross-linking effect between lecithin and the poly(DMAA/AM) network led to improved polymerization properties and elasticity. The lipid-based boundary layer at the hydrogel surface endowed the self-lubrication of the hydrogel filament. The extruded hydrogel filaments exhibited excellent mechanical properties and weavability, which were expected to play a realistic role in soft robots and bioengineering.

Carbon monoxide oxidation catalysed by defective palladium chloride: DFT calculations, EXAFS, and in situ DRIRS measurements.

We examined the potential catalytic role of the palladium chloride catalyst in CO oxidation using density functional theory and experimental investigations. The active plane of the palladium chloride catalyst is identified as (140). We found that the defective PdCl2(140) surface is able to facilitate the activation of O2 and subsequently promote the oxidation of CO. The most significant reaction channel, the Eley-Rideal mechanism (MER1), proceeds first by a peroxo-type (OOCO) intermediate formation, second by O adsorption with the first CO2 release, then by the second CO attraction and the second CO2 formation, and finally by the second CO2 desorption and restoration of the defective PdCl2(140) surface. The rate-determining step is the formation of the second CO2 in the whole catalytic cycle. Compared to the previously reported catalytic systems, the reaction activation barrier (0.54 eV) of CO oxidation in the PdCl2 catalyst is low, indicating PdCl2 as a potential high-performance catalyst for CO oxidation. The present results enrich our understanding of CO oxidation of Pd-based catalysts and provide a basis for fabricating Pd-based catalysts with high activity.

Insights into the reaction mechanism of CO oxidative coupling to dimethyl oxalate over palladium: a combined DFT and IR study.

Oxidative coupling of toxic pollutant CO to form the platform raw chemical material dimethyl oxalate (DMO) has been industrialized however the catalytic mechanism has been unknown so far. The reaction mechanism of CO oxidative coupling to form DMO on a Pd(111) surface has been investigated using density functional theory (DFT) and in situ diffuse reflectance infrared (DRIR) spectroscopy. DFT calculations and in situ DRIRS measurements indicate that two co-adsorbed intermediates COOMe and OCCO, initiate the reaction. C-C coupling occurs earlier due to a low coupling barrier and small steric hindrance. The results also suggest that Pd(111) is selective towards DMO over DMC, and that CO pre-adsorption and CO in excess effectively enhance the yield of DMO. The microscopic elucidation of this important reaction suggests improvements in coal-to-EG (CTEG) production which can be applied in practice to effectively enhance the yield and reduce the cost. The results may help with further fine-tuning and designing of high-efficient noble metal catalysts.