Here, we report novel highly transparent and photoactive multicomponent films for enhanced photocatalytic applications. Some films are based on intimately interfaced TiO2 nanoparticles and few-layer graphene (FLG) assembled through an environmentally friendly aqueous layer-by-layer (LbL) process. In contrast to reduced graphene oxide-based systems, directly exfoliated FLG was employed in order to preserve the intrinsic electronic conductivity of graphene and promote an efficient interfacial charge separation. The highly transparent and nanoporous LbL architecture minimizes photon scattering and enables precise control of film thickness, TiO2 loading, and photon absorption. The incorporation of FLG strongly improves charge separation, limits charge recombination, and reduces catalyst deactivation through enhanced storage of sulfur-containing byproducts. The photocatalytic activity was evaluated through the photo-oxidation of diethyl sulfide (DES), used as a model compound for mustard gas. TiO2/FLG multilayers exhibit photocatalytic activities up to 35-fold higher than conventional drop-cast TiO2 coatings and up to 6-fold higher than LbL films without FLG at comparable TiO2 loadings. Beyond the material composition itself, these results demonstrate that transparent and nanoporous LbL nanoarchitectures provide a powerful strategy for optimizing photon management and interfacial charge transfer in photocatalytic coatings.

Photocatalysts based on TiO2 modified with metals or various oxides are among the most widely used in the photocatalytic conversion of CO2 and H2O to CH4 by using solar energy. However, obtaining photocatalysts with high specific surface area and active sites that provide CO2 adsorption, activation, and hydrogen generation through water oxidation remains a challenge for efficient CH4 production. Here, a series of xRu-modified titanium dioxide (with x = 1, 3, 5 wt %) mesoporous photocatalysts with high surface area were prepared for the reduction of CO2 to CH4 under visible light. Experimental results showed that the properties of the obtained Ti1-xRuxClyO2-y and Ti1-xRuxO2 materials depend on the ruthenium concentration and the heat treatment of the TiO2 support. The evidence of the synergistic action of these parameters on the photocatalytic activity and selectivity in CO2 photoreduction under light irradiation represents a significant result of this study. The selectivity toward CH4 was explained as an effect of the surface basicity. Thus, the highest selectivities to CH4 (90 and 100%) were obtained for the samples with the highest basicity values obtained through the CO2-TDP measurements. High values of activity and selectivity were obtained in the artificial photosynthesis reaction by modifying mesoporous TiO2 by calcination and immobilization of Ru in various concentrations.

The urgent need to decarbonize the chemical industry is placing growing emphasis on the electrification of industrial processes. Dry methane reforming (DRM) offers a promising route for syngas (H 2 /CO) production through the simultaneous conversion of two major greenhouse gases, CO 2 and CH 4 . However, the process is hampered by modest catalytic performance and fast deactivation. In this study, we address these limitations by implementing localized, rapid magnetic induction heating (IH), using a graphene-coated NiCo/SiC catalyst as a susceptor, which ensures efficient heat delivery and enhanced reaction control. The results clearly evidence that IH significantly enhances both the catalytic activity and long-term stability of the DRM process at relatively low reaction temperatures. Importantly, this approach is compatible with a wide range of existing catalyst systems, including industrial formulations, and offers a practical pathway for retrofitting conventional reactors. Beyond performance gains, IH also shows potential as a strategy for chemical energy storage, aligning with current electrification and sustainability goals in the chemical sector.

The reduction of a NHC-cinnamyl nickel(II) organometallic complex through the use of different MeMgBr or MeMgCl reagents led to two types of NHC-olefin-coordinated nickel nanoparticles. Both of these unsupported nickel-NHC based nanomaterials behaved under hydrogen pressure as effective and selective catalysts operating at low temperature (<= 80 degrees C), pressure (<= 20 bar) and loading (<= 6 mol%) for the reductions of broad scopes of alkenes, alkynes, imines and heterocycles, including a challenging tetra-substituted alkene. Among these two nickel-NHC nanocatalysts, the one generated with MeMgCl showed a significant high catalytic activity with high yields and could stand the comparison with Raney nickel and state-of-the-art nickel nanocatalysts. For example, by studying the hydrogenation of 1-phenylcyclohexene in ethanol at 60 degrees C under 10 bar of H2, 3 mol% of this catalyst achieved the reaction within a single hour on a 5 mmol/0.8 g substrate scale with a yield of 96 %, a turnover number (TON) of 32 and a turnover frequency (TOF) of 32. Characterizations confirmed the coordination of the NHC-olefin ligands to the nickel nanoparticles, the reduced state of the nickel and the (poly-) crystallinity of the nanoparticles.

This study investigates the influence of polyurethane acrylate (PUA) content on the cavitation resistance of UV-cured epoxy acrylate (EPA)-PUA polymer networks. Four blends containing 0, 15, 30, and 45 wt% PUA were prepared and characterized to understand the relationship between mechanical properties and cavitation resistance. Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and nanoindentation were used to confirm that increasing PUA content in the epoxy matrix enhanced material deformability. Cavitation tests performed according to ASTM G32 revealed that increasing PUA content improved cavitation resistance, as evidenced by longer incubation periods before surface damage and fewer pits and cracks. Notably, nanoindentation conducted on cavitated surfaces showed a hardening effect during the incubation phase, particularly in the 45% PUA blend, which was attributed to plastic deformation induced by cavitation. These findings highlight the role of material deformability in absorbing energy from collapsing bubble, making UV-cured EPA-PUA blends promising candidates for applications requiring polymeric coatings resistant to cavitation erosion.

Multicomponent post-polymerization modification (PPM) reactions offer a powerful strategy for rapidly diversifying polymers, yet their potential for systematically exploring structure-property-function relationships remains largely unexplored. Herein, we report an electrophilic multicomponent molecular editing strategy that enables the construction of a polybutadiene-derived molecular design space through systematic variation of cyclic ethers and N- or O-based nucleophiles. By combining three cyclic ethers with six nucleophiles, an 18-member library was generated, allowing systematic variation of spacer architecture, polarity, and intermolecular interactions. The resulting design space was mapped across thermal and selected morphological and mobility dimensions, revealing that relatively small molecular variations induce substantial changes in macroscopic material behavior. In particular, P9 exhibited distinct nanoscale organization and proton relaxation behavior, illustrating how subtle structural variation translates into differences in morphology and molecular dynamics. Mapping these complementary landscapes guided the selection of P11, with its balanced combination of functionality and physicochemical properties, as a candidate electrolyte additive for Li-S batteries. Electrochemical evaluation revealed that P11 alters the sulfur redox response and impedance response and increases the Coulombic efficiency, resulting in a more gradual capacity decay relative to the cell containing the baseline electrolyte, while also increasing polarization and reducing the accessible capacity. Quantitative sensitivity analysis translated the multidimensional property landscapes into transferable design rules, identifying nucleophile identity as the dominant handle for functionalization degree and thermal stability, whereas the glass transition temperatures exhibited a more distributed dependence on both molecular inputs. From a broader perspective, this work establishes multicomponent molecular editing as a platform for systematically navigating multidimensional polymer design space, extracting molecular design rules, and translating molecular diversification into application-directed material selection.

The development of high-impact denture base formulations that are suitable for digital light processing (DLP) 3D printing is demanding. Indeed, a combination of high flexural strength/modulus and high fracture toughness is required. In this contribution, eight urethane macromonomers (UMs1-8) were synthesized in a one-pot, two-step procedure. Several rigid diols were first reacted with two equivalents of trimethylhexamethylene diisocyanate. The resulting diisocyanates were subsequently end-capped with a free-radically polymerizable monomer bearing a hydroxy group. UMs1-8 were combined with the monofunctional monomer (octahydro-4,7-methano-1H-indenyl)methyl acrylate and a poly(ε-caprolactone)-polydimethylsiloxane-poly(ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer (BCP1) as a toughening agent. The double-bond conversion, glass transition temperature (Tg), and mechanical properties (flexural strength/modulus, fracture toughness) of corresponding light-cured materials were measured (cured in a mold using a light-curing unit). The results showed that the incorporation of BCP1 was highly efficient at significantly increasing the fracture toughness, as long as the obtained networks exhibited a low crosslink density. The structure of the urethane macromonomer (nature of the rigid group in the spacer; nature and number of polymerizable groups) was demonstrated to be crucial to reach the desired properties (balance between flexural strength/modulus and fracture toughness). Amongst the evaluated macromonomers, UM1 and UM2 were particularly promising. By correctly adjusting the BCP1 content, light-cured formulations based on those two urethane dimethacrylates were able to fulfill ISO20795-1:2013 standard requirements regarding high-impact materials. These formulations are therefore suitable for the development of 3D printable high-impact denture bases.

Easy and rapid preparations of magnetic Co- and Pd-containing mesoporous carbons (IM1, IM2 and DM) from green phenolic resins, amphiphilic templates and metallic salts via two synthetic routes are reported. Catalysts IM1 and IM2 are prepared via an indirect method involving two steps, i.e., the preparation of Co-containing mesoporous carbons with different Co contents (2.5 and 12.5%) and the further introduction of Pd (2.3%) via impregnation using a solution of a Pd salt and a process of thermal reduction. The mesoporous carbon obtained contains two distinct crystalline metallic phases, i.e., Co particles of 5.0 nm (IM1) and Pd nanoparticles of ~1.3 nm (IM1), while the increase in Co content triggers higher Co particle sizes of 23 nm and Pd particle sizes of 1.3 and 6.8 nm (IM2). Differently, the catalyst DM is prepared via direct synthesis, in one step, including all precursors and both metal salts. This results in Pd50-Co50 nanoalloys of 6.5 nm uniformly dispersed in the carbon matrix. The reactivity and reusability of catalysts IM1, IM2 and DM were then ascertained in organic synthesis for hydrogenations of nitroarenes and enones. It turned out that no reactions were observed in the presence of the catalyst DM due to the presence of Co in Pd50-Co50, which deactivates the catalytic activity of Pd. Gratifyingly, catalysts IM1 and IM2 were very efficient for mild hydrogenations of both nitroarenes and enones using only 5 mequiv. of supported Pd in EtOH at room temperature. The smaller Pd particle sizes (1.3 nm) and the high surface-to-volume area are probably responsible for the high reactivity observed. Catalysts IM1 and IM2 can be recovered by application of an external magnetic field. However, a more efficient magnetic recovery of catalyst IM2 compared to IM1 was observed due to its higher Co content. Catalyst IM2 can be successfully reused at least seven times without a loss of efficiency. Finally, almost-Pd-free products can be obtained directly after reaction without any purification step, since the Pd leaching is very low (<0.1% of the initial amount), thus decreasing waste and increasing the reaction’s efficiency.

This work explores the use of plasma-enhanced chemical vapor deposition (PE-CVD) to deposit a C-coating on binder-free, self-standing electrodes (SSEs). The C-coating consists of a nanocrystalline graphite thin film with crystalline domains measuring approximate to 14 nm. Regardless of the fabrication pyrolysis temperature of SSE, an increase in crystallite size and a reduction in interlayer space and defects is observed after C-coating and post-treatment at 1500 degrees C. Pyrolysis of the SSE at 900 degrees C induce better coverage with the nanographitic layer during PE-CVD , but prevents the development of closed pores during post-treatment at 1500 degrees C. In contrast, a large number of closed pores form when the SSE is pyrolyzed at 1500 degrees C. However, no difference in performance is observed between the C-coated SSE pyrolyzed at 900 and 1500 degrees C and post-annealed at 1500 degrees C, therefore, lower temperature can be advantageously used for the pyrolysis step. Nevertheless, post-treatment at 1500 degrees C is necessary to enhance performance. For both materials, the graphite coating minimized the undesirable reactions with the electrolyte, leading to more stable and conductive solid electrolyte interphase, which improves iCE (from 91.0% to 92.5%). A high reversible capacity of 320 mAh g-1 is also obtained, and the higher coating's conductivity is beneficial for rate capability.

Photocurable denture bases require both rigidity (high flexural strength and modulus) and high fracture toughness (to prevent cracking or breaking under mechanical stress). These antagonist properties can be provided by the incorporation of block copolymers (BCPs) due to their unique self-assembly properties conferring an overall improvement of fracture toughness and mechanical properties to denture base materials. In the present work, it was shown that poly(methyl methacrylate)-block-poly(dimethyl siloxane)-block-poly(methyl methacrylate) (PMMA-PDMS-PMMA) triblock copolymers are highly efficient toughening agents for (meth)acrylic resins, resulting in a significantly improved fracture toughness without compromising the mechanical strength or processing. The influence of the PMMA:PDMS block ratio and the weight fraction of triblock copolymer (3-10 wt %) in the resin was investigated and revealed that the most efficient toughening triblock copolymer is composed of PMMA and PDMS blocks having the similar molecular weight of 8000 g mol-1. The highest fracture toughness value (Kmax = 2,25 MPa m1/2) was obtained with this BCP at a concentration of 5 wt% in the resin, an improvement of 180 % compared to the BCP free resin. Small angle X-ray scattering measurements revealed that self-assembly of BCPs led to the formation of spherical micelles that transform to small clusters after curing if the compatible PMMA block is sufficiently long compared to the incompatible PDMS block. Otherwise, large aggregates were observed. Transmission electron microscopy confirmed the SAXS results, showing the clusters of spherical micelles. As toughening agents, PMMA-PDMS-PMMA BCPs showed better performance than the reference polycaprolactone-polysiloxane (PCL-PDMS-PCL) one. The influence of the nature of the compatible block (PMMA versus PCL) and of the PMMA:PDMS block ratio on the fracture toughness of radical-cured resin systems was clearly demonstrated in this study. The most promising formulation was shown to be suitable for digital light processing 3D printing.

Traffic-related particulate matter (PM) is a significant public health concern in urban areas. This study evaluates a novel, passive air filtration prototype installed along a high-traffic ring road in Strasbourg, France. The filtration process focuses on a porous polyester fiber matrix coated with a thin layer of vegetable oil. Over a 14-week period, the prototype achieved a total PM capture rate of up to 84 +/- 6 g. m(-2). Chemical analysis revealed that the majority of trapped particles originated from tire and pavement abrasion, with a minor contribution from metallic particles from the brake system. The filtration performance can be varied with meteorological conditions, which was explained by the use of weather monitoring and interpolation models. Regression models further demonstrated an influence of the oil viscosity on the captured PM quantity. Compared to existing passive air filtration systems, this concept offers a material with a very low-pressure drop, a critical factor for passive performance, enhanced by the coating liquid layer. Furthermore, the system addresses practical deployment challenges through its washability and reusability, significantly reducing waste associated with PM collection after filtration. These findings underscore the potential of this low-maintenance, scalable passive filtration concept for targeted PM exposure reduction near roadways and in sensitive urban settings.

OBJECTIVE:The objective of this work is to evaluate an innovative toughening technology for the development of 3D printable high impact denture base materials. METHODS:Urethane dimethacrylate DMA1 was synthesized in a two-step, one-pot reaction, starting from tricyclo[5.2.1.0(2,6)]decanedimethanol. Poly(ɛ-caprolactone)-polydimethylsiloxane-poly(ɛ-caprolactone) (PCL-PDMS-PCL) triblock copolymers BCPs1-3, exhibiting various PCL block length, were prepared from a bis(3-aminopropyl) terminated polydimethylsiloxane (2000 g mol-1) by ring-opening polymerization of ε-caprolactone (CL). DMA1/(octahydro-4,7-methano-1H-indenyl)methyl acrylate (OMIMA) 1/1 (wt/wt) formulations containing various amounts of BCPs1-3 were prepared. The flexural strength/modulus and the fracture toughness of light-cured materials were measured according to ISO 20795-1:2013. The double bond conversion (DBC) and glass transition temperature (Tg) were determined by NIR spectroscopy and DMTA measurements, respectively. SAXS experiments were performed on dispersions of BCP2 at different concentrations, before and after the light-curing step. The nanomorphology of cured specimens was characterized by scanning transmission electron microscopy (STEM), whereas the fracture surfaces of the single-edge notched beam (SENB) specimens were analyzed by scanning electron microscopy (SEM). A monoblock denture of the lower jaw was 3D printed from the most promising formulation using the PrograPrint system (Ivoclar, Liechtenstein). RESULTS:The addition of BCPs1-3 to the DMA1/OMIMA mixture led to a decrease of the mechanical properties (flexural strength/modulus) as well as to a significant improvement of the fracture toughness. It was demonstrated that the PDMS/PCL block ratio plays a significant role on the toughening properties. The BCP2 based material provided the highest flexural strength value. The evaluation of formulations containing different contents of BCP2 showed that 4.5 wt% was ideal. Indeed, the corresponding light-cured material fulfilled the ISO 20795-1:2013 requirements for high impact denture bases. SAXS and STEM measurements clearly showed that BCP2 was able to self-assemble in the monomer mixture, leading to the formation of a nanostructure after curing. A monoblock denture of the lower jaw was successfully 3D printed using the most promising formulation. SIGNIFICANCE:By carefully selecting the nature of the components, the use of block copolymers as toughening agents in a urethane dimethacrylate macromonomer/monofunctional monomer mixture can efficiently lead to the formulation of 3D printable high impact denture bases.

In this study, we investigate near-field photopolymerization at the tips of gold nanobipyramids (AuNBPs) under linearly polarized irradiation conditions with femtosecond pulses in the near infrared region. TEM was used to visualize the localisation and spatial extend of the polymer resulting from the near-field photopolymerization. The single-tilt mode in TEM provides 3D information of the position of the nanoparticle on the substrate and the polymer lobes. In particular, we demonstrate that photopolymerization is localized mainly at the tips of AuNBPs, in line with the electromagnetic field distribution expected by simulations. We observed experimentally that when AuNBPs lie on the substrate via a facet, asymmetrical polymerization occurred: while polymerization is constrained by the substrate on the side in contact with the surface, we showed the possibility of fabricating a nano-sized polymer volume in 3D via near-field photopolymerization. These results illustrate the great control of photopolymerization at the nanoscale and represent a major step towards 3D fabrication at nanometer resolution.

Wet-chemistry-synthesized gold nanourchins (Au NUs), characterized by spiky morphologies with spherical cores, exhibit complex and geometry-dependent plasmonic field enhancement properties distinct from those of symmetrical nanostructures. While plasmon hybridization and mode coupling in branched nanostructures have been broadly studied, the specific optical behavior of Au NUs-particularly regarding spike length distribution and ultrafast dynamics-remains underexplored. This study investigates the steady-state and transient absorption spectra of Au NUs with 50-80 nm cores and 5-20 nm spikes, revealing multiple resonance bands. Transient absorption spectroscopy at various excitation wavelengths confirmed the presence of distinct resonances. Electromagnetic simulations based on TEM tomography-inspired models identified two key extinction bands: a green-wavelength dark mode resonance and a red/nIR spike-induced resonance attributed to the lightning rod effect. Simulations further showed that short, uniformly distributed spikes (aspect ratio <= 1) weakly excite dark resonances, while longer spikes (aspect ratio >1) induce hybridized longitudinal resonances and significant redshifts. Broad spike length distributions result in multiple coexisting resonances, aligning with experimental extinction spectra. A preliminary surface-enhanced Raman scattering study using 2-naphthalene thiol confirmed stronger enhancement for long-spiked Au NUs under 785 nm excitation, validating the field enhancement potential of the identified resonances.

Saponite-like materials have a wide range of potential applications, especially in heterogeneous catalysis. Despite the simplicity of the synthesis, the mechanisms of the formation of saponite are not well understood yet. The aim of the present study was to investigate a possible correlation between the coordination of Al in the solid phase and in the solution. For this, samples were prepared by varying the initial OH:Si molar ratio from 0.18 to 2.14, leading to a pH in the supernatant after the hydrothermal treatment of 6.7 to 12.7, respectively. The characterization of the material was performed by combining nuclear magnetic resonance (NMR) and X-ray absorption near edge structure (XANES) spectroscopies, and good agreement was obtained between the two techniques. Between pH7 and pH10, 60-65% of aluminum was found to be in tetrahedral coordination, while this percentage increased above pH10 (up to 81%). These results correlated with the speciation of the aluminum in aqueous solution. Indeed, above pH10, all available aluminum was in the soluble form Al(OH)(4)(-).

For mild and ecofriendly polymerization conditions, Redox Initiating Systems (RISs) are more and more attractive. Indeed, the redox polymerization can be carried out at room temperature without any external energetic stimulus. Moreover, these latter processes can be very efficient under air and without purification of the monomers/resins. In this work, new redox initiating systems based on dihydropyridines are reported. An excellent reactivity is found in presence of copper complexes as catalyst, acid and peroxide. A full control of the gel time is possible by the selection of the appropriated reactant concentrations. These systems were characterized by optical pyrometry experiments as well as FTIR spectroscopy. Tack-free surfaces as well as potential photoactivation for on-demand polymerization can be obtained.

Direct outdoor air depollution represents an interesting path for preventing indirect disease. In the present work, a simple and efficient PMs trapping media based on the use of an oil-coated structured polymer media was developed for passive trapping of various PMs, ranging from coarse (PM10), to fine (PM2.5) and ultra-fine (PM1) dimension in outdoor environment. The device can be easily regenerated by a simple washing with a mixture of water and detergent followed by a new oil coating cycle. The total PM loading mass of the passive trap and the recovered PMs are analyzed through different techniques and confirm the great efficiency of such filter to trap various PMs when exposed to a high traffic road. The spent filter can be regenerated through a simple washing step and can be repeatedly re-used with similar PM loading mass. The high and long-lasting total PM loading mass were also supported by numerical simulations based on computational fluid dynamics, also used to propose an optimization implementation of such system for future deployment at scale.

The analysis of the local distribution of the electric field, induced by localized surface plasmon resonance (LSPR), is crucial for selecting the morphology of gold nanoparticles (AuNPs) for specific applications. The reported study is based on an LSPR-induced near-field two-photon photopolymerization (NF2P) reaction. The initiation of NF2P is triggered by LSPR-enhanced near-field light, while in the far-field, oxygen inhibits this reaction. The spatial extent of the NF2P reaction is compared to the local electric field distribution depending on AuNP morphologies, established by numerical simulations. Overall, our results demonstrate that the photopolymerization is not only driven by the local near-field enhancement but also strongly depends on the topologies of nano-object, and the photopolymerization extension was more confined in anisotropic and sharp structures compared to isotropic ones. Additionally, we showcased its capability to confine polymerization reactions within nanoscale volumes with the possibility of controlling the localization of polymer lobes at a single triangle apex, for instance, via light polarization.

Photocuring 3D printing of materials exhibiting high fracture toughness and excellent mechanical properties (flexural strength/modulus) is challenging. Nowadays, most of the photocurable 3D printing resins are based on a mixture of multifunctional (meth)acrylates and provide therefore brittle materials. This article describes further developments of a toughening strategy based on the incorporation of block copolymers in low crosslink density methacrylate-based materials. Six dimethacrylates bearing a bisphenol A core and urethane groups are successfully synthesized. Various spacers between the bisphenol A core and the methacrylate groups are selected. Each monomer is combined with (octahydro-4,7-methano-1H-indenyl)methyl acrylate as a monofunctional monomer and a poly(epsilon-caprolactone)-polydimethylsiloxane-poly(epsilon-caprolactone) triblock copolymer is added as toughener. It is shown that the addition of the triblock copolymer results for all mixtures in a strong increase of the fracture toughness. Moreover, the higher the amount of monofunctional monomer, the stronger the increase. The nature of the urethane dimethacrylate is found to have a significant influence on the fracture toughness, flexural strength, and flexural modulus of cured materials. Two of the synthesized dimethacrylates are identified as promising candidates for the development of fracture-tough photocuring 3D printing materials. Innovative photocurable resins based on novel urethane macromonomers, a monofunctional acrylate, and a triblock copolymer, are evaluated for the preparation of fracture tough denture base materials. This article highlights the high efficiency of triblock copolymers as toughening agents in low crosslink density dimethacrylate networks. image