Photopolymerization of Limonene Dioxide and Vegetable Oils as Biobased 3D-Printing Stereolithographic Formulation.

Epoxidized vegetable oils and limonene dioxide, a bis-epoxide derived from the terpene limonene, are photo-copolymerized to yield highly crosslinked networks with high conversion of all epoxide groups at ambient temperature. However, the slow polymerization of such biobased formulation polymerizes is not compatible for a use in a commercial SLA 3D printer. Adding an acrylated epoxidized vegetable oil to the bis-epoxide leads to a decrease of curing time and an increase in LDO conversion to polymer.

In Operando Photoswitching of Cu Oxidation States in Cu-Based Plasmonic Heterogeneous Photocatalysis for Efficient H Evolution.

Metal nanoparticles (NP) supported on TiO are known to be efficient photocatalysts for solar-to-chemical energy conversion. While TiO decorated with copper NPs has the potential to become an attractive system, the poor oxidative stability of Cu severely limits its applicability. In this work, we demonstrate that, when Cu NPs supported on TiO nanobelts (NBs) are engaged in the photocatalytic generation of H from water under light illumination, Cu is not only oxidized in CuO but also dissolved under the form of Cu/Cu ions, leading to a continuous reconstruction of nanoparticles via Ostwald ripening.

Effect of the metal-support interaction in platinum anchoring on heteroatom-doped graphene for enhanced oxygen reduction reaction.

Three kinds of Pt anchoring on heteroatom-doped graphene were synthesised and their effects on catalytic performance were discussed. The introduction of N and P into graphene is helpful to decrease the Pt particle size with a homogeneous distribution and favor the electronic configuration for the ORR.

Carbon Dots for Carbon Dummies: The Quantum and The Molecular Questions Among Some Others.

Carbon Dots (CDs) are carbon nanoparticles which were discovered in 2004. Despite two decades of intensive work from the scientific community and a colossal amount of gathered experimental data, no definitive consensus exists to date on several key aspects such as the actual definition of CDs and the origin of their emissive properties. This review proposes a critical evaluation of these fundamental questions.

Ultra-High T Thermoset Fibers Obtained by Electrospinning of Functional Polynorbornenes.

Insertion polynorbornenes (PBNEs) are rigid-rod polymers that have very high glass transition temperatures (T). In this study, two functional PNBEs were electrospun in the presence of a variety of cross-linkers, resulting in fibers with Ts greater than 300 °C. The fibers are long (several mm), rigid, and with diameters that can be tuned in the range 300 nm-10 μm.

The Unusual Conductivity of Na in PEO-Based Statistical Copolymer Solid Electrolytes: When Less Means More.

The low conductivity of Na electrolytes in solid polymer electrolytes (SPEs) curtails the development of Na polymer batteries. In this study, NaClO (3-24 wt %, 90-9:1 O:Na) is dissolved in statistical copolymers of ethylene oxide (EO) and propylene oxide (PO) (0-20 mol %). Remarkably, the conductivity of these SPEs increases as the concentration of Na decreases, thus departing from the usual Nernstian behavior.

Graphitic Dots Combining Photophysical Characteristics of Organic Molecular Fluorophores and Inorganic Quantum Dots.

Thanks to their photophysical properties, both organic molecular fluorophores (MFs) and inorganic quantum dots (QDs) are extensively used for bioimaging applications. However, limitations such as photobleaching for the former or blinking, size, and toxicity for the latter still constitute a challenge for numerous applications. We report here that embedding MFs in graphitic carbon dots (GDs) results in fluorophores which entirely tackle this challenge.

Enhancement of Scattering and Near Field of TiO-Au Nanohybrids Using a Silver Resonator for Efficient Plasmonic Photocatalysis.

Recently, localized surface plasmon resonances (SPRs) of metallic nanoparticles (NPs) have been widely used to construct plasmonic nanohybrids for heterogeneous photocatalysis. For example, the combination of plasmonic Au NPs and TiO provides pure TiO visible-light activity. The SPR effect induces an electric field and consequently enhances light scattering and absorption, favoring the transfer of photon energy to hot carriers for catalytic reactions.

N, P-Codoped Graphene Dots Supported on N-Doped 3D Graphene as Metal-Free Catalysts for Oxygen Reduction.

Nitrogen and phosphorus-codoped graphene dots supported on nitrogen-doped three-dimensional graphene (N, P-GDs/N-3DG) have been synthesized by a facile freeze-annealing process. On the surface of the 3D interconnected porous structure, the N, P-GDs are uniformly dispersed. The as-prepared N, P-GDs/N-3DG material served as a metal-free catalyst for oxygen reduction reaction (ORR) in an alkaline medium and evaluated by a rotating ring-disk electrode.

Lanthanide dodecyl sulfates, a potent family of catalysts for the preparation of biobased epoxy thermosets.

Lanthanide dodecyl sulfates, LnDS, are remarkably effective to catalyze the reaction of diepoxides with diamines in the liquid and solid states, a key reaction in the formation of epoxy thermosets. Among all lanthanides, the lanthanum complex LaNa(DS)(HO) is the most active, allowing a decrease of 60 kJ mol of the activation energy between polyethylene imine and limonene dioxide, a biobased epoxy monomer.

Recent Progress in Two-Dimensional Layered Double Hydroxides and Their Derivatives for Supercapacitors.

High-performance supercapacitors have attracted great attention due to their high power, fast charging/discharging, long lifetime, and high safety. However, the generally low energy density and overall device performance of supercapacitors limit their applications. In recent years, the design of rational electrode materials has proven to be an effective pathway to improve the capacitive performances of supercapacitors.

Diffusion Control of Organic Cathode Materials in Lithium Metal Battery.

Organic cathode materials for lithium batteries are becoming increasingly popular because they have high theoretical redox voltage, high gravimetric capacity, low cost, easy processing and sustainability. However, their development is limited by their solubility in the electrolyte, which leads to rapid deterioration of the battery upon cycling. We developed a Janus membrane, which consists of two layers - a commercial polypropylene separator (Celgard) and a 300-600 nm layer of exfoliated graphite that was applied by a simple and environmentally friendly process.

Water and Carbon Dioxide: A Unique Solvent for the Catalytic Polymerization of Ethylene in Miniemulsion.

The catalytic polymerization of ethylene is performed in water pressurized with CO . The size of the initial monomer droplets and of the resulting polymer particles can be varied by simply changing the CO pressure. Furthermore, at identical ethylene partial pressure, the polymerizations performed in the presence of CO are significantly faster than in its absence.

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes.

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity.

Efficient Upconverting Multiferroic Core@Shell Photocatalysts: Visible-to-Near-Infrared Photon Harvesting.

We report the two-step synthesis of a core@shell nanohybrid material for visible-to-near-infrared (NIR) photocatalysis. The core is constituted of NaGdF:Er, Yb upconverting nanoparticles (UCNPs). A bismuth ferrite (BFO) shell is assembled around the UCNPs via a hydrothermal process.

Controlled-release of formulations encapsulated in light-resistant colloidosomal microcapsules for the management of lepidopteran pests of crops.

() based formulations have been widely used to control lepidopteran pests in agriculture and forestry. One of their weaknesses is their short residual activity when sprayed in the field. Using Pickering emulsions, mixtures of spores and crystals from three serovars were successfully encapsulated in colloïdosomal microparticles (50 μm) using innocuous chemicals (acrylic particles, sunflower oil, iron oxide nanoparticles, ethanol and water).

Engineering the Absorption and Field Enhancement Properties of Au-TiO2 Nanohybrids via Whispering Gallery Mode Resonances for Photocatalytic Water Splitting.

Recently, surface plasmon resonance (SPR) effects have been widely used to construct photocatalysts which are active in the visible spectral region. Such plasmonic photocatalysts usually comprise a semiconductor material transparent in the visible range (such as TiO2) and plasmonic nano-objects (e.g.

TiO2@Carbon Photocatalysts: The Effect of Carbon Thickness on Catalysis.

Nanocomposites composed of TiO2 and carbon materials (C) are widely popular photocatalysts because they combine the advantages of TiO2 (good UV photocatalytic activity, low cost, and stability) to the enhanced charge carrier separation and lower charge transfer resistance brought by carbon. However, the presence of carbon can also be detrimental to the photocatalytic performance as it can block the passage of light and prevent the reactant from accessing the TiO2 surface. Here using a novel interfacial in situ polymer encapsulation-graphitization method, where a glucose-containing polymer was grown directly on the surface of the TiO2, we have prepared uniform TiO2@C core-shell structures.

Bypassing the lack of reactivity of -substituted norbornenes with the catalytic rectification-insertion mechanism.

The catalytic 1,2-insertion polymerization of polar norbornenes (NBEs) leads to the formation of functional rigid macromolecules with exceptional thermal, optical and mechanical properties. However, this remarkable reaction is plagued by the low reactivity of the polar monomers, and most notably of those bearing a functional group in position. We have examined the polymerization mechanism of NBEs bearing one or two COMe groups either in or position catalyzed by the so-called naked allyl Pd SbF catalyst ().

TiO2@C core-shell nanoparticles formed by polymeric nano-encapsulation.

TiO2 semiconducting nanoparticles are known to be photocatalysts of moderate activity due to their high band-gap and high rate of electron-hole recombination. The formation of a shell of carbon around the core of TiO2, i.e.

Enhanced photocatalytic property of reduced graphene oxide/TiO2 nanobelt surface heterostructures constructed by an in situ photochemical reduction method.

A facile method is proposed to assemble graphene oxide (GO) on the surface of a TiO2 nanobelt followed by an in situ photocatalytic reduction to form reduced graphene oxide (rGO)/TiO2 nanobelt surface heterostructures. The special colloidal properties of GO and TiO2 nanobelt are exploited as well as the photocatalytic properties of TiO2 . Using water-ethanol solvent mixtures, GO nanosheets are tightly wrapped around the surface of the TiO2 nanobelts through an aggregation process and are then reduced in situ under UV-light irradiation to form rGO/TiO2 nanobelt surface heterostructures.

Supramolecular complexes of multivalent cholesterol-containing polymers to solubilize carbon nanotubes in apolar organic solvents.

Copolymers of 2-ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl-2-hydroxymethacrylate (CEM) were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation.

Probing the Regiochemistry of Acrylate Catalytic Insertion Polymerization via Cyclocopolymerization of Allyl Acrylate and Ethylene.

When palladium phosphine sulfonate catalysts were used, ethylene and allyl acrylate were copolymerized. The copolymer structure was analyzed by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) and was found to contain both δ-valerolactone and γ-butyrolactones inserted within the chain. These cyclic structures were determined to be the outcome of 1,2 allyl insertions and 2,1 acrylate insertions except when the acrylate was cyclopolymerized: in this case, regiochemistry of the insertion was 1,2.

Structure-activity relationship of palladium phosphanesulfonates: toward highly active palladium-based polymerization catalysts.

Palladium phosphanesulfonate [R(2)P(C(6)H(4)-o-SO(3))PdMeL] catalysts permit the copolymerization of an exceptional large number of functional olefins with ethylene. However, these catalysts usually have reduced activity. We here have conducted a systematic study on the influence of the phosphane substituent, R, on activity and molecular weight.

Supported bilayer on a nanopatterned membrane as model PAMPA membranes.

Parallel-artificial membrane permeation assay (PAMPA) is widely used to rapidly measure drug permeability across a biological membrane. We have prepared model PAMPAs by supporting a lipid bilayer on a hydrated polymeric cushion adsorbed at the surface of a nanoporous alumina filter. In contrast to conventional PAMPAs, the natural fluidity of the bilayer is expected to be conserved in these model PAMPAs.