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Layered hybrid organic–inorganic metal‐halide perovskites (HOIPs) can acquire chirality from molecules incorporated into their structure showing exciting possibilities in optoelectronics and spintronics. However, researchers have focused their attention on the study of bulk compounds, namely unstable and toxic Pb HOIPs. Herein, the chiroptical properties of R‐ and S‐β‐methylphenethylammonium Mn chloride HOIPs are reported in both the bulk and the few‐layer limit as exfoliated flakes. Red photoluminescence (PL) emission originating from the octahedrally coordinated Mn2+ is observed, with a PL shift to longer wavelengths when passing from bulk to flakes. Circular dichroism and circularly polarized PL mirrored‐signals for enantiomers are found in bulk samples, while in flakes, a degree of circularly polarized emission (P) of up to 17% at 80 K is achieved, comparable to Pb‐based HOIPs. Moreover, angle‐resolved PL measurements on flakes show that the PL emission and P are isotropic. These findings highlight the potential of these HOIPs from bulk to flakes for spin‐optoelectronic applications. [ABSTRACT FROM AUTHOR]

The inorganic content and the catalytic performance pose metal‐loaded enzyme nanoflowers as promising candidates for developing bioelectrodes capable of functioning without the external addition of a redox mediator. However, these protein‐inorganic hybrids have yet to be successfully applied in combination with electrode materials. Herein, the synthesis procedure of these bionanomaterials is reproposed to precisely control the morphology, composition, and performance of this particular protein‐mineral hybrid, formed by glucose oxidase and cobalt phosphate. This approach aims to enhance the adherence and electron mobility between the enzyme and a carbon electrode. The strategy relies on dressing the protein in a tailored thin nanogel with multivalent chemical motifs. The functional groups of the polymer facilitate the fast protein sequence‐independent biomineralization. Furthermore, the engineered enzymes enable the fabrication of robust cobalt‐loaded enzyme inorganic hybrids with exceptional protein loads, exceeding 90% immobilization yields. Notably, these engineered biohybrids can be readily deposited onto flat electrode surfaces without requiring chemical pre‐treatment. The resulting bioelectrodes are robust and exhibit electrochemical responses even without the addition of a redox mediator, suggesting that cobalt complexes promote electron wiring between the active site of the enzyme and the electrode. [ABSTRACT FROM AUTHOR]

Therapeutic deep eutectic solvents (THEDES) are an emerging family of eutectic mixtures gaining increasing interest in the biomedical space. The immobilization of THEDES into polymer networks allows bioactive eutectogels to expand their application scope to topical drug delivery. Herein, this work presents the first set of elastomeric eutectogels constructed by supporting a therapeutic eutectic system with skin permeation ability in a protein scaffold dynamically crosslinked by a natural polyphenol. In this ionic eutectic, gelatin undergoes gelation through an unexpected mechanism in striking contrast with classical hydrogels, which is herein thoroughly studied. Interestingly, the polyphenol controls the conformation of the protein structure, enabling tuning up the mechanical and viscoelastic behavior of the dynamic eutectogel networks from elastic to hyperelastic. The resultant protein eutectogels exhibit strain‐hardening behavior, thermoreversible gel‐to‐sol transition, and excellent adhesive performance. Furthermore, these versatile materials retain the bioactivity of the liquid THEDES and favor skin occlusion, assisting the delivery of both hydrophilic and hydrophobic substances in ex vivo porcine skin in a time‐dependent penetration process. These ultrastretchable eutectogels show new interplays between protein scaffolds and eutectic mixtures, paving the way for innovative therapeutic soft materials. [ABSTRACT FROM AUTHOR]

Germanium–tin (GeSn) microdisks are promising structures for complementary metal–oxide–semiconductor‐compatible lasing. Their emission properties depend on Sn concentration, strain, and operating temperature. Critically, the band structure of the alloy varies along the disk due to different lattice deformations associated with mechanical constraints. An experimental and numerical study of Ge1−xSnx microdisk with Sn concentration between 8.5 and 14 at% is reported. Combining finite element method calculations, micro‐Raman and X‐ray diffraction spectroscopy enables a comprehensive understanding of mechanical deformation, where computational predictions are experimentally validated, leading to a robust model and insight into the strain landscape. Through micro‐photoluminescence experiments, the temperature dependence of the bandgap of Ge1−xSnx is parametrized using the Varshni formula with respect to strain and Sn content. These results are the input for spatially dependent band structure calculations based on deformation potential theory. It is observed that Sn content and temperature have comparable effects on the bandgap, yielding a decrease of more than 20 meV for an increase of 1 at% or 100 K, respectively. The impact of the strain gradient is also analyzed. These findings correlate structural properties to emission wavelength and spectral width of microdisk lasers, thus demonstrating the importance of material‐related consideration on the design of optoelectronic microstructures. [ABSTRACT FROM AUTHOR]

Trigonal tellurium (Te) has attracted researchers' attention due to its transport and optical properties, which include electrical magneto-chiral anisotropy, spin polarization and bulk photovoltaic effect. It is the anisotropic and chiral crystal structure of Te that drive these properties, so the determination of its crystallographic orientation and handedness is key to their study. Here we explore the structural dynamics of Te bulk crystals by angle-dependent linearly polarized Raman spectroscopy and symmetry rules in three different crystallographic orientations. The angle-dependent intensity of the modes allows us to determine the arrangement of the helical chains and distinguish between crystallographic planes parallel and perpendicular to the chain axis. Furthermore, under different configurations of circularly polarized Raman measurements and crystal orientations, we observe the shift of two phonon modes only in the (0 0 1) plane. The shift is positive or negative depending on the handedness of the crystals, which we determine univocally by chemical etching. Our analysis of three different crystal faces of Te highlights the importance of selecting the proper orientation and crystallographic plane when investigating the transport and optical properties of this material. These results offer insight into the crystal structure and symmetry in other anisotropic and chiral materials, and open new paths to select a suitable crystal orientation when fabricating devices. [ABSTRACT FROM AUTHOR]

Cadmium mercury selenide (CdHgSe) nanocrystals exhibit a unique combination of low‐energy optical absorption and emission, which can be tuned from the visible to the infrared range through both quantum confinement and adjustment of their composition. Owing to this advantage, such nanocrystals have been studied as a promising narrow‐band infrared light emitter. However, the electroluminescence of CdHgSe‐based nanocrystals has remained largely unexplored, despite their potential for emitting light in the telecom wavelength range. Further benefits to their optical properties are expected from their shape control, in particular the formation of 2D nanocrystals, as well as from a proper design of their heterostructures. In this work, a colloidal synthesis of CdHgSe/ZnCdS core/shell nanoplatelets (NPLs) starting from CdSe template NPLs employing a cation exchange strategy is developed. The heterostructures synthesized exhibit photoluminescence that can be tuned from ≈1300 to 1500 nm. These near‐infrared‐active NPLs are employed in light‐emitting diodes, demonstrating low turn‐on voltage and high external quantum efficiency. [ABSTRACT FROM AUTHOR]

Background: Childhood myopia represents a global concern with increasing prevalence in recent decades. Lifestyle factors significantly impact myopia. Aim: To evaluate lifestyle factors in myopic children from a metropolitan area in Europe. Methods: This was a descriptive study including myopic subjects aged 4–18 years. Patient demographic and clinical data were collected, including cycloplegic refraction in spherical equivalent refraction (SER) and axial length (AL). In addition, a questionnaire on lifestyle factors was conducted between September 2022 and April 2023. Results: A total of 321 myopic children were included, aged 10.72 ± 3.05 years, of whom 51.4% were boys, with SER −2.25 ± 1.9 D and AL 24.54 ± 0.98 mm. The mean age of myopia onset was 7.69 ± 3.05 years. A total of 59.8% had family history of myopia. Those children who had <2 h/day of screen time (on weekdays) presented SER −2 ± 1.91 D, compared to those who had >2 h/day, SER: −2.50 ±1.88 D (p = 0.009). Children who spent <2 h/day doing near work after school were less myopic compared to those who spent >2 h/day (SER: −1.75 ± 1.83 vs. SER: −2.75 ± 1.82, respectively, p = 0.03). However, no significant association was observed between SER and AL and time spent outdoors nor between SER and AL and academic performance (p > 0.05). Conclusions: Screen time and near-work time appear to be lifestyle factors related to myopia. [ABSTRACT FROM AUTHOR]

This study investigates the potential of utilizing three food wastes: cheese whey (CW), beet molasses (BM), and corn steep liquor (CSL) as alternative nutrient sources for the cultivation of the diatom Phaeodactylum tricornutum, a promising source of polyunsaturated eicosapentaenoic acid (EPA) and the carotenoid fucoxanthin. The CW media tested did not significantly impact the growth rate of P. tricornutum; however, CW hydrolysate significantly enhances cell growth. BM in cultivation medium enhances biomass production and fucoxanthin yield. The optimization of the new food waste medium was conducted through the application of a response surface methodology (RSM) using hydrolyzed CW, BM, and CSL as factors. The results showed a significant positive impact of these factors (p < 0.005), with an optimized biomass yield of 2.35 g L−1 and a fucoxanthin yield of 3.64 mg L−1 using a medium composed of 33 mL L−1 of CW, 2.3 g L−1 of BM, and 2.24 g L−1 of CSL. The experimental results reported in this study showed that some food by-products from a biorefinery perspective could be utilized for the efficient production of fucoxanthin and other high-added-value products such as eicosapentaenoic acid (EPA). [ABSTRACT FROM AUTHOR]

Long-chain polyunsaturated fatty acids (LC-PUFAs) have multiple beneficial effects on human health, in particular docosahexaenoic acid (DHA, 22:6, n-3) and eicosapentaenoic acid (EPA, 20:5, n-3). A variety of microorganisms has been used for the commercial production of non-animal-source LC-PUFAs. The oomycetes of the Pythium family are promising EPA producers, and in this work, the optimization of Pythium irregulare growth using food industry by-products and wastes as cheap sources of nutrients was carried out. Sugar cane molasses (SCM), spent brewery yeast (SBY), cheese whey (CW), and expired orange juice (EFJ) were tested. A combination of SBY as a source of nitrogen and EFJ as a source of organic carbon resulted in the best outcome among the other sustainable media ingredients. The optimization of the new medium was conducted through a response surface methodology using EFJ and SBY as factors. The results show a significant positive impact of these factors on biomass productivity (p < 0.005), with an optimized biomass yield of 14.22 g L−1, a lipid yield of 2.23 g L−1, and an EPA concentration of 155 mg L−1. [ABSTRACT FROM AUTHOR]

When doped into a certain range of charge carrier concentrations, MoS2 departs from its pristine semiconducting character to become a strongly correlated material characterized by exotic phenomena such as charge density waves or superconductivity. However, the required doping levels are typically achieved using ionic‐liquid gating or air‐sensitive alkali‐ion intercalation, which are not compatible with standard device fabrication processes. Here, the emergence of superconductivity and a charge density wave phase in air‐stable organic cation intercalated MoS2 crystals are reported. By selecting two different molecular guests, it is shown that these correlated electronic phases depend dramatically on the intercalated cation, demonstrating the potential of organic ion intercalation to finely tune the properties of 2D materials. Moreover, it is found that a fully developed zero‐resistance state is not reached in few‐nm‐thick flakes, indicating the presence of 3D superconductive paths that are severed by the mechanical exfoliation. This behavior is ascribed to an inhomogeneous charge carrier distribution, which is probed at the nanoscale using scanning near‐field optical microscopy. The results establish organic‐ion intercalated MoS2 as a platform to study the emergence and modulation of correlated electronic phases. [ABSTRACT FROM AUTHOR]

Understanding the structural and magnetic properties in layered hybrid organic‐inorganic metal halide perovskites (HOIPs) is key for their design and integration in spin‐electronic devices. Here, a systematic study is conducted on ten compounds to understand the effect of the transition metal (Cu2+, Mn2+, Co2+), organic spacer (alkyl‐ and aryl‐ammonium), and perovskite phase (Ruddlesden‐Popper and Dion‐Jacobson) on the properties of these materials. Temperature‐dependent Raman measurements show that the crystals' structural phase transitions are triggered by the motional freedom of the organic cations as well as by the flexibility of the inorganic metal‐halide lattice. In the case of Cu2+ HOIPs, an increase of the in‐plane anisotropy and a reduction of the octahedra interlayer distance is found to change the behavior of the HOIP from that of a 2D ferromagnet to that of a quasi‐3D antiferromagnet. Mn2+ HOIPs show inherent antiferromagnetic octahedra intralayer interactions and a phenomenologically rich magnetism, presenting spin‐canting, spin‐flop transitions, and metamagnetism controlled by the crystal anisotropy. Co2+ crystals with non‐linked tetrahedra show a dominant paramagnetic behavior irrespective of the organic spacer and the perovskite phase. This study demonstrates that the chemical flexibility of HOIPs can be exploited to develop novel layered magnetic materials with tailored magnetic properties. [ABSTRACT FROM AUTHOR]

Extraction of valuable bioactive compounds from olive leaves is a hot topic and the use of sustainable and green technologies is mandatory in terms of circular economy. In this way, the use of fermentation technologies showed very interesting results in terms of phenolic compound recovery. Because of that in this work the use of solid state fermentations, as valuable tool to improve the phenolic extraction has been checked. Aspergillus oryzae (in mycelium and spore form), Aspergillus awamori and Aspergillus niger were used as fermentation microrganisms. Phenolic compounds were determined by HPLC-ESI-TOF-MS and, to our knowledge, new compounds have been tentatively identified in olive leaves. Fermentation using mycelium of Aspergillus awamori, Aspergillus niger and Aspergillus oryzae were effective to increase both hydroxytyrosol and elenolic acid derivatives whereas the use of spores of Aspergillus oryzae caused a loss of hydroxytyrosoyl derivatives, contrary the content of elenolic derivatives are comparable with the other fermentation treatments and higher than control. The proposed fermentation processes using the mycelium of Aspergillus awamori, Aspergillus niger and Aspergillus oryzae lead to an increase the hydroxytyrosyl and elenolic acid derivatives and could be used at industrial scale to obtain enriched extracts. [ABSTRACT FROM AUTHOR]

Transition-metal dichalcogenide (TMD) nanosheets have become an intensively investigated topic in the field of 2D nanomaterials, especially due to the direct semiconductor nature, and the broken inversion symmetry in the odd-layer number, of some of their family members. These properties make TMDs attractive for different technological applications such as photovoltaics, optoelectronics, valleytronics, and hydrogen evolution reactions. Among them, MoX2 (X = S and Se) are turned to direct gap when their thickness is thinned down to monolayer, and thus, efforts toward obtaining large-scale monolayer TMDs are crucial for technological applications. Colloidal synthesis of TMDs has been developed in recent years, as it provides a cost-efficient and scalable way to produce few-layer TMDs having homogeneous size and thickness, yet obtaining a monolayer has proven challenging. Here, we present a method for the colloidal synthesis of mono- and few-layer MoX2 (X = S and Se) using elemental chalcogenide and metal chloride as precursors. Using a synthesis with slow injection of the MoCl5 precursor under a nitrogen atmosphere, and optimizing the synthesis parameters with a design of experiments approach, we obtained a MoX2 sample with the semiconducting (1H) phase and optical band gaps of 1.96 eV for 1H–MoS2 and 1.67 eV for 1H–MoSe2, respectively, consistent with a large monolayer yield in the ensemble. Both display photoluminescence at cryogenic and room temperature, paving the way for optical spectroscopy studies and photonic applications of colloidal TMD nanosheets. [ABSTRACT FROM AUTHOR]

The leaves of Annona cherimola Mill (cherimoya) are a potential source of phenolic compounds that have been shown to have beneficial properties. Therefore, this study focuses on establishing an ultrasonic-assisted extraction of phenolic compounds in cherimoya leaves using a sonotrode. For that purpose, a Box-Behnken design based on a response surface methodology (RSM) was used to optimize factors, such as amplitude, extraction time and solvent composition to obtain the maximum content of phenolic compounds by HPLC-MS and the maximum in-vitro antioxidant activity by DPPH, ABTS and FRAP assays in 'Fino de Jete' cherimoya leaves. The optimal conditions were 70% amplitude, 10 min and 40:60 ethanol/water (EtOH/H2O) (v/v). The results obtained under these optimum conditions by using a sonotrode were compared with those from an ultrasonic bath; briefly, recovery of phenolic compounds by sonotrode was 2.3 times higher than a bath. Therefore, these optimal conditions were applied to different varieties 'Campas', 'Fino de Jete' and 'Negrito Joven' harvested in the Tropical Coast of Granada (Spain). A total of 39 phenolic compounds were determined in these cherimoya leaf extracts, 24 phenolic compounds by HPLC-MS and 15 proanthocianidins by HPLC-FLD. 5-p-coumaroylquinic acid, lathyroside-7-O-α-l-rhamnopyranoside and quercetin hexose acetate were first identified in cherimoya leaves. The most concentrated phenolic compounds were the flavonoids, such as rutin and quercetin hexoside and proanthocyanidins including monomers. Almost no significant differences in the phenolic content in these cultivars were found (11–13 mg/g d.w. for phenolic compounds and 11–20 mg/g d.w. for proanthocyanidins). In addition, sonotrode ultrasonic-assisted extraction has been shown to be an efficient extraction technique in the phenolic recovery from cherimoya leaves that could be implemented on an industrial scale. [ABSTRACT FROM AUTHOR]

Metal‐halide perovskites (PSKs) are emergent materials for a large range of applications, and the layered double PSK architectures vastly enrich the opportunities to design their composition, structural properties, and optoelectronic behavior. The stability, crystal phase, and electronic bandgap depend strongly on the bonds and distortions of the octahedra lattice that are at the origin of the vibrational spectrum of these materials. This work investigates the structural dynamics of flakes of exfoliated layered Ag‐Bi bromide double PSKs by angle‐dependent polarized Raman spectroscopy and density functional theory modeling. The well‐defined orientation of the inorganic octahedra lattice with respect to the light polarization allows to correlate the angle‐dependent intensity of the Raman signal to the directionality and symmetry of the phonon modes. Low‐frequency vibrations are revealed for which a detailed microscopic and group theory assignment of the Raman modes is provided. The temperature‐dependent measurements across the phase transitions show marked changes in the phonon frequencies, reveal soft modes, and help to distinguish first from second‐order transitions as well as to determine their transition temperature. This provides highly valuable insights to improve the properties of this class of Pb‐free PSKs for applications in energy harvesting and optoelectronics. [ABSTRACT FROM AUTHOR]

Mixed‐dimensional systems host interesting phenomena that involve electron and ion transport along or across the interface, with promising applications in optoelectronic and electrochemical devices. Herein, a heterosystem consisting of a graphene monolayer with a colloidal Ag2S nanocrystal film atop, in which both ions and electrons are involved in photoelectrical effects, is studied. An investigation of the transport at the interface in different configurations by using a phototransistor configuration with graphene as a charge‐transport layer and semiconductor nanocrystals as a light‐sensitive layer is performed. The key feature of charge transfer is investigated as a function of gate voltage, frequency, and incident light power. A simple analytical model of the photoresponse is developed, to gain information on the device operation, revealing that the nanocrystals transfer electrons to graphene in the dark, but the opposite process occurs upon illumination. A frequency‐dependence analysis suggests a fractal interface between the two materials. This interface can be modified using solid‐state electrochemical reactions, leading to the formation of metallic Ag particles, which affect the graphene properties by additional doping, while keeping the photoresponse. Overall, these results provide analytical tools and guidelines for the evaluation of coupled electron/ion transport in hybrid systems. [ABSTRACT FROM AUTHOR]

In this work, we designed a novel nanocomposite proton-exchange membrane (PEM) based on sulfonated poly(ether ether ketone) (SPEEK) and tantalum disulfide functionalized with terminal sulfonate groups (S-TaS2). The PEMs are prepared through a solution-casting method and exploited in direct methanol fuel cells (DMFCs). Two-dimensional S-TaS2 nanoflakes were prepared as a functional additive to produce the novel nanocomposite membrane for DMFCs due to their potential as a fuel barrier and an excellent proton conductor. To optimize the degree of sulfonation (DS) of SPEEK and the weight percentage (wt%) of S-TaS2 nanoflakes in PEMs, we used the central composite design of the response surface method. The optimum PEM was obtained for SPEEK DS of 1.9% and a weight fraction (wt%) of S-TaS2 nanoflakes of 70.2%. The optimized membrane shows a water uptake of 45.72%, a membrane swelling of 9.64%, a proton conductivity of 96.24 mS cm−1, a methanol permeability of 2.66 × 10−7 cm2 s−1, and a selectivity of 36.18 × 104 S s cm−3. Moreover, SPEEK/S-TaS2 membranes show superior thermal and chemical stabilities compared to those of pristine SPEEK. The DMFC fabricated with the SPEEK/S-TaS2 membrane has reached the maximum power densities of 64.55 mW cm−2 and 161.18 mW cm−2 at 30 °C and 80 °C, respectively, which are ∼78% higher than the values obtained with the pristine SPEEK membrane. Our results demonstrate that SPEEK/S-TaS2 membranes have a great potential for DMFC applications. [ABSTRACT FROM AUTHOR]

Ion migration is associated with hysteresis observed in halide perovskite-based solar cells and light-emitting diodes, however, it is crucial for their effective performance in memory devices. In the halide perovskites field, a direct link between the average/local structure and the preferred ion migration hopping pathway has yet to be established. Herein, we utilize the solvent acidolysis crystallization technique to grow various halide-deficient methylammonium copper halide crystals where perovskite-type layers are found. Through synchrotron X-ray powder diffraction (XRPD) and pair distribution function (PDF) analyses, we identify the halogen vacancy site in the copper halide octahedra, the octahedra tilting, and the thermal vibrations of the atoms around their average positions. We correlate the variations in these parameters to the hysteresis observed in the current–voltage curves and subsequently to the ON/OFF ratios of proof-of-concept memory devices fabricated using inert Pt electrodes. Furthermore, our best ON/OFF ratio of ∼10 from our Pb-free devices compares well to the results obtained from two-dimensional Pb-based devices utilizing inert electrodes. [ABSTRACT FROM AUTHOR]

Olive leaves contain bioactive compounds that have been shown to activate AMP-activated protein kinase (AMPK), which decreases intracellular lipid accumulation. Microwave-assisted extraction (MAE) is a green extraction technique that is frequently used in the recovery of phenolic compounds from plants. Thus, in this study, a Box-Behnken design was used to optimize MAE conditions such as temperature, percentage of ethanol and extraction time to obtain the maximum content of total compounds and compounds that activate AMPK. To this end, all extracts were characterized by High-Performance Liquid Chromatography Coupled to Electrospray Ionization Time-of-Flight Mass Spectrometry (HPLC-ESI-TOF-MS). The optimum conditions to obtain the highest content of total compounds were 123 °C, 100% of ethanol/water (v/v) and 23 min, whereas the optimum conditions for the highest amount of compounds that activate AMPK were 111 °C, 42% of ethanol/water (v/v) and 23 min. Thus, a multi-analysis by desirability was carried out to establish MAE optimal conditions for both responses. The optimum conditions were 111 °C, 100% EtOH and 23 min with a desirability of 0.97, which means that the responses are close to their individual optimal values. As a result, the olive leaf extract obtained at these optimal MAE conditions has great potential to be effective in the treatment of obesity. [ABSTRACT FROM AUTHOR]

Layered semiconductors of the IIIA–VIA group have attracted considerable attention in (opto)electronic applications thanks to their atomically thin structures and their thickness‐dependent optical and electronic properties, which promise ultrafast response and high sensitivity. In particular, 2D indium selenide (InSe) has emerged as a promising candidate for the realization of thin‐film field effect transistors and phototransistors due to its high intrinsic mobility (>102 cm2 V−1 s−1) and the direct optical transitions in an energy range suitable for visible and near‐infrared light detection. A key requirement for the exploitation of large‐scale (opto)electronic applications relies on the development of low‐cost and industrially relevant 2D material production processes, such as liquid phase exfoliation, combined with the availability of high‐throughput device fabrication methods. Here, a β polymorph of indium selenide (β‐InSe) is exfoliated in isopropanol and spray‐coated InSe‐based photodetectors are demonstrated, exhibiting high responsivity to visible light (maximum value of 274 A W−1 under blue excitation 455 nm) and fast response time (15 ms). The devices show a gate‐dependent conduction with an n‐channel transistor behavior. Overall, this study establishes that liquid phase exfoliated β‐InSe is a valid candidate for printed high‐performance photodetectors, which is critical for the development of industrial‐scale 2D material‐based optoelectronic devices. [ABSTRACT FROM AUTHOR]

Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudodirect optical gap. Theoretical studies predict that its 2D form is a potential photocatalyst for water splitting reactions. Herein, the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single‐/few‐layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media is reported. In 0.5 m H2SO4, the GaSe photoelectrodes display the best PEC performance, corresponding to a ratiometric power‐saved metric for HER (Φsaved,HER) of 0.09% and a ratiometric power‐saved metric for OER (Φsaved,OER) of 0.25%. When used as PEC‐type photodetectors, GaSe photoelectrodes show a responsivity of ≈0.16 A W−1 upon 455 nm illumination at a light intensity of 63.5 µW cm−2 and applied potential of −0.3 V versus reversible hydrogen electrode (RHE). Stability tests of GaSe photodetectors demonstrated a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 m H2SO4 for HER. In contrast, degradation of photoelectrodes occurred in both alkaline and anodic operation due to the highly oxidizing environment and O2‐induced (photo)oxidation effects. The results provide new insight into the PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC‐type photodetectors, and (bio)sensors. [ABSTRACT FROM AUTHOR]

The design of efficient and cost-effective catalysts for the hydrogen evolution reaction (HER) is the key for molecular hydrogen (H2) production from electrochemical water splitting. Transition metal dichalcogenides (MX2), most notably group-6 MX2 (e.g., MoS2 and WS2), are appealing catalysts for the HER alternative to the best, but highly expensive, Pt-group elements. However, their HER activity is typically restricted to their edge sites rather than their basal plane. Furthermore, their semiconducting properties hinder an efficient electron transfer to the catalytic sites, which impedes a high rate of H2 production. Herein, we exploit liquid-phase exfoliation-produced metallic (1H, 2H and 3R) NbS2 nanoflakes, belonging to the class of metallic layered group-5 MX2, to overcome the abovementioned limitations. Both chemical treatment with hygroscopic Li salt and electrochemical in operando self-nanostructuring are exploited to improve the NbS2 nanoflake HER activity. The combination of NbS2 with other MX2, in our case MoSe2, also provides heterogeneous catalysts accelerating the HER kinetics of the individual counterparts. The designed NbS2-based catalysts exhibit an overpotential at a cathodic current of 10 mA cm−2 (η10) as low as 0.10 and 0.22 V vs. RHE in 0.5 M H2SO4 and 1 M KOH, respectively. In 0.5 M H2SO4, the HER activity of the NbS2-based catalysts is also superior to those of the Pt/C benchmark at current densities higher than 80 mA cm−2. Our work provides general guidelines for a scalable and cost-effective exploitation of NbS2, as well as the entire MX2 portfolio, for attaining a viable H2 production through electrochemical routes. [ABSTRACT FROM AUTHOR]