Ceria-doped titania photocatalysts (ceria loading 0.25–5.0 wt%) were synthesized by hydrothermal methods for water remediation. Nanotubes (CeTNTx) and nanoparticles (CeTNPx) were obtained. Ceria doping was applied to tune the electronic properties of nanostructured titania, boosting its photocatalytic activity. CeTNT nanostructures contained anatase as the only titania phase, whereas the CeTNP series consisted of both anatase and rutile polymorphs. The Ce addition induced a decrease in the energy gap, allowing enhancement of visible light harvesting. The photodegradation of methylene blue, MB, in aqueous solution was chosen to study the influence of the morphology and the ceria loading on the photocatalytic response, under UV and solar light. Both CeO₂–TiO₂ nanoparticles and nanotubes were found to be very active under UV light. The highest MB degradation rates were obtained for the 0.25 wt% CeO₂ doping, for both nanotubes and nanoparticles (0.123 and 0.146 min⁻¹, respectively), able to photodegrade completely the dye after 120 min. The two samples are stable after a 3-cycle reusability test. The photo-response under simulated solar light confirmed that doping titania with ceria allows harvesting visible light absorption, enhancing its photoactivity. A maximum efficiency of 85% under simulated sunlight at a degradation rate of 0.054 min−1 was obtained. Transient photoluminescence confirmed that MB acts as a charge scavenger for the composite system. These results pointed out ceria-doped titania nanostructures as a promising class of photocatalysts for the degradation of dyes and other hazardous organic compounds in wastewater.

In this study we present and discuss p-n heterostructures for photodetection. The hybrid structures consist of CeO2:ZnO-Cu2O, featuring different concentrations of CeO2, fabricated by using hydrothermal co-growth for CeO2 and ZnO, and sputtering deposition for Cu2O. As the concentration of CeO2 in the ZnO pristine nanorods was increased, the structural, optical and functional features of the materials showed relevant changes, in terms of crystalline domains and optical bandgap. After Cu2O deposition, the ternary materials were tested as UV photodectors, showing very good performance in terms of fast response and decay times. Specifically, we found that the CeO2:ZnO-Cu2O devices maintain a stable current under light irradiation, whose value was dependent on the CeO2 amount incorporated in the ZnO 1D nanostructures. Among all tested configurations, the 5.5 % hybrid CeO2:ZnO-Cu2O exhibits the highest current efficiency, accompanied by rapid rise and decay times. Our investigation suggests that the CeO2:ZnO-Cu2O configuration holds great potential for optoelectronic applications, particularly in the development of UV photodetectors.

The brewery industry annually produces huge amounts of byproducts that represent an underutilized, yet valuable, source of biobased compounds. In this contribution, the two major beer wastes, that is, spent grains and spent yeasts, have been transformed into carbon dots (CDs) by a simple, scalable, and ecofriendly hydrothermal approach. The prepared CDs have been characterized from the chemical, morphological, and optical points of view, highlighting a high level of N-doping, because of the chemical composition of the starting material rich in proteins, photoluminescence emission centered at 420 nm, and lifetime in the range of 5.5–7.5 ns. With the aim of producing a reusable catalytic system for wastewater treatment, CDs have been entrapped into a polyvinyl alcohol matrix and tested for their dye removal ability. The results demonstrate that methylene blue can be efficiently adsorbed from water solutions into the composite hydrogel and subsequently fully degraded by UV irradiation.

The synthesis, characterization and photoreduction ability of a new class of carbon dots made from fish scales is here described. Fish scales are a waste material that contains mainly chitin, one of the most abundant natural biopolymers, and collagen. These components make the scales rich, not only in carbon, hydrogen and oxygen, but also in nitrogen. These self-nitrogen-doped carbonaceous nanostructured photocatalyst were synthesized from fish scales by a hydrothermal method in the absence of any other reagents. The morphology, structure and optical properties of these materials were investigated. Their photocatalytic activity was compared with the one of conventional nitrogen-doped carbon dots made from citric acid and diethylenetriamine in the photoreduction reaction of methyl viologen.

Carbon fiber, despite its exceptional properties, remains underutilized due to monetary and environmental concerns. Concurrently, the imminent challenge associated with rising quantities of End-of-Life CFRP (carbon fiber reinforced polymer) demands the further development of recycling strategies. This study focuses on optimizing the recycling process parameters of pyrolysis and oxidation thermal treatment to maximize the retention of mechanical properties in the recycled fibers in the shortest process time. To assess the result of the pyrolysis, single fiber tensile tests were executed to measure strength and stiffness. Additionally, microscopy and spectroscopy studies were carried out to evaluate fiber geometry as well as surface quality. At the laboratory scale, experiments demonstrated that the combination of pyrolysis and oxidation yields clean, reusable fibers with mechanical properties suitable for secondary applications. The influence of various treatment parameters on the strength and stiffness of the recycled fibers was explored, establishing a clear correlation. The outcome is a set of optimized parameters that contribute to mechanical property retention, including a novel recycling method that allows for reduced processing times, as short as 10 min. This work paves the way for a more eco-friendly and cost-effective approach to harnessing the potential of carbon fiber in a wide range of applications while mitigating environmental concerns associated with landfill disposal.

The potential of recycling carbon fiber reinforced polymers (CFRP) as a sustainable solution for waste management is yet to be fully understood. This study reports on the evolution of mechanical, and chemical properties of reclaimed carbon fibers when recycled multiple times via pyrolysis and partial oxidation. The performed work aims at filling the knowledge gap related to repetitive recycling when moving towards a circular flow of resources. A recycling process existing at industrial scale is used to ensure the relevance and usefulness of the results in the current industry scene. Two sets of three identical model composites are recycled using distinct recycling parameters, and their properties are characterized at the end of each recycling cycle. Results show that recycling can lead to an increase in stiffness but can have a negative impact on strength of recovered fibers. Mechanical behaviour shows recovered fibers suitable for secondary applications with medium performance requirements after two recycling cycles. The findings highlight the importance of understanding the material properties evolution during recycling processes. This research contributes to the development of sustainable waste management strategies and a more environmentally friendly future.

In this paper we report the study of down-shifting silica-zirconia glass and glass-ceramic films doped by Tb³⁺ ions and Ag nanoaggregates, which combine the typical spectral properties of the rare-earth-ions with the broadband sensitizing effect of the metal nanostructures. Na-Tb co-doped silica-zirconia samples were obtained by a modified sol-gel route. Dip-coating deposition followed by annealing for solvent evaporation and matrix densification were repeated several times, obtaining a homogeneous crack-free film. A final treatment at 700 °C or 1000 °C was performed to control the nanoscale structural properties of the samples, resulting respectively in a glass (G) or a glass-ceramic (GC), where tetragonal zirconia nanocrystals are surrounded by an amorphous silica matrix. Ag introduction was then achieved by ion-exchange in a molten salt bath, followed by annealing in air to control the migration and aggregation of the metal ions. The comparison of the structural, compositional and optical properties are presented for G and GC samples, providing evidence of highly efficient photoluminescence enhancement in both systems, slightly better in G than in GC samples, with a remarkable increase of the green Tb³⁺ PL emission at 330 nm excitation: 12 times for G and 8 times for GC samples. Furthermore, after Ag-exchange, the shape of Tb³⁺ excitation resembles the one of Ag ions/nanoaggregates, with a broad significant absorption in the whole UV-blue spectral region. This broadband enhanced downshifting could find potential applications in lighting devices and in PV solar cells.

The cationic Cu(I) complex [Cu(N^N)2]+, where N^N is bis(indazol-1-yl)phenylmethane, was synthesized as chloride or tetrafluoroborate salt by reacting CuCl or [Cu(NCCH3)4][BF4] with bis(indazol-1-yl)phenylmethane under mild conditions. The structure of [Cu(N^N)2]Cl was ascertained by single-crystal X-ray diffraction. The complex exhibited bright yellow emission upon excitation with near UV and violet light, attributed to triplet LLCT/MLCT transitions on the basis of experimental data and computational outcomes.

In order to design and tailor materials for a specific application like gas sensors, the synthesis route is of great importance. Undoped and rhodium-doped barium titanate powders were successfully synthesized by two routes; oxalate route and classic route (a modified conventional route where solid-state reactions and thermal evaporation induced precipitation takes place). Both powders were calcined at different temperatures. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX) and Brunauer-Emmet-Teller (BET) analyses are employed to identify the phases and polymorphs, to determine the morphology, the chemical composition and the specific surface area of the synthesized materials, respectively. The so-called oxalate route yields pure BaTiO₃ phase for undoped samples at 700 °C and 900 °C (containing both cubic and tetragonal structures), while the classic route-synthesized powder contains additional phases such as BaCO₃, TiO₂ and BaTi₂O₅. Samples of both synthesis routes prepared by the addition of Rh contain no metallic or oxide phase of rhodium. Instead, it was observed that Ti was substituted by Rh at temperatures 700 °C and 900 °C and there was some change in the composition of BaTiO₃ polymorph (increase of tetragonal structure). Heat-treatments above these temperatures show that rhodium saturates out of the perovskite lattice at 1000 °C, yielding other secondary phases such as Ba₃RhTi₂O₉ behind. Well-defined and less agglomerated spherical nanoparticles are obtained by the oxalic route, while the classic route yields particles with an undefined morphology forming very large block-like agglomerates. The surface area of the synthesized materials is higher with the oxalate route than with the classic route (4 times at 900 °C). The presence of the oxalate ligand with its steric hindrance that promotes the uniform distribution and the homogeneity of reactants could be responsible for the great difference observed between the powders prepared by two preparation routes.

Self-powered photodetectors operating in the UV–visible–NIR window made of environmentally friendly, earth abundant, and cheap materials are appealing systems to exploit natural solar radiation without external power sources. In this study, we propose a new p–n junction nanostructure, based on a ZnO–Co3O4 core–shell nanowire (NW) system, with a suitable electronic band structure and improved light absorption, charge transport, and charge collection, to build an efficient UV–visible–NIR p–n heterojunction photodetector. Ultrathin Co3O4 films (in the range 1–15 nm) were sputter-deposited on hydrothermally grown ZnO NW arrays. The effect of a thin layer of the Al2O3 buffer layer between ZnO and Co3O4 was investigated, which may inhibit charge recombination, boosting device performance. The photoresponse of the ZnO–Al2O3–Co3O4 system at zero bias is 6 times higher compared to that of ZnO–Co3O4. The responsivity (R) and specific detectivity (D*) of the best device were 21.80 mA W–1and 4.12 × 1012 Jones, respectively. These results suggest a novel p–n junction structure to develop all-oxide UV–vis photodetectors based on stable, nontoxic, low-cost materials.

In this work, we present all-oxide p-n junction core-shell nanowires (NWs) as fast and stable self-powered photodetectors. Hydrothermally grown n-type ZnO NWs were conformal covered by different thicknesses (up to 420 nm) of p-type copper oxide layers through metalorganic chemical vapor deposition (MOCVD). The ZnO NWs exhibit a single crystalline Wurtzite structure, preferentially grown along the [002] direction, and energy gap E_g=3.24 eV. Depending on the deposition temperature, the copper oxide shell exhibits either a crystalline cubic structure of pure Cu₂O phase (MOCVD at 250 °C) or a cubic structure of Cu₂O with the presence of CuO phase impurities (MOCVD at 300 °C), with energy gap of 2.48 eV. The electrical measurements indicate the formation of a p-n junction after the deposition of the copper oxide layer. The core-shell photodetectors present a photoresponsivity at 0 V bias voltage up to 7.7 µA/W and time response ≤0.09 s, the fastest ever reported for oxide photodetectors in the visible range, and among the fastest including photodetectors with response limited to the UV region. The bare ZnO NWs have slow photoresponsivity, without recovery after the end of photo-stimulation. The fast time response for the core-shell structures is due to the presence of the p-n junctions, which enables fast exciton separation and charge extraction. Additionally, the suitable electronic structure of the ZnO-Cu₂O heterojunction enables self-powering of the device at 0 V bias voltage. These results represent a significant advancement in the development of low-cost, high efficiency and self-powered photodetectors, highlighting the need of fine tuning the morphology, composition and electronic properties of p-n junctions to maximize device performances.

Self-standing, 1-dimensional (1D) structures of p-type metal oxide (MOx) have been the focus of considerable attention, due to their unique properties in energy storage and solar light conversion. However, the practical performance of p-type MOx is intrinsically limited by their interfacial defects and strong charge recombination losses. Single crystalline assembly can significantly reduce recombination at interface and grain boundaries. Here, we present a one-step route based on plasma assisted physical vapor deposition (PVD), for the rational and scalable synthesis of single crystalline 1D vertically aligned Co3O4 tapered nanorods (NRs). The effect of PVD parameters (deposition pressure, temperature and duration) in tuning the morphology, composition and crystalline structure of resultant NRs is investigated. Crystallographic data obtained from X-ray diffraction and high-resolution transmission electron microscopy (TEM) indicated the single crystalline nature of NRs with [111] facet preferred orientation. The NRs present two optical band gaps at about 1.48 eV and 2.1 eV. Current–voltage (I–V) characteristic of the Co3O4 NRs electrodes, 400 nm long, present two times higher current density at −1 V forward bias, compared to the benchmarking thin film counterpart. These array structures exhibit good electrochemical performance in lithium-ion adsorption–desorption processes. Among all, the longest Co3O4 NRs electrodes delivers a 1438.4 F g−1 at current density of 0.5 mA cm−2 and presents 98% capacitance retention after 200 charge–discharge cycles. The very low values of charge transfer resistance (Rct = 5.2 Ω for 400 nm long NRs) of the NRs testifies their high conductivity. Plasma assisted PVD is demonstrated as a facile technique for synthesizing high quality 1D structures of Co3O4, which can be of interest for further development of different desirable 1D systems based on transition MOx.

Direct stacking of n‐type and p‐type metal oxide (MOx) semiconductors is one of the appealing directions toward low cost and environmentally friendly photovoltaics (PVs). However, the main shortcoming, hindering the PV performance of MOx heterojunction devices is attributed to the tradeoff between light absorption and maximized carrier extraction in p‐type MOx. In this work, we demonstrate that the nanorod (NR) geometry of Co₃O₄ light absorber with a nearly ideal bandgap of ∼1.48 eV, can remove this hurdle through strong internal light trapping of adjacent one‐dimensional (1D) structure and enhanced carrier mobility. The inverted n‐on‐p configuration of the core‐shell 1D heterojunction, obtained by depositing a thin TiO₂ n‐type layer, resulted in enlarged charge generation compared to the typical p‐on‐n counterpart device. Fine‐tuning of Co₃O₄ NRs length, permits PV investigation of the heterojunctions with respect to absorber layers thickness. The optimized Co₃O₄ NRs/TiO₂ heterojunction (30 nm Co₃O₄ NR length) presented a record high open circuit photovoltage (V_oc) of (0.52 ± 0.03) V under 1 sun irradiation. Impedance analysis of the heterojunctions, indicates formation of the p⁺‐p depletion. The presented work can highlight some vital venues to enhance photoconversion efficiency of the all‐oxide heterojunctions while introducing a pioneer contender as inverted (n‐on‐p) MOx heterojunction.

Characterizing carrier redistribution due to optical field modulation in a plasmonic hot-electron/semiconductor junction can be used to raise the framework for harnessing the carrier decay of plasmonic metals in more efficient conversion systems. In this work we comprehensively studied the carrier redistribution mechanisms of a 1-dimensional (1D) metal-semiconductor Schottky architecture, holding the dual feature of a hot-electron plasmonic system and a simple metal/semiconductor junction. We obtained a strongly enhanced external quantum efficiency (EQE) of the plasmonic Ag decorated ZnO semiconductor in both the band-edge region of ZnO and the corresponding plasmonic absorption profile of the Ag NPs (visible region). Simultaneously, the insertion of an insulating Al2O3 intermediate layer between Ag NPs and ZnO resulted in a parallel distinction of the two main non-radiative carrier transfer mechanisms of plasmonic NPs, i.e. direct electron transfer (DET) and plasmonic induced resonance energy transfer (PIRET). The multi-wavelength transient pump-probe spectroscopy indicated the very fast plasmonic radiative transfer dynamics of the system in <500 fs below 389 nm. We demonstrate a 13% increase of photogenerated current in ZnO upon visible irradiation as a result of non-radiative plasmonic hot-electron injection from Ag NPs. Overall, our device encompasses several effective solutions for designing a plasmonic system featuring non-radiative electron-electron plasmonic dephasing and high photoconversion efficiencies.

Published by American Chemical Society.An inorganic wide-bandgap hole transport layer (HTL), copper(I) thiocyanate (CuSCN), is employed in inorganic planar hydrothermally deposited Sb2S3 solar cells. With excellent hole transport properties and uniform compact morphology, the solution-processed CuSCN layer suppresses the leakage current and improves charge selectivity in an n-i-p-type solar cell structure. The device without the HTL (FTO/CdS/Sb2S3/Au) delivers a modest power conversion efficiency (PCE) of 1.54%, which increases to 2.46% with the introduction of CuSCN (FTO/CdS/Sb2S3/CuSCN/Au). This PCE is a significant improvement compared with the previous reports of planar Sb2S3 solar cells employing CuSCN. CuSCN is therefore a promising alternative to expensive and inherently unstable organic HTLs. In addition, CuSCN makes an excellent optically transparent (with average transmittance >90% in the visible region) and shunt-blocking HTL layer in pinhole-prone ultrathin(<100 nm) semitransparent absorber layers grown by green and facile hydrothermal deposition. A semitransparent device is fabricated using an ultrathin Au layer (∼10 nm) with a PCE of 2.13% and an average visible transmittance of 13.7%.

Semitransparent thin film solar cells based on wide bandgap absorber Sb2S3 have immense potential in building integrated photovoltaic (BIPV) applications. A typical thin film Sb2S3 solar cell using low-cost solution-based methods (such as hydrothermal deposition) utilizes a toxic CdS film with a narrow bandgap (2.4 eV) as the electron transport layer (ETL). Wide bandgap (3.1–3.4 eV) non-toxic TiO2 meets the optoelectronic requirements for a Cd-free ETL alternative but the hydrothermal deposition of Sb2S3 on TiO2 results in a non-uniform island-like growth, which is unsuitable for semitransparent applications (utilizing less than 100 nm Sb2S3). Therefore, in this study, using the successive ionic layer adsorption and reaction (SILAR) method, an ultrathin ZnS layer (1–3 nm) is coated on TiO2 as a surface modification layer to improve the nucleation and growth characteristics of Sb2S3 during hydrothermal deposition. The introduction of ZnS results in a pinhole-free compact mirrorlike Sb2S3 film similar to that obtained on CdS. The optimized solar cells based on CdS, TiO2, and TiO2-ZnS ETLs showed photoconversion efficiencies (PCEs) of 5.2 %, 5.1 %, and 4.3 %, respectively. A comprehensive comparative study is then reported highlighting the relationship between morphology, optoelectronic properties, and photovoltaic performance of the Sb2S3 films grown on the three ETLs. Furthermore, utilizing the excellent film morphology of Sb2S3 on TiO2-ZnS ETL, semitransparent solar cells were fabricated using an ultrathin Au (<10 nm) electrode. Semitransparent solar cells using 65 and 80 nm Sb2S3 absorber layers on TiO2-ZnS obtained PCEs (and average visible transmittances, AVTs) of 3.3 % (11.2 %) and 3.6 % (8.8 %), respectively. These results are critical to the development of the BIPV sector through environmentally friendly and non-critical materials-based solutions.

Sb₂S₃ is an emerging inorganic photovoltaic absorber material with attractive properties such as high absorption coefficient, stability, earth-abundance, non-toxicity, and low-temperature solution processability. Furthermore, with a bandgap of ca. 1.7 eV, it can also be used in semitransparent or tandem solar cell applications. Here, an inorganic wide-bandgap hole transport layer (HTL), copper thiocyanate (CuSCN), is used in an Sb₂S₃ solar cell employing a simple planar geometry. The compact and highly transparent CuSCN HTL was compatible with the low-cost, blade-coated carbon/Ag electrode and a semitransparent solar cell device. With Au and carbon/Ag electrodes, chemical bath deposited Sb2S3 solar cells achieved power conversion efficiencies (PCEs) of 1.75% and 1.95%, respectively. At the same time, a preliminary semitransparent Sb₂S₃ device with an ultrathin Au (similar to 15 nm) electrode showed a good average visible transmittance (AVT) of 26.7% at a PCE of 1.65%.

Semitransparent photovoltaic (STPV) solar cells offer an immense opportunity to expand the scope of photovoltaics to special applications such as windows, facades, skylights, and so on. These new opportunities have encouraged researchers to develop STPVs using traditional thin-film solar cell technologies (amorphous-Si, CdTe, and CIGS or emerging solar cells (organic, perovskites, and dye-sensitized). There are considerable improvements in both power conversion efficiency (PCE) and semitransparency of these STPV devices. This review studies the device structure of state-of-the-art STPV devices and thereby analyzes the different approaches toward maximizing the product of PCE and average visible transmittance. The origins of PCE losses during the opaque-to-semitransparent transition in the different STPV technologies are discussed. In addition, critical practical aspects relevant to all STPV devices, such as compatibility of the top transparent electrode with the device structure, buffer layer optimization, light management engineering, scale-up, and stability, are also reported. This overview is expected to facilitate researchers across different technologies to identify and overcome the challenges toward achieving higher light utilization efficiencies in STPVs.

Photoelectrochemical (PEC) water splittingreactions are promising for sustainable hydrogen productionfrom renewable sources. We report here, the preparation of α-Fe₂O₃/Fe₃O₄ composite films via a single-step chemical vapordeposition of [Fe(O^tBu)₃]₂ and their use as efficient photoanode materials in PEC setups. Film thickness and phase segregation was controlled by varying the deposition time and corroborated through cross-section Raman spectroscopy and scanning electron microscopy. The highest water oxidationactivity (0.48 mA/cm² at 1.23 V vs RHE) using intermittent AM 1.5 G (100 mW/cm²) standard illumination was found forhybrid films with a thickness of 11 μm. This phenomenon is attributed to an improved electron transport resulting from ahigher magnetite content toward the substrate interface and an increased light absorption due to the hematite layer mainly located at the top surface of the film. The observed high efficiency of α-Fe₂O₃/Fe₃O₄ nanocomposite photoanodes is attributed to the close proximity and establishment of 3D interfaces between the weakly ferro- (Fe₂O₃) and ferrimagnetic (Fe₃O₄) oxides, which in view of their differential chemical constitution andvalence states of Fe ions (Fe²⁺/Fe³⁺) can enhance the charge separation and thus the overall electrical conductivity of the layer.

There is an urgent need to develop real-time gas sensors capable of detection under hot-gas (> 400 °C) flow, for applications such as exhaust emission control. In this context, Rh-doped BaTiO3 has been prepared by a co-precipitation route and heat-treated at 900 °C under 2% hydrogen to obtain in-situ Rh-nanoparticle decoration of submicron BaTiO₃ particles. X-ray diffraction, Raman, and X-Ray photoelectron spectrometry analysis confirm the presence of Barium Titanate phases and the substitution of Ti⁴⁺ by Rh³⁺. According to the analytic evidence, thermal hydrogen treatment leads probably to Rhodium diffusion out of titanate lattice, yielding a self-decoration of the nano-sized Barium Titanate particles. Further NO-sensing tests revealed that the sensors produced by deposition of this in-situ Rh-loaded BaTiO₃ on the interdigitated electrodes (IDE) yield a significant increase of selectivity and response (∼18 % for 200 ppm NO) towards NO, for the first time, under a hot-gas environment reaching up to 900 °C as synthetic humid air being the carrier gas. The calculated response and recovery times are reasonable, and observed reproducibility confirms suitability to practical applications. Relying on the carried investigations, this good sensing performance can be explained by the creation of excessive oxygen vacancies resulting from Rhodium's surface diffusion. Moreover, it is to claim that excellent catalytic activity of Rhodium plays a key role in enhancing NO-sensing performance.

Theory predicts that tetragonal polymeric C60 will undergo a phase transition into a metallic phase at pressures around 20 GPa. Raman and structural experiments at high pressures confirmed formation of a new phase above 20 GPa although the question about its electrical properties was still open. We report on the first simultaneous in situ study of vibrational and electrical properties of two-dimensional (2D) tetragonal C60 polymer at pressures up to 30 GPa in a diamond anvil cell (DAC) specially designed for this purpose. Our results reveal an anomaly in Raman spectra and a drop in electrical resistance of the sample at 20-25 GPa. We tentatively associate this anomalous behaviour with a phase transition into the conductive phase although its metallic character is yet to be proven.At high pressures the Raman spectra exhibit a high degree of disorder. Upon pressure release the order was partially restored and, more importantly, a significant amount of the initial 2D polymeric phase was recovered.

Rationalizing material features according to the adopted synthetic strategy, aiming then to tune them on demand, is among the most relevant purposes of investigation in materials science. Herein, the systematic analysis of the dependence of graphitic carbon nitride (g-C3N4) physical characteristics on the decomposition temperature of urea, rationalizing the impact of synthetic temperature on several characteristics of the materials (degree of N–H condensation, carbon vs nitrogen content, structural parameters, photoluminescence lifetime, surface area, pores volume), is discussed. g-C3N4 nanostructures are fabricated by thermal decomposition of urea at different temperatures under ambient atmosphere, obtaining an almost ideal stoichiometry (C/N = 0.72) when setting the temperature at 600 °C. The samples show structural, textural, compositional, and optical differences directly depending on the fabrication temperature: specific surface area, pore volume and size, intralayer distance, and speed of radiative recombination of photogenerated charges are proportionally enhanced by increasing the synthesis temperature. The role played by all the physicochemical features of the prepared samples in promoting the catalytic degradation of Rhodamine B is investigated, highlighting their synergistic role in enhancing the catalytic efficiency. Significant differences in the dye degradation are recorded when using either UV or solar simulated light, demonstrating that Rhodamine B photosensitization rules the process.

The synthesis of MgB2-based materials under high pressure gave the possibility to suppress the evaporation of magnesium and to obtain near theoretically dense nanograined structures with high superconducting, thermal conducting, and mechanical characteristics: critical current densities of 1.8-1.0×106 A/cm2 in the self-field and 103 A/cm2 in a magnetic field of 8 T at 20 K, 5-3×105 A/cm2 in self-field at 30 K, the corresponding critical fields being Hc2=15 T at 22 K and irreversible fields Hirr=13 T at 20 K, and Hirr=3.5 T at 30 K, thermal conduction of 53±2 W/(m{dot operator}K), the Vickers hardness HV=10.12±0.2 GPa under a load of 148.8 N and the fracture toughness K1 C=7.6±2.0 MPa{dot operator}m0.5 under the same load, the Young modulus E=213 GPa. Estimation of quenching current and AC losses allowed the conclusion that high-pressure-prepared materials are promising for application in transformer-type fault current limiters working at 20-30 K.

Superconducting (SC) and mechanical properties of spark plasma (or SPS) produced MgB 2 -based materials allow their efficient applications in fault current limiters, superconducting electromotors, pumps, generators, magnetic bearings, etc. The synthesized from Mg and B at 50 MPa, 1050 °C for 30 min material has a density of 2.52 g/cm 3, critical current density, j c = 7.1·10 5 A/cm 2 at 10 K , 5.4·10 5 A/cm 2 at 20 K, and 9·10 4 A/cm 2 at 35 K in zero magnetic field; at 20 K its field of irreversibility B irr(20)=7 T and upper critical field B c2(20)=11 T; microhardness H V=10.5 GPa and fracture toughness K 1C =1.7 MPa·m 1/2 at 4.9 N-load. SPS-manufactured in- situ MgB 2- based materials usually have somewhat higher j c than sintered ex-situ. The pressure variations from 16 to 96 MPa during the SPS-process did not affect material SC characteristics significantly; the j c at 10-20 K was slightly higher and the material density was higher by 11%, when pressures of 50-96 MPa were used. The structure of SPS-produced MgB 2 material contains Mg-B-O inclusions and inclusions of higher borides (of compositions near MgB 4, MgB 7, MgB 12, MgB 17, MgB 20), which can be pinning centers. The presence of higher borides in the MgB 2 structure can be revealed by the SEM and Raman spectroscopy.

A variety of samples made via different routes were investigated. Samples are nanostructured (average grain sizes are about 20 nm). The advantage of high-pressure (HP)-manufactured (2 GPa, 800-1050 degrees C, 1 h) MgB2 bulk is the possibility to get almost theoretically dense (1-2% porosity) material with very high critical current densities reaching at 20 K, in 0-1 T j(c) = 1.2 - 1.0 . 10(6) A/cm(2) (with 10% SiC doping) and j(c) = 9.2 - 7.3 10(5) A/cm(2) (without doping). Mechanical properties are also very high: fracture toughness up to 4.4 +/- 0.04 MPa . m(0.5) and 7.6 +/- 2.0 MPa . m(0.5) at 148.8 N load for MgB2 undoped and doped with 10% Ta, respectively. The HP-synthesized material at moderate temperature (2 GPa, 600 degrees C, 1 h) from B with high amount of impurity C (3.15%) and H (0.87%) has j(c) = 10(3) A/cm(2) in 8 T field at 20 K, highest irreversibility fields (at 18.4 K H-irr = 15 T) and upper critical fields (at 22 K H-C2 = 15 T) but 17% porosity. HP materials with stoichiometry near MgB12 can have T-c = 37 K and j(c) = 6 . 10(4) A/cm(2) at 0 T and H-irr = 5 T at 20 K. The spark plasma synthesized (SPS) material (50 MPa, 600-1050 degrees C 1.3 h, without additions), demonstrated at 20 K, in 0-1 T j(c) = 4.5 - 4 10(5) A/cm(2). Dispersed inclusions of higher magnesium borides, which are usually present in MgB2 structure and obviously create new pinning centers can be revealed by Raman spectroscopy (for the first time a spectrum of MgB7 was obtained). Tests of quench behavior, losses on MgB2 rings and material thermal conductivity show promising properties for fault current limiters. Due to high critical fields, the material can be used for magnets.

MgB2-based nanostructural materials with rather high oxygen concentration (5-14 wt.%) and dispersed grains of higher borides (MgB12, MgB7) high-pressure (2 GPa or 30 MPa) synthesized (in-situ) or sintered (ex-situ) demonstrated high superconducting characteristics (critical current density, jc, up to 1.8-1.0106 A/cm2 in the self magnetic field and 103 in 8 T field at 20 K, 3-1.5105 A/cm2 in the self field at 35 K, upper critical field up to HC2 = 15 T at 22 K, field of irreversibility Hirr =13 T at 20 K). The additives (Ti, SiC) and synthesis or sintering temperature can affect the segregation of oxygen and formation of oxygen-enriched Mg-B-O inclusions in the material structure, thus reducing the amount of oxygen in the material matrix as well as the formation of higher borides grains, which affects an increase of the critical current density. The record high HC2 and Hirr have been registered for the material high-pressure (2 GPa) synthesized from Mg and B at 600 oC having 17% porosity and more than 7 wt.% of oxygen. The attained values of the critical current, AC losses and thermal conductivity make the materials promising for application for fault current limiters and electromotors. The structural and superconducting (SC) characteristics of the material with matrix close to MgB12 in stoichiometry has been studied and the SC transition Tc=37 K as well as jc= 5×104 A/cm2 at 20 K in the self field were registered, its Raman spectrum demonstrated metal-like behavior.

Catalysts capable of improving the performance of oxygen evolution reaction (OER) and oxygen reduction reactions (ORR) are essential for the advancement of renewable energy technologies. Herein, Ag-decorated vertically aligned MoS2 nanoflakes are developed via magnetron co-sputtering and investigated as electrocatalyst towards OER and ORR. Due to the presence of silver, the catalyst shows more than 1.5 times an increase in the roughness-normalized rate of OER, featuring a very low Tafel slope (58.6 mv dec⁻¹), thus suggesting that the catalyst surface favors the thermodynamics of hydroxyl radical (OH•) adsorption with the deprotonation steps being the rate-determining steps. The improved performance is attributed to the strong interactions between OOH intermediates and the Ag surface which reduces the activation energy. Rotating ring disk electrode (RRDE) analysis shows that the net disk currents on the Ag-MoS2 sample are two times higher at 0.65 V compared to MoS2, demonstrating the co-catalysis effect of silver doping. Based on the rate constant values, Ag-MoS2 proceeds through a mixed 4 electron and a 2 + 2 serial route reduction mechanism, in which the ionized hydrogen peroxide is formed as a mobile intermediate. The presence of silver decreases the electron transfer number and increases the peroxide yield due to the interplay of a 2 + 2 electron reduction pathway. A 2.5–6 times faster conversion rate of peroxide to OH- observed due to the presence of silver, indicating its effective cocatalyst nature. This strategy can help in designing a highly active bifunctional catalyst that has great potential as a viable alternative to precious-metal-based catalysts.Graphica

Hydrogen evolution reaction through electrolysis holds great potential as a clean, renewable, and sustainable energy source. Platinum-based catalysts are the most efficient to catalyze and convert water into molecular hydrogen; however, their large-scale application is prevented by scarcity and cost of Pt. In this work, we propose a new ternary composite of Ag2S, MoS2, and reduced graphene oxide (RGO) flakes via a one-pot synthesis. The RGO support assists the growth of two-dimensional MoS2 nanosheets partially covered by silver sulfides as revealed by high-resolution transmission electron microscopy. Compared with the bare MoS2 and MoS2/RGO, the Ag2S/MoS2 anchored on the RGO surface (the ternary system Ag2S/MoS2/RGO) demonstrated a high catalytic activity toward hydrogen evolution reaction (HER). Its superior electrochemical activity toward HER is evidenced by the positively shifted (−190 mV vs reversible hydrogen electrode (RHE)) overpotential at a current density of −10 mA/cm2 and a small Tafel slope (56 mV/dec) compared with a bare and binary system. The Ag2S/MoS2/RGO ternary catalyst at an overpotential of −200 mV demonstrated a turnover frequency equal to 0.38 s–1. Electrochemical impedance spectroscopy was applied to understand the charge-transfer resistance; the ternary sample shows a very small charge-transfer resistance (98 Ω) at −155 mV vs RHE. Such a large improvement can be attributed to the synergistic effect resulting from the enhanced active site density of both sulfides and to the improved electrical conductivity at the interfaces between MoS2 and Ag2S. This ternary catalyst opens up further optimization strategies to design a stable and cheap catalyst for hydrogen evolution reaction, which holds great promise for the development of a clean energy landscape.

Hydrogen production as alternative energy source is still a challenge due to the lack of efficient and inexpensive catalysts, alternative to platinum. Thus, stable, earth abundant, and inexpensive catalysts are of prime need for hydrogen production via hydrogen evolution reaction (HER). Herein, we present an efficient and stable electrocatalyst composed of earth abundant TiO2 nanorods decorated with molybdenum disulfide thin nanosheets, a few nanometers thick. We grew rutile TiO2 nanorods via the hydrothermal method on conducting glass substrate, and then we nucleated the molybdenum disulfide nanosheets as the top layer. This composite possesses excellent hydrogen evolution activity in both acidic and alkaline media at considerably low overpotentials (350 mV and 700 mV in acidic and alkaline media, respectively) and small Tafel slopes (48 and 60 mV/dec in acidic and alkaline conditions, respectively), which are better than several transition metal dichalcogenides, such as pure molybdenum disulfide and cobalt diselenide. A good stability in acidic and alkaline media is reported here for the new MoS2/TiO2 electrocatalyst. These results demonstrate the potential of composite electrocatalysts for HER based on earth abundant, cost-effective, and environmentally friendly materials, which can also be of interest for a broader range of scalable applications in renewable energies, such as lithium sulfur batteries, solar cells, and fuel cells.

The combination of the ability to absorb most of the solar radiation and simultaneously suppress infrared re-radiation allows selective solar absorbers (SSAs) to maximize solar energy to heat conversion, which is critical to several advanced applications. The intrinsic spectral selective materials are rare in nature and only a few demonstrated complete solar absorption. Typically, intrinsic materials exhibit high performances when integrated into complex multilayered solar absorber systems due to their limited spectral selectivity and solar absorption. In this study, we propose CoSbx (2 < x < 3) as a new exceptionally efficient SSA. Here we demonstrate that the low bandgap nature of CoSbx endows broadband solar absorption (0.96) over the solar spectral range and simultaneous low emissivity (0.18) in the mid-infrared region, resulting in a remarkable intrinsic spectral solar selectivity of 5.3. Under 1 sun illumination, the heat concentrates on the surface of the CoSbx thin film, and an impressive temperature of 101.7 °C is reached, demonstrating the highest value among reported intrinsic SSAs. Furthermore, the CoSbx was tested for solar water evaporation achieving an evaporation rate of 1.4 kg m−2 h−1. This study could expand the use of narrow bandgap semiconductors as efficient intrinsic SSAs with high surface temperatures in solar applications.

Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R3, where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing ID/IG ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.

Room temperature atmospheric plasma treatments are widely used to activate and control chemical functionalities at surfaces. Here, we investigated the effect of atmospheric pressure plasma jet (APPJ) treatments in reducing atmosphere (Ar/1‰ H2 mixture) on the photoluminescence (PL) properties of single crystal ZnO nanorods (NRs) grown through hydrothermal synthesis on fluorine-doped tin oxide glass substrates. The results were compared with a standard annealing process in air at 300 °C. Steady-state photoluminescence showed strong suppression of the defect emission in ZnO NRs for both plasma and thermal treatments. On the other side, the APPJ process induced an increase in PL quantum efficiency (QE), while the annealing does not show any improvement. The QE in the plasma treated samples was mainly determined by the near band-edge emission, which increased 5–6 fold compared to the as-prepared samples. This behavior suggests that the quenching of the defect emission is related to the substitution of hydrogen probably in zinc vacancies (VZn), while the enhancement of UV emission is due to doping originated by interstitial hydrogen (Hi), which diffuses out during annealing. Our results demonstrate that atmospheric pressure plasma can induce a similar hydrogen doping as ordinarily used vacuum processes and highlight that the APPJ treatments are not limited to the surfaces but can lead to subsurface modifications. APPJ processes at room temperature and under ambient air conditions are stable, convenient, and efficient methods, compared to thermal treatments to improve the optical and surface properties of ZnO NRs, and remarkably increase the efficiency of UV emission.

Harnessing energy lost in the form of heat is an important challenge today. Organic thermoelectric materials (TE) can convert lost heat into electricity at relatively low temperature. Single-walled carbon nanotubes (SWCNTs) are known to boost the TE properties of organic-based materials at room temperature (TR). However, the TE performance decreases with the increasing temperature, which restricts the working temperature region of the devices. Here, we present a three steps investigation: initially, the influence of the net of SWCNTs on TE properties of polymer matrix; secondly, creation of hybrid fillers via SWCNTs treatment with gold chloride; lastly, chemical post-treatment of obtained systems in the temperature range 325–410 K. In the process of HAuCl4 aerosolization (gold chloride treatment) on the surface of nanotubes, different ionic conformations (Au and AuCl4−) can be formed. For this reason, we performed a theoretical investigation on the influence of ionic conformations on SWCNTs on the electronic structure. Implementation of SWCNTs net into polymer matrix alongside gold chloride doping and chemical post-treatment successfully increased the power factor of the system in the temperature interval from 300 to 410 K. These results demonstrate the potential of combined approach in creation of hybrid fillers based on organic/inorganic materials with chemical post-treatment in boosting the thermoelectric performance within the whole operating temperature of polymer-based composite alongside the importance of theoretical modeling in tuning the electronic structure of composite systems through a material-by-design approach.

Polymer-based composites are of high interest in the field of thermoelectric (TE) materials because of their properties: abundance, low thermal conductivity, and nontoxicity. In applications, like TE for wearable energy harvesting, where low operating temperatures are required, polymer composites demonstrate compatible with the targeted specifications. The main challenge is reaching high TE efficiency. Fillers and chemical treatments can be used to enhance TE performance of the polymer matrix. The combined application of vertically aligned carbon nanotubes forest (VA-CNTF) is demonstrated as fillers and chemical post-treatment to obtain high-efficiency TE composites, by dispersing VA-CNTF into a poly (3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. The VA-CNTF keeps the functional properties even in flexible substrates. The morphology, structure, composition, and functional features of the composites are thoroughly investigated. A dramatic increase of power factor is observed at the lowest operating temperature difference ever reported. The highest Seebeck coefficient and electrical conductivity are 58.7 μV K^-1 and 1131 S cm^-1, respectively. The highest power factor after treatment is twice as high in untreated samples. The results demonstrate the potential for the combined application of VA-CNTF and chemical post-treatment, in boosting the TE properties of composite polymers toward the development of high efficiency, low-temperature, flexible TEs.

Thermoelectric (TE) materials are highly important due to their ability to convert wasted heat energy into electricity. Among the different TE materials, organic-based or polymer-based TE systems are among the most promising due to their sustainability, non-toxicity and good electrical properties. In our research, we have investigated for the first time the application of vertically aligned carbon nanotubes forest (VA-CNTF) as a filler for TE composite; compared to unconnected carbon nanotubes (CNT), which are typically used in polymer/CNT composites, dry pulled VA-CNTF sheets have more ordered structure, which is supposed to improve the TE efficiency of the material. VA-CNTF and short unoriented multiwalled carbon nanotubes (MWCNT) were used as fillers of a polymeric matrix, to prepare TE composites. Various stacking configurations were explored by using CNTF. All the samples were examined by scanning electron microscopy (SEM), micro-Raman spectroscopy, and four-point probe electrical measurements; MWCNT-based samples were used as benchmarking systems.

The results revealed a dramatic increase of the Seebeck coefficient up to 46 μV/K for the VA-CNTF-based sample, while the best MWCNTs-based sample (MWCNT concentration 50 wt%) provided only 21.49, which is roughly the Seebeck coefficient of pure polymer. This research represents the first application of VA-CNTF as a promising material for TE systems and demonstrates that oriented nanoforests and related CNT sheets are a very perspective material for promising developments in the field.

Luminescent solar concentrators (LSCs) are large-area sunlight collectors coupled to small area solar cells, for efficient solar-to-electricity conversion. The three key points for the successful market penetration of LSCs are: (i) removal of light losses due to reabsorption during light collection; (ii) high light-to-electrical power conversion efficiency of the final device; (iii) long-term stability of the LSC structure related to the stability of both the matrix and the luminophores. Among various types of fluorophores, carbon quantum dots (C-dots) offer a wide absorption spectrum, high quantum yield, non-toxicity, environmental friendliness, low-cost, and eco-friendly synthetic methods. However, they are characterized by a relatively small Stokes shift, compared to inorganic quantum dots, which limits the highest external optical efficiency that can be obtained for a large-area single-layer LSC (>100 cm²) based on C-dots below 2%. Herein, we report highly efficient large-area LSCs (100–225 cm²) based on colloidal C-dots synthesized via a space-confined vacuum-heating approach. This one batch reaction could produce Gram-scale C-dots with a high quantum yield (QY) (∼65%) using eco-friendly citric acid and urea as precursors. Thanks to their very narrow size distribution, the C-dots produced via the space-confined vacuum-heating approach had a large Stokes shift of 0.53 eV, 50% larger than C-dots synthesized via a standard solvothermal reaction using the same precursors with a similar absorption range. The large-area LSC (15 × 15 × 0.5 cm³) prepared by using polyvinyl pyrrolidone (PVP) polymer as a matrix exhibited an external optical efficiency of 2.2% (under natural sun irradiation, 60 mW cm⁻², uncharacterized spectrum). After coupling to silicon solar cells, the LSC exhibited a power conversion efficiency (PCE) of 1.13% under natural sunlight illumination (20 mW cm⁻², uncharacterized spectrum). These unprecedented results were obtained by completely suppressing the reabsorption losses during light collection, as proved by optical spectroscopy. These findings demonstrate the possibility of obtaining eco-friendly, high-efficiency, large-area LSCs through scalable production techniques, paving the way to the lab-to-fab transition of this kind of devices.