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Multifunctional Bi- and Fe-modified carbon xerogel composites (CXBiFe), with different Fe concentrations, were obtained by a resorcinol–formaldehyde sol–gel method, followed by drying in ambient conditions and pyrolysis treatment. The morphological and structural characterization performed by X-ray diffraction (XRD), Raman spectroscopy, N2 adsorption/desorption porosimetry, scanning electron microscopy (SEM) and scanning/transmission electron microscopy (STEM) analyses, indicates the formation of carbon-based nanocomposites with integrated Bi and Fe oxide nanoparticles. At higher Fe concentrations, Bi-Fe-O interactions lead to the formation of hybrid nanostructures and off-stoichiometric Bi2Fe4O9 mullite-like structures together with an excess of iron oxide nanoparticles. To examine the effect of the Fe content on the electrochemical performance of the CXBiFe composites, the obtained powders were initially dispersed in a chitosan solution and applied on the surface of glassy carbon electrodes. Then, the multifunctional character of the CXBiFe systems is assessed by involving the obtained modified electrodes for the detection of different analytes, such as biomarkers (hydrogen peroxide) and heavy metal ions (i.e., Pb2+). The achieved results indicate a drop in the detection limit for H2O2 as Fe content increases. Even though the current results suggest that the surface modifications of the Bi phase with Fe and O impurities lower Pb2+ detection efficiencies, Pb2+ sensing well below the admitted concentrations for drinkable water is also noticed.

A series of thiocyanate‐free bis(tridentate) ruthenium(II) complexes incorporating 1,2,3‐triazole‐derived NNN‐, NCN‐, and CNC‐coordinating ligands has been employed for sensitizing ZnO photoanodes for dye‐sensitized solar cells (DSSCs). Additionally, the first use of the TEMPO+/TEMPO (2,2,6,6‐tetramethyl‐piperidine‐1‐oxyl) redox mediator as a surrogate for the I3−/I− redox couple in ZnO nanostructured DSSCs is presented. Compared with I3−/I−‐based electrolytes, shorter charge lifetimes and diffusion lengths were determined for the TEMPO+/TEMPO‐based electrolyte. Nonetheless, similar power conversion efficiencies (PCEs) were achieved with both electrolytes for the RuNCN and RuCNC complexes, whereas higher PCEs are enabled by the iodine‐free electrolyte in case of RuNNN. The combination of the molecular sensitizers and the TEMPO‐based electrolyte exhibits relatively high external quantum efficiency (EQE) and promising PCEs, ranging from 4.48 to 1.47 %, which are—in part—comparable to that of ZnO‐DSSCs with the benchmark N749 black dye. The TEMPO‐based electrolyte also exhibits less absorption compared with its I3−/I− counterpart, a favorable feature for enhancing the light harvesting ability of the photoanode. Furthermore, the results show the effect of the dye‐sensitization procedure on the PCE values: The use of ethanol as the solvent compared with methanol increases the DSSC's efficiency, which is attributed to improved chemisorption of the sensitizer onto the ZnO surface.

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In order to obtain a multifunctional nanocomposite material-for electrochemical sensors and photocatalytic applications, structures based on Bi, Fe and TiO2 were grown inside carbon xerogel supports (BiFeCX and BiFeCX-TiO2). First, a wet polymer containing Bi and Fe salts was obtained by following a modified resorcinol-formaldehyde based sol–gel route, followed by drying in ambient conditions, and pyrolysis under inert atmosphere. Then, through TiCl4 hydrolysis, TiO2 nanoparticles were deposited on the BiFeCX xerogel leading to BiFeCX-TiO2. The morphological and structural characterization of the investigated nanocomposites consisted in X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and N2 adsorption measurements, revealing porous carbon structures with embedded nanoparticles and the particularities driven by the pyrolysis and TiCl4 treatment. The new modified electrodes based on BiFeCX or BiFeCX-TiO2 nanocomposite materials, kept in a chitosan matrix (Chi) and deposited on a glassy carbon (GC) electrode surface (GC/Chi-BiFeCX or GC/Chi-BiFeCX-TiO2), were obtained and investigated for Pb(II) voltammetric detection and H2O2 amperometric detection. Moreover, the BiFeCX-TiO2 nanocomposite was tested for the photocatalytic degradation of methyl orange. The great potential of BiFeCX nanocomposite material for developing electrochemical sensors, or BiFeCX-TiO2 for sensors application and photocatalytic application was demonstrated.

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C–Bi–Fe) represent an interesting model of carbon nanostructures decorated with multifunctional nanoparticles (NPs) with applicability for electrochemical sensors and catalysts. The present study addresses the fundamental aspects of the catalyzed growth of nano-graphites in C–Bi–Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C–Bi–Fe xerogel is investigated using different pyrolysis treatments. At lower temperatures (~750°C), hybrid bismuth iron oxide (BFO) NPs are frequently observed, while graphitization manifests under more specific conditions such as higher temperatures (~1,050°C) and reduction yields. An in situ heating TEM experiment reveals graphitization activity between 800 and 900°C. NP motion is directly correlated with textural changes of the carbon support due to the catalyzed growth of graphitic nanoshells and nanofibers as confirmed by HR-TEM and electron tomography (ET) for the graphitized sample. An exponential growth model for the catalyst dynamics enables the approximation of activation energies as 0.68 and 0.29–0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst–feed gas interactions are considered as the main constraints to enhanced growth.