Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

Achieving fabrication of highly transparent Y2O3 ceramics via air pre-sintering by deionization treatment of suspension

An easy albeit quite effective deionization suspension treatment was adopted to alleviate the detrimental effects related to the hydrolysis of Y₂O₃ in an aqueous medium. Fabrication of highly transparent Y₂O₃ ceramics with a fine grain size via air pre-sintering and post–hot isostatic pressing (HIP) treatment without using any sintering additive was achieved using the treated suspensions. The hydrolysis issue of Y₂O₃ powder in an aqueous medium was effectively alleviated by using deionization treatment, and a well-dispersed suspension with a low concentration of dissolved Y³⁺ species was obtained. The dispersed suspensions were consolidated by the centrifugal casting method, and the green bodies derived from the suspension of 35.0 vol% solid loading showed an improved homogeneity with a relative density of 52.1%. Fully dense Y₂O₃ transparent ceramic with high transparency was obtained by pre-sintering consolidated green compacts at a low temperature of 1400°C for 16 h in air followed by a post-HIP treatment at 1550°C for 2 h under 200 MPa pressure. The sample had a fine average grain size of 690 nm. The in-line transmittance of the sample reached 83.3% and 81.8% at 1100 nm and 800 nm, respectively, very close to the theoretical values of Y₂O₃.     

Application of Polyimide-based Microfluidic Devices on Acid-catalyzed Hydrolysis of Dimethoxypropane

Microfluidic devices intensify transport phenomena and can improve chemical processes. New manufacturing processes and materials are perpetually developed due to constantly growing interest in process intensification. In this contribution, the authors present the design and application of polyimide-foil-based microfluidic mixing devices manufactured by reactive ion etching. As appropriate model reaction system, acid-catalyzed 2,2-dimethoxypropane (DMP) hydrolysis was chosen and investigated in three different mixing structure with varying flow rate. Energy dissipation rates were calculated to estimate mixing performances. The results show good mixing quality for Reynolds numbers between 10 and 100 and similar mixing times scales for all investigated microstructured mixers.     

Fabrication of paper based carbon/graphene/ZnO aerogel composite decorated by polyaniline nanostructure: Investigation of electrochemical properties

The cellulose derived carbon/graphene/ZnO aerogel composite was prepared as an electrode in order to investigate the electrochemical properties. Carbon aerogel was synthesized using paper as an available cellulose source, and the composite was obtained through a new and simple preparation method including the immersion of monolithic carbon aerogel in graphene oxide/Zn²⁺ suspension and subsequent chemical reduction and freeze drying. The morphology, functional groups and crystalline structure of the samples were studied with Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffraction Spectroscopy (XRD), respectively. Electrochemical performance of the prepared binder free electrodes was examined using Cyclic Voltammetry (CV), Galvanostatic Charge-Discharge (GCD) and Electrochemical Impedance Spectroscopy (EIS). The data revealed that flexible carbon/graphene/ZnO composite resulted in a low density (0.035 g cm⁻³) electrode with the capacitance of 900 mF cm⁻² at a high current density of 10 mA cm⁻², lower IR drop and high cyclic stability (capacitance retention of 96%) after 1000 cycles, at 10 mA cm⁻². These features were due to the presence of 3D porous conductive network, highly reduced graphene oxide, and the formation of ZnO nanoparticles on graphene sheets. Moreover, polyaniline (PANI) was introduced to carbon/graphene/ZnO composite electrode using electro-oxidation method at different reaction time and aniline concentration in order to achieve remarkably improved capacitance of 2500 mF cm⁻² (at 10 mA cm⁻²) and low charge transfer resistance. Also, after the supercapacitor device assembly, the capacitance was retained. Based on the results, the synthesized composite is a promising material for new generation of lightweight freestanding electrodes with the high electrochemical performance.     

Nano fibrillated cellulose-based foam by Pickering emulsion: Preparation,characterizations, and application as dye adsorbent

An ecofriendly and biodegradable porous structure was prepared from drying aqueous foams based on nano fibrillated cellulose (NFC), extracted from softwood pulp by subcritical water/CO₂ treatment (SC-NFC). The primary aim of this work was to use the modified SC-NFC as stabilizer for a water-based Pickering emulsion which upon drying, yielded porous cellulosic materials, a good dye adsorbent. In order to exploit the carboxymethylated SC-NFC (CMSC-NFC, with a degree of substitution of 0.35 and a charge density of 649 μeqv/g) as a stabilizer for water-based Pickering emulsion in subsequent step, an optimized quantity of octyl amine (30 mg/g of SC-NFC) was added to make them partially hydrophobic. A series of dry foam structures were prepared by varying the concentrations of treated CMSC-NFCs and 4 wt% was found to be the optimum concentration to yield foam with high porosity (99%) and low density (0.038 g/cc) along with high compression strength (0.24 MPa), superior to the conventionally extracted NFC. The foams were applied to capture as high as 98% of methylene blue dyes, making them a potential green candidate for treating industrial effluent. In addition, the dye adsorption kinetics and isotherms were found to be well suited with second order kinetics and Langmuir isotherm models.     

Deacetylated Cellulose Acetate/Polyurethane Composite Nanofiber Membranes with Highly Efficient Oil/Water Separation and Excellent Mechanical Properties

Nowadays, oil pollution has become more serious, which causes great threats both to the ecological environment and human life. In this study, a novel type of multifunctional deacetylated cellulose acetate/polyurethane (d-M_CA:M_TPU) composite nanofiber membranes for oil/water separation are successfully fabricated by electrospinning, which show super-amphiphilicity in air, super-hydrophilicity in oil, and oleophobicity in water. All the d-M_CA:M_TPU composite nanofiber membranes with different mass ratios can be used as water-removing, oil-removing, and emulsion separation substance only by gravity driving force. The highest separation flux for water and oil reaches up to 37 000 and 74 000 L m⁻² h⁻¹, respectively, and all the separation efficiencies are more than 99%. They have outstanding comprehensive mechanics performance, which can be controlled by simply adjusting the mass ratios. They show excellent antifouling and self-cleaning ability, endowing powerful cyclic stability and reusability. Those results show that d-M_CA:M_TPU composite nanofiber membranes have great application prospects in oil/water separation.     

Poly(lactide)/cellulose nanocrystal nanocomposites by high-shear mixing

There is currently considerable interest in developing stiff, strong, tough, and heat resistant poly(lactide) (PLA) based materials with improved melt elasticity in response to the increasing demand for sustainable plastics. However, simultaneous optimization of stiffness, strength, and toughness is a challenge for any material, and commercial PLA is well-known to be inherently brittle and temperature-sensitive and to show poor melt elasticity. In this study, we report that high-shear mixing with cellulose nanocrystals (CNC) leads to significant improvements in the toughness, heat resistance, and melt elasticity of PLA while further enhancing its already outstanding room temperature stiffness and strength. This is evidenced by (i) one-fold increase in the elastic modulus (6.48 GPa), (ii) 43% increase in the tensile strength (87.1 MPa), (iii) one-fold increase in the strain at break (∼6%), (iv) two-fold increase in the impact strength (44.2 kJ/m²), (v) 113-fold increase in the storage modulus at 90°C (787.8 MPa), and (vi) 10³-fold increase in the melt elasticity at 190°C and 1 rad/s (∼10⁵ Pa) via the addition of 30 wt% CNC. It is hence possible to produce industrially viable, stiff, strong, tough, and heat resistant green materials with improved melt elasticity through high-shear mixing.     

Surface modification of cellulose nanocrystals towards new materials development

Cellulose nanocrystals (CNCs) are a kind of sustainable nanoparticle from biomass, which are widely used as reinforcing filler and assembly building block for high-performance composites and function materials including biomaterial, optics, and so forth. Here, their unique advantages in material applications were reviewed based on their rod-like morphology, crystalline structure, dimension-related effects, and multi-level order structure. Then, we focused on the molecular engineering of CNCs, including the structure and physicochemical properties of their surface, along with surface modification methods and steric effects. We further discussed the performance-improvement and functionalization methods based on multi-component complex systems, together with the effects of surface molecular engineering on the performance and functions. Meanwhile, methods of optimizing orientation in uniaxial arrays were discussed along with those of enhancing photoluminescence efficiency via surface chemical modification and substance coordination. In the end, we prospected the design, development, and construction methods of new CNCs materials.     

Biocomposites of Epoxidized Natural Rubber/Poly(lactic acid) Modified with Natural Fillers (Part I)

The study aimed to prepare sustainable and degradable elastic blends of epoxidized natural rubber (ENR) with poly(lactic acid) (PLA) that were reinforced with flax fiber (FF) and montmorillonite (MMT), simultaneously filling the gap in the literature regarding the PLA-containing polymer blends filled with natural additives. The performed study reveals that FF incorporation into ENR/PLA blend may cause a significant improvement in tensile strength from (10 ± 1) MPa for the reference material to (19 ± 2) MPa for the fibers-filled blend. Additionally, it was found that MMT employment in the role of the filler might contribute to ENR/PLA plasticization and considerably promote the blend elongation up to 600%. This proves the successful creation of the unique and eco-friendly PLA-containing polymer blend exhibiting high elasticity. Moreover, thanks to the performed accelerated thermo-oxidative and ultraviolet (UV) aging, it was established that MMT incorporation may delay the degradation of ENR/PLA blends under the abovementioned conditions. Additionally, mold tests revealed that plant-derived fiber addition might highly enhance the ENR/PLA blend’s biodeterioration potential enabling faster and more efficient growth of microorganisms. Therefore, materials presented in this research may become competitive and eco-friendly alternatives to commonly utilized petro-based polymeric products.     

Improving gelling properties of myofibrillar proteins incorporating with cellulose micro/nanofibres

The effects of cellulose microfibres (CMFs, Average size: 100 ± 5 μm) and cellulose nanofibres (CNFs, Average size: 60 ± 3 nm) on the properties of myofibrillar protein (MP) gels from duck breast meat were studied. The results demonstrated that CMFs and CNFs were mostly connected to MP by non-covalent bonds, the diffusion and cross-linking of MP molecules was promoted, and a denser and more complete gel network was formed. With the increases of CMFs and CNFs concentration (0–10%), the hardness was increased by 13.15% and 19.78% for CMFs10% and CNFs10% gels, respectively, and the elasticity was increased by 40% and 80%, respectively. At the same concentration (0–10%), the increase in gel hardness, viscoelasticity and immobilised water content was greater in the CNFs-MP group than in the CMFs-MP group. The CNFs-MP group had a tighter gel network, and CNFs had a better potential to improve the gelation performance of MP.