Probing CO2 Reduction Pathways for Copper Catalysis Using an Ionic Liquid as a Chemical Trapping Agent

The key to fully leveraging the potential of the electrochemical CO₂ reduction reaction (CO2RR) to achieve a sustainable solar‐power‐based economy is the development of high‐performance electrocatalysts. The development process relies heavily on trial and error methods due to poor mechanistic understanding of the reaction. Demonstrated here is that ionic liquids (ILs) can be employed as a chemical trapping agent to probe CO2RR mechanistic pathways. This method is implemented by introducing a small amount of an IL ([BMIm][NTf₂]) to a copper foam catalyst, on which a wide range of CO2RR products, including formate, CO, alcohols, and hydrocarbons, can be produced. The IL can selectively suppress the formation of ethylene, ethanol and n‐propanol while having little impact on others. Thus, reaction networks leading to various products can be disentangled. The results shed new light on the mechanistic understanding of the CO2RR, and provide guidelines for modulating the CO2RR properties. Chemical trapping using an IL adds to the toolbox to deduce the mechanistic understanding of electrocatalysis and could be applied to other reactions as well.     

Shear-induced lamellar ionic liquid-crystal foam

In a recent paper we reported an experimental study of two N-alkylimidazolium salts. These ionic compounds exhibit liquid crystalline behaviour with melting points above 50°C in bulk. However, if they are sheared, a (possibly non-equilibrium) lamellar phase forms at room temperature. Upon shearing a thin film of the material between microscope slides, textures were observed that are strikingly similar to liquid (wet) foams. The images obtained from polarising optical microscopy (POM) were found to share many of the known quantitative properties of a two-dimensional foam coarsening process. Here we report an experimental study of this foam using a shearing system coupled with POM. The structure and evolution of the foam are investigated through the image analysis of time sequences of micrographs obtained for well-controlled sets of physical parameters (sample thickness, shear rate and temperature). In particular, we find that there is a threshold shear rate below which no foam can form. Above this threshold, a steady-state foam pattern is obtained where the mean cell area generally decreases with increasing shear rate. Furthermore, the steady-state internal cell angles and distribution of the cell number of sides deviate from their equilibrium (i.e. zero-shear) values.     

低密度对二乙烯基苯泡沫的优化制备

针对惯性约束聚变(ICF)物理实验对具有微加工能力低密度CH泡沫材料的需求,介绍了对二乙烯基苯泡沫的高内相乳液（HIPE）法制备工艺,并讨论了引发剂含量、乳化剂含量、苯乙烯的比例和无机添加剂等对泡沫形貌结构的影响,获得了低密度对二乙烯基苯泡沫的优化制备配方。不同密度对二乙烯基苯泡沫的形貌结构、力学性能和加工性能的表征结果表明：所得泡沫由开孔状球形孔构成,球形孔的直径在1~10 μm之间,孔壁上具有直径为0.2~2.0 μm的圆形孔洞结构;在密度为50 mg/cm3时,泡沫具有5 MPa的弹性模量;通过微加工技术能够获得ICF所需柱状和片状低密度泡沫微靶样品,样品最小尺寸可达100 μm。     

Lupin Protein Isolate Structure Diversity in Frozen-Cast Foams: Effects of Transglutaminases and Edible Fats

This study addresses an innovative approach to generate aerated foods with appealing texture through the utilization of lupin protein isolate (LPI) in combination with edible fats. We show the impact of transglutaminases (TGs; SB6 and commercial), glycerol (Gly), soy lecithin (Lec) and linoleic acid (LA) on the micro- and nanostructure of health promoting solid foods created from LPI and fats blends. 3-D tomographic images of LPI with TG revealed that SB6 contributed to an exceptional bubble spatial organization. The inclusion of Gly and Lec decreased protein polymerization and also induced the formation of a porous layered material. LA promoted protein polymerization and formation of homogeneous thick layers in the LPI matrix. Thus, the LPI is a promising protein resource which when in blend with additives is able to create diverse food structures. Much focus has been placed on the great foamability of LPI and here we show the resulting microstructure of LPI foams, and how these were improved with addition of TGs. New food applications for LPI can arise with the addition of food grade dispersant Lec and essential fatty-acid LA, by improved puffiness, and their contributing as replacer of chemical leavening additives in gluten-free products.     

Biobased porous acoustical absorbers made from polyurethane and waste tire particles

The production of flexible polyurethane foams (FPF) with good acoustical performance to control sound and noise and incorporating bio/recycled raw materials is an interesting alternative to conventional acoustic absorbent materials. In this sense, biobased polyols like glycerol (GLY) or hydroxylated methyl esters derived from tung oil (HMETO) as multifunctional polyols, and waste tire particles (WTP) as fillers of low thermal conductivity and good capability for acoustical absorption, are prospective feedstocks for FPF preparation. In this work, FPF were prepared by adding different amounts of these components to a formulation based on a commercial polyether polyol. Results of scanning electron microscopy (SEM) analysis, compression tests and normal-incidence sound absorption coefficient (α_N) measurements are presented and discussed. The addition of WTP or GLY to the commercial formulation enhanced both the modulus and yield stress of the obtained FPF in all cases. Moreover, a high recovery of the applied strain (>90%) was attained 24 h after the compression tests. On the other hand, the normal-incidence sound absorption coefficient, α_N, reached high values mostly at the highest evaluated frequencies (α_N ∼0.62–0.89 at 2000 Hz and α_N ∼0.70–0.91 at 5000 Hz). SEM micrographs revealed that the foams obtained present a combination of open and closed cell structure and both the modifiers and particles tend to decrease the cell size.     

Atmospheric plasma treatment of porous polymer constructs for tissue engineering applications

Porous 3D polymer scaffolds prepared by TIPS from PLGA (53:47) and PS are intrinsically hydrophobic which prohibits the wetting of such porous media by water. This limits the application of these materials for the fabrication of scaffolds as supports for cell adhesion/spreading. Here we demonstrate that the interior surfaces of polymer scaffolds can be effectively modified using atmospheric air plasma (AP). Polymer films (2D) were also modified as control. The surface properties of wet 2D and 3D scaffolds were characterised using zeta-potential and wettability measurements. These techniques were used as the primary screening methods to assess surface chemistry and the wettability of wet polymer constructs prior and after the surface treatment. The surfaces of the original polymers are rather hydrophobic as highlighted but contain acidic functional groups. Increased exposure to AP improved the water wetting of the treated surfaces because of the formation of a variety of oxygen and nitrogen containing functions. The morphology and pore structure was assessed using SEM and a liquid displacement test. The PLGA and PS foam samples have central regions which are open porous interconnected networks with maximum pore diameters of 49 microm for PLGA and 73 microm for PS foams.     

Polymer‐Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal–Organic Frameworks

A template‐assisted polymer‐derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron‐modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m² g^?1 and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal–organic frameworks (MOFs) directly within the open‐cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO₂ uptake of 2.2 %.     

A Phytic Acid Induced Super‐Amphiphilic Multifunctional 3D Graphene‐Based Foam

Surfaces with super‐amphiphilicity have attracted tremendous interest for fundamental and applied research owing to their special affinity to both oil and water. It is generally believed that 3D graphenes are monoliths with strongly hydrophobic surfaces. Herein, we demonstrate the preparation of a 3D super‐amphiphilic (that is, highly hydrophilic and oleophilic) graphene‐based assembly in a single‐step using phytic acid acting as both a gelator and as a dopant. The product shows both hydrophilic and oleophilic intelligence, and this overcomes the drawbacks of presently known hydrophobic 3D graphene assemblies. It can absorb water and oils alike. The utility of the new material was demonstrated by designing a heterogeneous catalytic system through incorporation of a zeolite into its amphiphilic 3D scaffold. The resulting bulk network was shown to enable efficient epoxidation of alkenes without prior addition of a co‐solvent or stirring. This catalyst also can be recovered and re‐used, thereby providing a clean catalytic process with simplified work‐up.     

Measurement of gas solubility in linear/branched PP melts

A magnetic suspension balance was employed in experiments to measure gas solubility in the polymer melts. The gas solubilities of CO₂ and N₂ in both linear and branched Polypropylene (PP) were investigated. The swollen volumes predicted by the Sanchez–Lacombe equation of state (EOS) and Simha–Somcynsky EOS were applied to incorporate the buoyancy effect, which is essential for the accurate measurement of solubility data. The effects of the branched structure on the swollen volume and gas solubility were discussed. It was observed that the long chain branched PP exhibited less expandability than the linear PP, due to the entangled molecular chain structure. Therefore, the total amount of gas that was able to dissolve into the long chain branched PP turned out to be less. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2497–2508, 2007