TiO2/PDA Multilayer Nanocomposites with Exceptionally Sharp Large-Scale Interfaces and Nitrogen Doping Gradient.

The evolving field of photocatalysis requires the development of new functional materials, particularly those suitable for large-scale commercial systems. One particularly promising approach is the creation of hybrid organic/inorganic materials. Despite being extensively studied, materials such as polydopamine (PDA) and titanium oxide continue to show significant promise for use in such applications. Nitrogen-doped titanium oxide and free-standing PDA films obtained at the air/water interface are particularly interesting. This study introduces a straightforward and reproducible approach for synthesizing a novel class of large-scale multilayer nanocomposites. The method involves the alternate layering of high-quality materials at the air/water interface combined with precise atomic layer deposition techniques, resulting in a gradient nitrogen doping of titanium oxide layers with exceptionally sharp oxide/polymer interfaces. The analysis confirmed the presence of nitrogen in the interstitial and substitutional sites of the TiO2 lattice while maintaining the 2D-like structure of the PDA films. These chemical and structural characteristics translate into a reduction of the band gap by over 0.63 eV and an increase in the photogenerated current by over 60% compared with pure amorphous TiO2. Furthermore, the nanocomposites demonstrate excellent stability during the 1 h continuous photocurrent generation test.

Tunable TiO2-BN-Pd nanofibers by combining electrospinning and atomic layer deposition to enhance photodegradation of acetaminophen.

The demand for fresh and clean water sources is increasing globally, and there is a need to develop novel routes to eliminate micropollutants and other harmful species from water. Photocatalysis is a promising alternative green technology that has shown great performance in the degradation of persistent pollutants. Titanium dioxide is the most used catalyst owing to its attractive physico-chemical properties, but this semiconductor presents limitations in the photocatalysis process due to the high band gap and the fast recombination of the photogenerated carriers. Herein, a novel photocatalyst has been developed, based on titanium dioxide nanofibers (TiO2 NFs) synthesized by electrospinning. The TiO2 NFs were coated by atomic layer deposition (ALD) to grow boron nitride (BN) and palladium (Pd) on their surface. The UV-Vis spectroscopy measurements confirmed the increase of the band gap and the extension of the spectral response to the visible range. The obtained TiO2/BN/Pd nanofibers were then tested for photocatalysis, and showed a drastic increase of acetaminophen (ACT) degradation (>90%), compared to only 20% degradation obtained with pure TiO2 after 4 h of visible light irradiation. The high photocatalytic activity was attributed to the good dispersion of Pd NPs on TiO2-BN nanofibers, leading to a higher transfer of photoexcited hole carriers and a decrease of photogenerated electron-charge recombination. To confirm its reusability, recycling tests on the hybrid photocatalyst TiO2/BN/Pd have been performed, showing a good stability over 5 cycles under UV and visible light. In addition, toxicity tests as well as quenching tests were carried out to check the toxicity of the byproducts formed and to determine active species responsible for the degradation. The results presented in this work demonstrate the potential of TiO2/BN/Pd nanomaterials, and open new prospects for the preparation of tunable photocatalysts.

3D Self-Supported Nitrogen-Doped Carbon Nanofiber Electrodes Incorporated Co/CoOx Nanoparticles: Application to Dyes Degradation by Electro-Fenton-Based Process.

We developed free-standing nitrogen-doped carbon nanofiber (CNF) electrodes incorporating Co/CoOx nanoparticles (NPs) as a new cathode material for removing Acid Orange 7 (AO7; a dye for wool) from wastewater by the heterogeneous electro-Fenton reaction. We produced the free-standing N-doped CNF electrodes by electrospinning a polyacrylonitrile (PAN) and cobalt acetate solution followed by thermal carbonation of the cobalt acetate/PAN nanofibers under a nitrogen atmosphere. We then investigated electro-Fenton-based removal of AO7 from wastewater with the free-standing N-doped-CNFs-Co/CoOx electrodes, in the presence or not of Fe2+ ions as a co-catalyst. The electrochemical analysis showed the high stability of the prepared N-doped-CNF-Co/CoOx electrodes in electrochemical oxidation experiments with excellent degradation of AO7 (20 mM) at acidic to near neutral pH values (3 and 6). Electro-Fenton oxidation at 10 mA/cm2 direct current for 40 min using the N-doped-CNF-Co/CoOx electrodes loaded with 25 wt% of Co/CoOx NPs led to complete AO7 solution decolorization with total organic carbon (TOC) removal values of 92.4% at pH 3 and 93.3% at pH 6. The newly developed N-doped-CNF-Co/CoOx electrodes are an effective alternative technique for wastewater pre-treatment before the biological treatment.

Synthesis of PLA-poly(ether urethane)-PLA copolymers and design of biodegradable anti-adhesive membranes for orthopaedic applications.

Peritendinous adhesions cause chronic pain and disability. Leading causes are trauma to tendons and surrounding tissues and immobilization after surgery. Adhesions occur between 24 hours to 6 weeks after surgery. Anti-adhesion barriers are currently the best option available to prevent peritendinous adhesions, but are ineffective and difficult to use. We developed an anti-adhesive membrane that can be easily applied during tendon surgery and effectively prevent adhesions. The membrane is based on a new triblock copolymer, is non-toxic, can be bio-eliminated, and has a degradation rate of more than 6 weeks for optimal anti-adhesion effect. We synthesized and characterized poly(ether urethane) (PEU) from poly(ethylene glycol). Triblock copolymers poly(lactic acid)-PEU-poly(lactic acid) (PLA-PEU-PLA) were then synthesized from PEU with PLA blocks of different lengths, and characterized. The membranes were shaped by hot molding and their mechanical properties, contact angle, water uptake, the kinetics of in vitro degradation and cytotoxicity were studied. Mechanical properties were developed according to the needs of orthopaedic surgeons. Results showed that membranes maintained their filmogenic integrity, have a degradation rate for optimal adhesion prevention, can be bioeliminated and biocompatible suggesting that they could be safely and effectively used as anti-adhesion orthopaedic devices. These results support the use of PLA-PEU-PLA membranes as a medical device, however, the effectiveness of the membranes in vivo needs to be further evaluated. A future study using an in vivo rat model of postoperative peritendinous adhesions is currently being developed.

Palladium/Carbon Nanofibers by Combining Atomic Layer Deposition and Electrospinning for Organic Pollutant Degradation.

As organic dyes are a major source of pollution, it is important to develop novel and efficient heterogeneous catalysts with high activity for their degradation. In this work, two innovative techniques, atomic layer deposition and electrospinning, were used to prepare palladium nanoparticles (Pd NPs) supported on carbon nanofibers (CNFs). The sample morphology was investigated using scanning and transmission electron microscopy. This showed the presence of nanofibers of several micrometers in length and with a mean diameter of 200 nm. Moreover, the size of the highly dispersed Pd NPs was about 7 nm. X-ray photoelectron spectroscopy visually validated the inclusion of metallic Pd. The prepared nano-catalysts were then used to reduce methyl orange (MO) in the presence of sodium borohydride (NaBH4). The Freundlich isotherm model was the most suitable model to explain the adsorption equilibrium for MO onto the Pd/CNF catalysts. Using 5 mL MO dye-solution (0.0305 mM) and 1 mL NaBH4 (0.026 mM), a 98.9% of catalytic activity was achieved in 240 min by 0.01 g of the prepared nano-catalysts Pd/C (0.016 M). Finally, no loss of catalytic activity was observed when such catalysts were used again. These results represent a promising avenue for the degradation of organic pollutants and for heterogeneous catalysis.

Atomic layer deposition of Pd nanoparticles on self-supported carbon-Ni/NiO-Pd nanofiber electrodes for electrochemical hydrogen and oxygen evolution reactions.

The most critical challenge in hydrogen fuel production is to develop efficient, eco-friendly, low-cost electrocatalysts for water splitting. In this study, self-supported carbon nanofiber (CNF) electrodes decorated with nickel/nickel oxide (Ni/NiO) and palladium (Pd) nanoparticles (NPs) were prepared by combining electrospinning, peroxidation, and thermal carbonation with atomic layer deposition (ALD), and then employed for hydrogen evolution and oxygen evolution reactions (HER/OER). The best CNF-Ni/NiO-Pd electrode displayed the lowest overpotential (63 mV and 1.6 V at j = 10 mA cm-2), a remarkably small Tafel slope (72 and 272 mV dec-1), and consequent exchange current density (1.15 and 22.4 mA cm-2) during HER and OER, respectively. The high chemical stability and improved electrocatalytic performance of the prepared electrodes can be explained by CNF functionalization via Ni/NiO NP encapsulation, the formation of graphitic layers that cover and protect the Ni/NiO NPs from corrosion, and ALD of Pd NPs at the surface of the self-supported CNF-Ni/NiO electrodes.