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This study explored the photocatalytic hydrogen evolution reaction (HER) using novel biohydrogel composites comprising chitosan, and a photocatalyst consisting in TiO 2 P25 decorated with Au and/or Cu mono- and bimetallic nanoparticles (NPs) to boost its optical and catalytic properties. Low loads of Cu and Au (1 mol%) were incorporated onto TiO 2 via a green photodeposition methodology. Characterization techniques confirmed the incorporation of decoration metals as well as improvements in the light absorption properties in the visible light interval (λ > 390 nm) and electron transfer capability of the semiconductors. Thereafter, Au and/or Cu NP-supported TiO 2 were incorporated into chitosan-based physically crosslinked hydrogels revealing significant interactions between chitosan functional groups (hydroxyls, amines and amides) with the NPs to ensure its encapsulation. These materials were evaluated as photocatalysts for the HER using water and methanol mixtures under simulated sunlight and visible light irradiation. Sample CuAuTiO 2 /ChTPP exhibited a maximum hydrogen generation of 1790 μmol g -1  h -1 under simulated sunlight irradiation, almost 12-folds higher compared with TiO 2 /ChTPP. Also, the nanocomposites revealed a similar tendency under visible light with a maximum hydrogen production of 590 μmol g -1  h -1 . These results agree with the efficiency of photoinduced charge separation revealed by transient photocurrent and EIS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

The synthesis of CuAu-based monometallic (MNPs) and bimetallic nanoparticles (BNPs) supported on chitosan-based hydrogels for their application as catalysts is presented. The hydrogels consisted of chitosan chains cross-linked with tripolyphosphate (TPP) in the form of beads with an approximate average diameter of 1.81 mm. The MNPs and BNPs were obtained by the adsorption of metallic ions and their subsequent reduction with hydrazine, achieving a metallic loading of 0.297 mmol per gram of dry sample, with average nanoparticle sizes that were found between 2.6 and 4.4 nm. Both processes, metal adsorption and the stabilization of the nanoparticles, are mainly attributed to the participation of chitosan hydroxyl, amine and amide functional groups. The materials revealed important absorption bands in the visible region of the light spectra, specifically between 520 and 590 nm, mainly attributed to LSPR given the nature of the MNPs and BNPs inside the hydrogels. Subsequently, the hydrogels were evaluated as catalysts against the reduction of 4-nitrophenol (4NP) into 4-aminophenol (4AP), followed by UV-visible spectroscopy. The kinetic advance of the reaction revealed important improvements in the catalytic activity of the materials by synergistic effect of BNPs and plasmonic enhancement under visible light irradiation, given the combination of metals and the light harvesting properties of the nanocomposites. Finally, the catalytic performance of hydrogels containing BNPs CuAu 3:1 showed an important selectivity, recyclability and reusability performance, due to the relevant interaction of the BNPs with the chitosan matrix, highlighting the potential of this nanocomposite as an effective catalyst, with a potential environmental application., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Angel Leiva and David Diaz reports was provided by National Agency for Research and Development, Spanish Ministry of Science, Innovation and Universities. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Hybrid nanofibers of a chitosan-polycaprolactone blend containing titanium dioxide nanoparticles TiO 2 NPs, were prepared through electrospinning to study their adsorption and photocatalytic degradation capabilities of the model organic water pollutants, rhodamine B, RhB. To obtain uniform and bead-free nanofibers, an optimization of the electrospinning parameters was performed. The optimization was carried out by systematically adjusting the solution conditions (solvent, concentration, and polymer ratio) and instrumental parameters (voltage, needle tip-collector distance, and flow). The obtained materials were characterized by FT-IR, TGA, DSC, SEM, TEM, mechanical tensile test, and water contact angle. The photoactivity was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of RhB. TiO 2 NPs were incorporated ex-situ into the polymer matrix, contributing to good mechanical properties and higher hydrophilicity of the material. The results showed that the presence of chitosan in the nanofibers significantly increased the adsorption of RhB and its photocatalytic degradation by TiO 2 NPs (5, 55 and 80 % of RhB degradation with NFs of PCL, TiO 2 /PCL and TiO 2 /CS-PCL, after 30 h of light irradiation, respectively), evidencing a synergistic effect between them. The results are attributed to an attraction of RhB by chitosan to the vicinity of TiO 2 NPs, favouring initial adsorption and degradation, phenomenon known as "bait-and-hook-and-destruct" effect., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Conductive and flexible bio-based materials consisting of chitosan films coated with conductive poly(3-hexylthiophene) (P3HT) were prepared. Thermal, optical, mechanical, morphological, wettability, and conductive properties were analyzed. In a very simple and effective method of chitosan film modification, a controlled volume of a P3HT solution was deposited onto a previously formed chitosan film, assisted by the spin coating method. Later, P3HT-coated chitosan films were doped by simple contact with an aqueous solution of HAuCl 4 . The use of HAuCl 4 becomes attractive because the reports on the doping process in this type of material using this reagent are still scarce and recent to date. In addition, since this acid is a well-known metal nanoparticle precursor, its use opens new future perspectives for these materials into new applications. The effect of P3HT concentration and doping times on film properties was studied. Attenuated total reflectance spectroscopy and UV-Vis spectroscopy allowed us to demonstrate that the presence of the P3HT coating and its doping induce significant changes in the vibrational modes and optoelectronic properties of samples. Additionally, the images obtained by scanning electron microscopy showed a well-distributed and homogeneous coating on the surface of chitosan films. Measured conductivity values of doped film samples fall in the range from 821.3 to 2017.4 S/m, representing, to the best of our knowledge, the highest values reported in the literature for chitosan/chitin-based materials. Indeed, these values are around or even higher than those obtained for some materials purely consisting of conductive polymers.

Using solution-casting method, binary blends of chitosan (CS) and poly (ethylene oxide) (PEO 100,000) containing Au nanoparticles (AuNPs) were prepared. Shifts in the melting temperature (Tm) and crystallization temperature (Tc) values for CS/PEO and CS/PEO/AuNPs blends were observed by calorimetric analysis. In general, CS/PEO/AuNPs blends tended to decompose at higher temperatures than neat polymers. From the FT-IR spectra, shifts in the main signals, such as -NH2, -OH and COC, were detected in the blends and were attributed to the polymer interactions and the incorporation of gold nanoparticles. In addition, the analysis of the blend topographies by atomic force microscopy (AFM) showed that at a higher CS content, more homogenous surfaces were observed. This behavior was attributed to the interactions present in the CS/PEO/AuNPs blends. Finally, theoretical analyses helped to confirm that the gold nanoparticles would be preferentially adsorbed onto the chitosan microdomains due to the interactions between acetyl and hydroxyl groups and Au atoms., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Graphical abstract A novel environmental friendly method to obtaining bio nanocomposites with interesting catalytic properties, based on chitosan and containing different amounts of gold nanoparticles is presented. The method only involves the use of the biopolymer chitosan and a precursor gold salt, without addition of supplementary reducing agents, the main stage of nanocomposites obtaining, takes place in solid phase induced only by heating. Highlights • Nanocomposites of chitosan with different amounts gold nanoparticles were prepared. • Gold nanoparticles were generated in situ by a new heat-induced process in solid phase. • It was possible to control the gold nanoparticles content and size in the nanocomposites. • The catalytic effect of nanocomposites depend on the gold nanoparticles content. Abstract A novel method to obtain catalytic bio-nanocomposites based on chitosan containing different amounts of gold nanoparticles generated in situ is reported. The formation of gold nanoparticles takes place in solid phase assisted by a heating induced process. This method only involves the use of chitosan biopolymer and a gold salt precursor. Unlike other methods the addition of external reducing and stabilizing agents to generate gold nanoparticles, is not needed because these roles are played by chitosan. Therefore, the striking properties of chitosan (e.g., high functionality, biodegradability and biocompatibility) are profited, in order to design a facile and green route of synthesis. Additionally, the described method allows to vary the amount and size of the gold nanoparticles contained in the bio-nanocomposite by using different gold ion compositions and temperatures of heating process. Finally, the bio-nanocomposite performance as heterogeneous catalyst on the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system was assessed. The results showed a significant catalytic effect that increases as the content of gold nanoparticles in the bio-nanocomposite also increases. [ABSTRACT FROM AUTHOR]