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. For example, in a 60:40 wt:wt mixture of LDO and epoxidized soybean oil, the conversions of both exocyclic and endocyclic epoxide groups of LDO are ≥95%. These formulations were successfully used in SLA 3D printers, leading to generation of hard and dry complex objects using biobased formulations.

In Operando Photoswitching of Cu Oxidation States in Cu-Based Plasmonic Heterogeneous Photocatalysis for Efficient H2 Evolution.

Metal nanoparticles (NP) supported on TiO2 are known to be efficient photocatalysts for solar-to-chemical energy conversion. While TiO2 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 TiO2 nanobelts (NBs) are engaged in the photocatalytic generation of H2 from water under light illumination, Cu is not only oxidized in CuO but also dissolved under the form of Cu+/Cu2+ ions, leading to a continuous reconstruction of nanoparticles via Ostwald ripening. By nanoencapsulating the CuOx (Cu/CuO/Cu2O) NPs by a few layers of carbon supported on TiO2 (TC@C), Ostwald ripening can be suppressed. Simultaneously, the resulting CuOx@C NPs are photoreduced under light illumination to generate Cu@C NPs. This photoswitching strategy allows the preparation of a Cu plasmonic photocatalyst with enhanced activity for H2 production. Remarkably, the photocatalyst is even active when illuminated with visible light, indicating a clear plasmonic enhancement of photocatalytic activity from the surface plasmonic resonance (SPR) effect of Cu NPs. Three-dimensional electromagnetic wave-frequency domain (3D-EWFD) simulations were conducted to confirm the SPR enhancement. This advance bodes for the development of scalable multifunctional Cu-based plasmonic photocatalysts for solar energy transfer.

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. Lay persons will also find here an alternative introduction to the CDs domain, including synthetic strategies, photophysical properties, as well as challenges and outlook of this exciting new area.

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

Insertion polynorbornenes (PBNEs) are rigid-rod polymers that have very high glass transition temperatures (Tg). In this study, two functional PNBEs were electrospun in the presence of a variety of cross-linkers, resulting in fibers with Tgs 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 electrospinning process can be used to encapsulate dyes or graphene dots. Due to the high cross-linking density of the fiber, dye leaching is prevented. In contrast with other rigid-rod polymers, electrospinning of PNBE is facile and can be performed at injection rates as high as 1 mL/min.

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, NaClO4 (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. Using a combination of calorimetric measurements and molecular dynamic simulations, this unusual phenomenon is attributed to the presence of physical cross-links generated by Na+ . As a result, polymers containing a low salt concentration (3 wt %) display a drastically enhanced ionic conductivity (up to 0.2 10-4  S cm-1 at 25 °C), thus paving the way for the design of all-solid-state PEO-based sodium batteries operational at room temperature.

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. Characterized by ultranarrow, bright, and excitation-independent emission devoid of blinking and photobleaching, these hybrid-featured nanoparticles also demonstrate their unique photophysical performances at the single-nanoparticle scale, making them appealing candidates for bioimaging applications.

Enhancement of Scattering and Near Field of TiO2-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 TiO2 provides pure TiO2 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. Numerous approaches have been dedicated to the improvement of SPR absorption in photocatalysts. Here, we have designed a core@shell-satellite nanohybrid catalyst whereby an Ag NP core, as a plasmonic resonator featuring unique dual functions of strong scattering and near-field enhancement, is encapsulated by SiO2 and TiO2 layers in sequence, with Au NPs on the outer surface, Ag@SiO2@TiO2-Au, for efficient plasmonic photocatalysis. By varying the size and number of Ag NP cores, the Au SPR can be tailored over the visible and near-infrared spectral region to reabsorb the scattered photons. In the presence of the Ag core, the incident light is efficiently confined in the reaction suspension by undergoing multiple scattering, thus leading to an increase of the optical path to the photocatalysis. Moreover, using numerical analysis and experimental verifications, we demonstrate that the Ag core also induces a strong near-field enhancement at the Au-TiO2 interface via SPR coupling with Au. Consequently, the activity of the TiO2-Au plasmonic photocatalyst is significantly enhanced, resulting in a high H2 production rate under visible light. Thus, the design of a single structural unit with strong scattering and field enhancement, induced by a plasmonic resonator, is a highly effective strategy to boost photocatalytic activity.

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

Lanthanide dodecyl sulfates, LnDSx, 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)4(H2O)2 is the most active, allowing a decrease of 60 kJ mol-1 of the activation energy between polyethylene imine and limonene dioxide, a biobased epoxy monomer.

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. The N, P-GDs/N-3DG catalyst exhibits excellent ORR activity, which is comparable to that of the commercial Pt/C catalyst. Furthermore, it exhibits a higher tolerance to methanol and better stability than the Pt/C. This enhanced electrochemical catalytic performance can be ascribed to the presence of abundant functional groups and edge defects. This study indicates that P-N bonded structures play a vital role as the active sites in ORR.

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. Layered double hydroxides (LDHs), have shown great potential in new-generation supercapacitors, due to their unique two-dimensional layered structures with a high surface area and tunable composition of the host layers and intercalation species. Herein, recent progress in LDH-based, LDH-derived, and composite-type electrode materials targeted for applications in supercapacitors, by tuning the chemical/metal composition, growth morphology, architectures, and device integration, is reviewed. The complicated relationships between the composition, morphology, structure, and capacitive performance are presented. A brief projection is given for the challenges and perspectives of LDHs for energy research.

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. The submicron graphite layer is only permeable to Li+ and it drastically improves the battery performance, as measured by capacity retention and high coulombic efficiency, even at 2C rates. Post-mortem analysis of the battery indicates that the new membrane protects the anode against corrosion, and cathode dissolution is reduced. This graphite-based membrane is expected to greatly expedite the deployment of batteries with organic cathodes.

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 CO2 . The size of the initial monomer droplets and of the resulting polymer particles can be varied by simply changing the CO2 pressure. Furthermore, at identical ethylene partial pressure, the polymerizations performed in the presence of CO2 are significantly faster than in its absence. Thus, the combination of CO2 and water is a promising green solvent for catalytic emulsion polymerizations.

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. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

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 NaGdF4:Er3+, Yb3+ upconverting nanoparticles (UCNPs). A bismuth ferrite (BFO) shell is assembled around the UCNPs via a hydrothermal process. The photocatalytic degradation assays of methylene orange and 4-chlorophenol reveal that these core@shell nanostructures possess remarkably enhanced reaction activity under visible and NIR irradiation, compared to the BFO powder alone and the BFO-UCNP mixture. Photo-charge scavenger tests and fluorescent assays indicate that hydroxyl radicals play a pivotal role in the photodegradation mechanism. The enhanced photoactivity of the core@shell structure is attributed to the NIR radiation which is converted into visible light by UCNPs, and which is then captured by BFO via a nonradiative luminescence resonance energy transfer process. Therefore, this core@shell architecture optimizes solar energy use by efficiently harvesting visible and NIR photons.

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

Bacillus thuringiensis (B. t.) 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 B. t. serovars were successfully encapsulated in colloïdosomal microparticles (50 µm) using innocuous chemicals (acrylic particles, sunflower oil, iron oxide nanoparticles, ethanol and water). A pH trigger mechanism was incorporated within the particles so that B. t. release occurred only at pH > 8.5 which corresponds to the midgut pH of the target pests. Laboratory assays performed on Trichoplusia ni (T. ni) larvae demonstrated that the microencapsulation process did not impair B. t. bioactivity. The best formulations were field-tested on three key lepidopteran pests that attack Brassica crops, i.e., the imported cabbageworm, the cabbage looper and the diamondback moth. After 12 days, the mean number of larvae was significantly lower in microencapsulated formulations than in a commercial B. t. formulation, and the effect of microencapsulated formulations was comparable to a chemical pesticide (lambda-cyhalothrin). Therefore, colloïdosomal microcapsule formulations successfully extend the bioactivity of B. t. for the management of lepidopteran pests of Brassica crops.

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., Au nanoparticles (Au NPs)). Specific SPRs, though, only partially cover the visible spectrum and feature weak light absorption. Here, we explore the unique role played by whispering gallery mode (WGM) resonances in the expression of the photocatalytic activity of plasmonic photocatalysts. Using numerical simulations, we demonstrate that, by solely exploiting a proper geometrical arrangement and WGM resonances in a TiO2 sphere, the plasmonic absorption can be extended over the entire visible range and can be increased by more than 40 times. Furthermore, the local electric field at the Au-TiO2 interface is also considerably enhanced. These results are experimentally corroborated, by means of absorption spectroscopy and Raman measurements. Accordingly, such WGM-assisted plasmonic photocatalysts, when employed in water splitting experiments, exhibit enhanced activity in the visible range. Our findings show a promising and straightforward way to design full solar spectrum photocatalysts.

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. The thickness of the carbon shell can be precisely and easily tuned between 0.5 and 8 nm by simply programming the polymer growth on TiO2. The resulting core@shell TiO2@C nanostructures are not black and they possess the highest activity for the photodegradation of organic compounds when the carbon shell thickness is 1-2 nm, corresponding to ∼3-5 graphene layers. Photoluminescence and photocurrent generation tests further confirm the crucial contribution of the carbon shell on charge carrier separation and transport. This in situ polymeric encapsulation approach allows for the careful tuning of the thickness of graphite-like carbon, and it potentially constitutes a general and efficient route to prepare other oxide@C catalysts, which can therefore largely expand the applications of nanomaterials in catalysis.

Bypassing the lack of reactivity of endo-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 endo position. We have examined the polymerization mechanism of NBEs bearing one or two CO2Me groups either in exo or endo position catalyzed by the so-called naked allyl Pd+ SbF6- catalyst (1). Although endo dimethyl ester of 5-norbornene-2,3-dicarboxylic acid (NBE(CO2Me)2) is polymerized by 1, two endo units are never inserted consecutively along the polymer chain. Indeed, 1 is a tandem catalyst which not only catalyzes the insertion of the monomer but also the isomerization of endo and exo isomers. Thus, the polymerization of endo monomers proceeds via a novel mechanism, coined rectification-insertion mechanism, whereby half of the endo monomers are rectified into exo ones prior insertion, leading to the formation of an alternating endo-exo copolymer using an endo only feedstock. With this mechanism, the lack of reactivity of endo norbornenes is bypassed, and the polymerization of predominantly endo polar NBEs bearing a variety of functionalities such as esters, imides, acids, aldehydes, alcohols, anhydrides, or alkyl bromides proceeds with catalyst loadings as low as 0.002 mol%.

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., the formation of TiO2@C nanoparticles, is believed to partly alleviate these problems. It is usually achieved by a hydrothermal treatment in a presence of a sugar derivative. We present here a novel method for the formation of highly uniform C shell around TiO2 nanoparticles. For this purpose, TiO2 nanoparticles were dispersed in water using an oligomeric dispersant prepared by Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization. Then the nanoparticles were engaged into an emulsion polymerization of acrylonitrile, resulting in the formation of a shell of polyacrylonitrile (PAN) around each TiO2 nanoparticles. Upon pyrolysis, the PAN was transformed into carbon, resulting in the formation of TiO2@C nanoparticles. The structure of the resulting particles was elucidated by X-Ray diffraction, FTIR, UV-VIS and Raman spectroscopy as well as TEM microscopy. Preliminary results about the use of the TiO2@C particles as photocatalysts for the splitting of water are presented. They indicate that the presence of the C shell is responsible for a significant enhancement of the photocurrent.