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1.
Nanoscale Adv ; 6(9): 2419-2430, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38694463

RESUMO

Molybdenum disulfide is an emerging 2D material with several potential applications in medicine. Therefore, it is crucial to ascertain its biocompatibility. Mast cells are immune cells that are found in many organs and tissues in contact with the extracellular environment, and can be cultured from progenitor cells present in the bone marrow. Given the long period required for differentiation and proliferation of primary mast cells, human mast cell lines have emerged as a tractable model for biological and toxicological studies. Here, we compare two types of industrial MoS2 using CD34+-derived primary human mast cells and the LAD2 cell line. Minimal effects were observed on early-stage activation endpoints such as ß-hexosaminidase release and expression of surface markers of mast cell activation. Transmission electron microscopy revealed limited uptake of the tested materials. Overall, MoS2 was found to be biocompatible, and the LAD2 cell line was validated as a useful in vitro model of mast cells.

2.
ACS Appl Mater Interfaces ; 16(11): 13706-13718, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38458613

RESUMO

The capacitance of electrode materials used in electrochemical double-layer capacitors (EDLCs) is currently limited by several factors, including inaccessible isolated micropores in high-surface area carbons, the finite density of states resulting in a quantum capacitance in series to Helmholtz double-layer capacitance, and the presence of surface impurities, such as functional groups and adsorbed species. To unlock the full potential of EDLC active materials and corresponding electrodes, several post-production treatments are commonly proposed to improve their capacitance and, thus, the energy density of the corresponding devices. In this work, we report a systematic study of the effect of a prototypical treatment, namely H2-assisted thermal treatment, on the chemical, structural, and thermal properties of activated carbon and corresponding electrodes. By combining multiple characterization techniques, we clarify the actual origins of the improvement of the performance (e.g., > +35% energy density for the investigated power densities in the 0.5-45 kW kg-1 range) of the EDLCs based on treated electrodes compared to the case based on the pristine electrodes. Contrary to previous works supporting a questionable graphitization of the activated carbon at temperatures <1000 °C, we found that a "surface graphitization" of the activated carbon, detected by spectroscopic analysis, is mainly associated with the desorption of surface contaminants. The elimination of surface impurities, including adsorbed species, improves the surface capacitance of the activated carbon (CsurfAC) by +37.1 and +36.3% at specific currents of 1 and 10 A g-1, respectively. Despite the presence of slight densification of the activated carbon upon the thermal treatment, the latter still improves the cell gravimetric capacitance normalized on the mass of the activated carbon only (CgAC), e.g., + 28% at 1 A g-1. Besides, our holistic approach identifies the change in the active material and binder contents as a concomitant cause of the increase of cell gravimetric capacitance (Cg), accounting for the mass of all of the electrode materials measured for treated electrodes compared to pristine ones. Overall, this study provides new insights into the relationship between the modifications of the electrode materials induced by H2-assisted thermal treatments and the performance of the resulting EDLCs.

3.
ACS Appl Energy Mater ; 6(22): 11560-11572, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-38037632

RESUMO

The search for safe electrolytes to promote the application of lithium-sulfur (Li-S) batteries may be supported by the investigation of viscous glyme solvents. Hence, electrolytes using nonflammable tetraethylene glycol dimethyl ether added by lowly viscous 1,3-dioxolane (DOL) are herein thoroughly investigated for sustainable Li-S cells. The electrolytes are characterized by low flammability, a thermal stability of ∼200 °C, ionic conductivity exceeding 10-3 S cm-1 at 25 °C, a Li+ transference number of ∼0.5, electrochemical stability window from 0 to ∼4.4 V vs Li+/Li, and a Li stripping-deposition overpotential of ∼0.02 V. The progressive increase of the DOL content from 5 to 15 wt % raises the activation energy for Li+ motion, lowers the transference number, slightly limits the anodic stability, and decreases the Li/electrolyte resistance. The electrolytes are used in Li-S cells with a composite consisting of sulfur and multiwalled carbon nanotubes mixed in the 90:10 weight ratio, exploiting an optimized current collector. The cathode is preliminarily studied in terms of structure, thermal behavior, and morphology and exploited in a cell using standard electrolyte. This cell performs over 200 cycles, with sulfur loading increased to 5.2 mg cm-2 and the electrolyte/sulfur (E/S) ratio decreased to 6 µL mg-1. The above sulfur cathode and the glyme-based electrolytes are subsequently combined in safe Li-S batteries, which exhibit cycle life and delivered capacity relevantly influenced by the DOL content within the studied concentration range.

4.
ACS Nano ; 17(24): 24919-24935, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38051272

RESUMO

Boron nitride (BN) nanomaterials have drawn a lot of interest in the material science community. However, extensive research is still needed to thoroughly analyze their safety profiles. Herein, we investigated the pulmonary impact and clearance of two-dimensional hexagonal boron nitride (h-BN) nanosheets and boron nitride nanotubes (BNNTs) in mice. Animals were exposed by single oropharyngeal aspiration to h-BN or BNNTs. On days 1, 7, and 28, bronchoalveolar lavage (BAL) fluids and lungs were collected. On one hand, adverse effects on lungs were evaluated using various approaches (e.g., immune response, histopathology, tissue remodeling, and genotoxicity). On the other hand, material deposition and clearance from the lungs were assessed. Two-dimensional h-BN did not cause any significant immune response or lung damage, although the presence of materials was confirmed by Raman spectroscopy. In addition, the low aspect ratio h-BN nanosheets were internalized rapidly by phagocytic cells present in alveoli, resulting in efficient clearance from the lungs. In contrast, high aspect ratio BNNTs caused a strong and long-lasting inflammatory response, characterized by sustained inflammation up to 28 days after exposure and the activation of both innate and adaptive immunity. Moreover, the presence of granulomatous structures and an indication of ongoing fibrosis as well as DNA damage in the lung parenchyma were evidenced with these materials. Concurrently, BNNTs were identified in lung sections for up to 28 days, suggesting long-term biopersistence, as previously demonstrated for other high aspect ratio nanomaterials with poor lung clearance such as multiwalled carbon nanotubes (MWCNTs). Overall, we reveal the safer toxicological profile of BN-based two-dimensional nanosheets in comparison to their nanotube counterparts. We also report strong similarities between BNNTs and MWCNTs in lung response, emphasizing their high aspect ratio as a major driver of their toxicity.


Assuntos
Nanoestruturas , Nanotubos de Carbono , Camundongos , Animais , Nanotubos de Carbono/toxicidade , Nanoestruturas/toxicidade , Pulmão/patologia , Compostos de Boro/toxicidade , Compostos de Boro/química
5.
ACS Appl Mater Interfaces ; 15(50): 58260-58273, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-38051559

RESUMO

Microglial cells play a critical role in glioblastoma multiforme (GBM) progression, which is considered a highly malignant brain cancer. The activation of microglia can either promote or inhibit GBM growth depending on the stage of the tumor development and on the microenvironment conditions. The current treatments for GBM have limited efficacy; therefore, there is an urgent need to develop novel and efficient strategies for drug delivery and targeting: in this context, a promising strategy consists of using nanoplatforms. This study investigates the microglial response and the therapeutic efficacy of dual-cell membrane-coated and doxorubicin-loaded hexagonal boron nitride nanoflakes tested on human microglia and GBM cells. Obtained results show promising therapeutic effects on glioma cells and an M2 microglia polarization, which refers to a specific phenotype or activation state that is associated with anti-inflammatory and tissue repair functions, highlighted through proteomic analysis.


Assuntos
Neoplasias Encefálicas , Glioblastoma , Humanos , Microglia , Proteômica , Glioblastoma/patologia , Doxorrubicina/farmacologia , Doxorrubicina/uso terapêutico , Neoplasias Encefálicas/patologia , Membrana Celular/patologia , Microambiente Tumoral/fisiologia , Linhagem Celular Tumoral
6.
J Am Chem Soc ; 145(39): 21419-21431, 2023 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-37747924

RESUMO

Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode for the HER composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru-Cu nanoheterostructures (Ru mass loading = 52 µg/cm2). Such an electrode exhibits a stable, over 250 h, low overpotential of 74 mV at -200 mA/cm2 for the HER in 1 M NaOH. The high activity of the electrode is attributed, by structural analysis, operando X-ray absorption spectroscopy, and first-principles simulations, to synergistic functionalities: (1) mechanically robust, vertically aligned Cu NRs with high electrical conductivity and porosity provide fast charge and gas transfer channels; (2) the Ru electronic structure, regulated by the size of Cu clusters at the surface, facilitates the water dissociation (Volmer step); (3) the Cu clusters grown atop Ru exhibit a close-to-zero Gibbs free energy of the hydrogen adsorption, promoting fast Heyrovsky/Tafel steps. An alkaline electrolyzer (AEL) coupling the proposed cathode and a stainless-steel anode can stably operate in both continuous (1 A/cm2 for over 200 h) and intermittent modes (accelerated stress tests). A techno-economic analysis predicts the minimal overall hydrogen production cost of US$2.12/kg in a 1 MW AEL plant of 30 year lifetime based on our AEL single cell, hitting the worldwide targets (US$2-2.5/kgH2).

7.
ACS Appl Mater Interfaces ; 15(33): 39218-39233, 2023 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-37552158

RESUMO

Lithium-oxygen (Li-O2) batteries are nowadays among the most appealing next-generation energy storage systems in view of a high theoretical capacity and the use of transition-metal-free cathodes. Nevertheless, the practical application of these batteries is still hindered by limited understanding of the relationships between cell components and performances. In this work, we investigate a Li-O2 battery by originally screening different gas diffusion layers (GDLs) characterized by low specific surface area (<40 m2 g-1) with relatively large pores (absence of micropores), graphitic character, and the presence of a fraction of the hydrophobic PTFE polymer on their surface (<20 wt %). The electrochemical characterization of Li-O2 cells using bare GDLs as the support indicates that the oxygen reduction reaction (ORR) occurs at potentials below 2.8 V vs Li+/Li, while the oxygen evolution reaction (OER) takes place at potentials higher than 3.6 V vs Li+/Li. Furthermore, the relatively high impedance of the Li-O2 cells at the pristine state remarkably decreases upon electrochemical activation achieved by voltammetry. The Li-O2 cells deliver high reversible capacities, ranging from ∼6 to ∼8 mA h cm-2 (referred to the geometric area of the GDLs). The Li-O2 battery performances are rationalized by the investigation of a practical Li+ diffusion coefficient (D) within the cell configuration adopted herein. The study reveals that D is higher during ORR than during OER, with values depending on the characteristics of the GDL and on the cell state of charge. Overall, D values range from ∼10-10 to ∼10-8 cm2 s-1 during the ORR and ∼10-17 to ∼10-11 cm2 s-1 during the OER. The most performing GDL is used as the support for the deposition of a substrate formed by few-layer graphene and multiwalled carbon nanotubes to improve the reaction in a Li-O2 cell operating with a maximum specific capacity of 1250 mA h g-1 (1 mA h cm-2) at a current density of 0.33 mA cm-2. XPS on the electrode tested in our Li-O2 cell setup suggests the formation of a stable solid electrolyte interphase at the surface which extends the cycle life.

8.
Nat Commun ; 14(1): 4680, 2023 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-37542064

RESUMO

Alkaline electrolyzers generally produce hydrogen at current densities below 0.5 A/cm2. Here, we design a cost-effective and robust cathode, consisting of electrodeposited Ru nanoparticles (mass loading ~ 53 µg/cm2) on vertically oriented Cu nanoplatelet arrays grown on metallic meshes. Such cathode is coupled with an anode based on stacked stainless steel meshes, which outperform NiFe hydroxide catalysts. Our electrolyzers exhibit current densities as high as 1 A/cm2 at 1.69 V and 3.6 A/cm2 at 2 V, reaching the performances of proton-exchange membrane electrolyzers. Also, our electrolyzers stably operate in continuous (1 A/cm2 for over 300 h) and intermittent modes. A total production cost of US$2.09/kgH2 is foreseen for a 1 MW plant (30-year lifetime) based on the proposed electrode technology, meeting the worldwide targets (US$2-2.5/kgH2). Hence, the use of a small amount of Ru in cathodes (~0.04 gRu per kW) is a promising strategy to solve the dichotomy between the capital and operational expenditures of conventional alkaline electrolyzers for high-throughput operation, while facing the scarcity issues of Pt-group metals.

9.
J Mater Chem A Mater ; 11(24): 12866-12875, 2023 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-37346737

RESUMO

Improving the perovskite/electron-transporting layer (ETL) interface is a crucial task to boost the performance of perovskite solar cells (PSCs). This is utterly fundamental in an inverted (p-i-n) configuration using fullerene-based ETLs. Here, we propose a scalable strategy to improve fullerene-based ETLs by incorporating high-quality few-layer graphene flakes (GFs), industrially produced through wet-jet milling exfoliation of graphite, into phenyl-C61-butyric acid methyl ester (PCBM). Our new composite ETL (GF:PCBM) can be processed into an ultrathin (∼10 nm), pinhole-free film atop the perovskite. We find that the presence of GFs in the PCBM matrix reduces defect-mediated recombination, while creating preferential paths for the extraction of electrons towards the current collector. The use of our GF-based composite ETL resulted in a significant enhancement in the open circuit voltage and fill factor of triple cation-based inverted PSCs, boosting the power conversion efficiency from ∼19% up to 20.8% upon the incorporation of GFs into the ETL.

10.
11.
Adv Mater ; 35(23): e2211037, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36994787

RESUMO

The integration of 2D materials in triboelectric nanogenerators (TENGs) is known to increase the mechanical-to-electrical power conversion efficiency. 2D materials are used in TENGs with multiple roles as triboelectric material, charge-trapping fillers, or as electrodes. Here, novel TENGs based on few-layers graphene (FLG) electrodes and stable gel electrolytes composed of liquid phase exfoliated 2D-transition metal dichalcogenides and polyvinyl alcohol are developed. TENGs embedding FLG and gel composites show competitive open-circuit voltage (≈ 300 V), instant peak power (530 mW m-2 ), and stability (> 11 months). These values correspond to a seven-fold higher electrical output compared to TENGs embedding bare FLG electrodes. It is demonstrated that such a significant improvement depends on the high electrical double-layer capacitance (EDLC) of FLG electrodes functionalized with the gel composites. The wet encapsulation of the TENGs is shown to be an effective strategy to increase their power output further highlighting the EDLC role. It is also shown that the EDLC is dependent upon the transition metal (W vs Mo) rather than the relative abundance of 1T or 2H phases. Overall, this work lays down the roots for novel sustainable electrochemical-(e)-TENGs developed exploiting strategies typically used in electrochemical capacitors.

12.
NanoImpact ; 29: 100451, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36626980

RESUMO

MoS2 has been increasingly used in place of graphene as a flexible and multifunctional 2D material in many biomedical applications such as cancer detection and drug delivery, which makes it crucial to evaluate downstream compatibility in human immune cells. Molybdenum is a component of stainless-steel stent implants and has previously been implicated in stent hypersensitivity. In view of this, it is important to ascertain the effect of MoS2 on allergy-relevant cells. Basophils are a less commonly used immune cell type. Unlike mast cells, basophils can be easily derived from primary human blood and can act as a sentinel for allergy. However, merely testing any one type of MoS2 in basophils could result in different biological results. We thus decided to compare 2D MoS2 from the two companies BeDimensional© (BD) and Biograph Solutions (BS), manufactured with two different but commonly exploited methods (BD, deoxycholate surfactant in a high-pressure liquid exfoliation, and BS using glycine in ball-milling exfoliation) to elucidate immunological end-points common to both MoS2 and to demonstrate the need for biological verification for end-users who may require a change of supplier. We report higher histamine production in human basophils with MoS2. No effects on either surface basophil activation markers CD63 and CD203c or reactive oxygen species (ROS) production and cell viability were observed. However, different cytokine production patterns were evidenced. IL-6 and IL-1ß but not TNF and GM-CSF were increased for both MoS2. BS-MoS2 increased IL-4, while BD-MoS2 decreased IL-4 and increased IL-13. Molybdate ion itself only increased IL-1ß and IL-4. Deoxycholate surfactant decreased viability at 18 h and increased ROS upon basophil activation. Therefore, these results demonstrate the safety of MoS2 in human basophils in general and highlight the importance of considering manufacturer additives and variability when selecting and investigating 2D materials such as MoS2.


Assuntos
Basófilos , Hipersensibilidade , Humanos , Molibdênio/metabolismo , Interleucina-4/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Hipersensibilidade/metabolismo , Ácido Desoxicólico/metabolismo
13.
Front Chem ; 10: 1045212, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36385988

RESUMO

We report high-current density operating alkaline (water) electrolyzers (AELs) based on platinum on Vulcan (Pt/C) cathodes and stainless-steel anodes. By optimizing the binder (Nafion ionomer) and Pt mass loading (mPt) content in the catalysts coating at the cathode side, the AEL can operate at the following (current density, voltage, energy efficiency -based on the hydrogen higher heating value-) conditions (1.0 A cm-2, 1.68 V, 87.8%) (2.0 A cm-2, 1.85 V, 79.9%) (7.0 A cm-2, 2.38 V, 62.3%). The optimal amount of binder content (25 wt%) also ensures stable AEL performances, as proved through dedicated intermittent (ON-OFF) accelerated stress tests and continuous operation at 1 A cm-2, for which a nearly zero average voltage increase rate was measured over 335 h. The designed AELs can therefore reach proton-exchange membrane electrolyzer-like performance, without relying on the use of scarce anode catalysts, namely, iridium. Contrary to common opinions, our preliminary techno-economic analysis shows that the Pt/C cathode-enabled high-current density operation of single cell AELs can also reduce substantially the impact of capital expenditures (CAPEX) on the overall cost of the green hydrogen, leading CAPEX to operating expenses (OPEX) cost ratio <10% for single cell current densities ≥0.8 A cm-2. Thus, we estimate a hydrogen production cost as low as $2.06 kgH2 -1 for a 30 years-lifetime 1 MW-scale AEL plant using Pt/C cathodes with mPt of 150 µg cm-2 and operating at single cell current densities of 0.6-0.8 A cm-2. Thus, Pt/C cathodes enable the realization of AELs that can efficiently operate at high current densities, leading to low OPEX while even benefiting the CAPEX due to their superior plant compactness compared to traditional AELs.

14.
ACS Nano ; 16(10): 16426-16442, 2022 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-36194759

RESUMO

Highly efficient and durable flexible solid-state supercapacitors (FSSSCs) are emerging as low-cost devices for portable and wearable electronics due to the elimination of leakage of toxic/corrosive liquid electrolytes and their capability to withstand elevated mechanical stresses. Nevertheless, the spread of FSSSCs requires the development of durable and highly conductive solid-state electrolytes, whose electrochemical characteristics must be competitive with those of traditional liquid electrolytes. Here, we propose an innovative composite solid-state electrolyte prepared by incorporating metallic two-dimensional group-5 transition metal dichalcogenides, namely, liquid-phase exfoliated functionalized niobium disulfide (f-NbS2) nanoflakes, into a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The terminal sulfonate groups in f-NbS2 nanoflakes interact with the sulfonic acid groups of SPEEK by forming a robust hydrogen bonding network. Consequently, the composite solid-state electrolyte is mechanically/dimensionally stable even at a degree of sulfonation of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical strength is 38.3 MPa, and thanks to an efficient proton transport through the Grotthuss mechanism, the proton conductivity is as high as 94.4 mS cm-1 at room temperature. To elucidate the importance of the interaction between the electrode materials (including active materials and binders) and the solid-state electrolyte, solid-state supercapacitors were produced using SPEEK and poly(vinylidene fluoride) as proton conducting and nonconducting binders, respectively. The use of our solid-state electrolyte in combination with proton-conducting SPEEK binder and carbonaceous electrode materials (mixture of activated carbon, single/few-layer graphene, and carbon black) results in a solid-state supercapacitor with a specific capacitance of 116 F g-1 at 0.02 A g-1, optimal rate capability (76 F g-1 at 10 A g-1), and electrochemical stability during galvanostatic charge/discharge cycling and folding/bending stresses.

15.
Nanoscale Adv ; 4(4): 1136-1144, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36131758

RESUMO

A comparative study on sulfur-based composite electrodes comprising different few-layer graphene contents prepared via a facile evaporation method is presented here. The active material production process employed here, exploring different sulfur-few layer graphene ratios, enabled tuning and optimization of the sample morphology, as confirmed via a scanning electron microscopy study. The results reveal that the graphene content is a crucial parameter yielding an optimized morphology of spherical particles composed of an elemental sulfur inner core covered by the carbonaceous compound. The electrodes are characterized in lithium metal half-cells in terms of cyclic voltammetry, galvanostatic cycling tests, rate capability and electrochemical impedance spectroscopy. Moreover, the lithium-ion diffusion coefficients of each sample are obtained by the Randles-Sevcik equation in order to evaluate the reliability of the electrochemical processes. The lithium metal half-cell with the sulfur carbon composite active material exploiting a spherical particle morphology delivers a high specific capacity of 950 mA h g-1 after 100 cycles at C/4 with a coulombic efficiency of 98%. An optimized sample, tuned in terms of sulfur content and morphology, shows superior performance, exhibiting capacities of 1128 mA h g-1 and 842 mA h g-1 over 80 cycles at C/4 and 2C, respectively.

16.
Energy Fuels ; 36(16): 9321-9328, 2022 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-36016761

RESUMO

Lithium-sulfur battery of practical interest requires thin-layer support to achieve acceptable volumetric energy density. However, the typical aluminum current collector of Li-ion battery cannot be efficiently used in the Li/S system due to the insulating nature of sulfur and a reaction mechanism involving electrodeposition of dissolved polysulfides. We study the electrochemical behavior of a Li/S battery using a carbon-coated Al current collector in which the low thickness, the high electronic conductivity, and, at the same time, the host ability for the reaction products are allowed by a binder-free few-layer graphene (FLG) substrate. The FLG enables a sulfur electrode having a thickness below 100 µm, fast kinetics, low impedance, and an initial capacity of 1000 mAh gS -1 with over 70% retention after 300 cycles. The Li/S cell using FLG shows volumetric and gravimetric energy densities of 300 Wh L-1 and 500 Wh kg-1, respectively, which are values well competing with commercially available Li-ion batteries.

17.
ACS Appl Mater Interfaces ; 14(30): 34963-34974, 2022 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-35876692

RESUMO

Bismuth telluride halides (BiTeX) are Rashba-type crystals with several potential applications ranging from spintronics and nonlinear optics to energy. Their layered structures and low cleavage energies allow their production in a two-dimensional form, opening the path to miniaturized device concepts. The possibility to exfoliate bulk BiTeX crystals in the liquid represents a useful tool to formulate a large variety of functional inks for large-scale and cost-effective device manufacturing. Nevertheless, the exfoliation of BiTeI by means of mechanical and electrochemical exfoliation proved to be challenging. In this work, we report the first ultrasonication-assisted liquid-phase exfoliation (LPE) of BiTeI crystals. By screening solvents with different surface tension and Hildebrandt parameters, we maximize the exfoliation efficiency by minimizing the Gibbs free energy of the mixture solvent/BiTeI crystal. The most effective solvents for the BiTeI exfoliation have a surface tension close to 28 mN m-1 and a Hildebrandt parameter between 19 and 25 MPa0.5. The morphological, structural, and chemical properties of the LPE-produced single-/few-layer BiTeI flakes (average thickness of ∼3 nm) are evaluated through microscopic and optical characterizations, confirming their crystallinity. Second-harmonic generation measurements confirm the non-centrosymmetric structure of both bulk and exfoliated materials, revealing a large nonlinear optical response of BiTeI flakes due to the presence of strong quantum confinement effects and the absence of typical phase-matching requirements encountered in bulk nonlinear crystals. We estimated a second-order nonlinearity at 0.8 eV of |χ(2)| ∼ 1 nm V-1, which is 10 times larger than in bulk BiTeI crystals and is of the same order of magnitude as in other semiconducting monolayers (e.g., MoS2).

18.
Nanoscale ; 14(16): 6152-6161, 2022 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-35389414

RESUMO

In this work, novel proton-exchange membranes (PEMs) based on sulfonated poly(ether ether ketone) (SPEEK) and two-dimensional (2D) sulfonated niobium disulphide (S-NbS2) nanoflakes are synthesized by a solution-casting method and used in vanadium redox flow batteries (VRFBs). The NbS2 nanoflakes are produced by liquid-phase exfoliation of their bulk counterpart and chemically functionalized with terminal sulfonate groups to improve dimensional and chemical stabilities, proton conductivity (σ) and fuel barrier properties of the as-produced membranes. The addition of S-NbS2 nanoflakes to SPEEK decreases the vanadium ion permeability from 5.42 × 10-7 to 2.34 × 10-7 cm2 min-1. Meanwhile, it increases the membrane σ and selectivity up to 94.35 mS cm-2 and 40.32 × 104 S min cm-3, respectively. The cell assembled with the optimized membrane incorporating 2.5 wt% of S-NbS2 nanoflakes (SPEEK:2.5% S-NbS2) exhibits high efficiency metrics, i.e., coulombic efficiency between 98.7 and 99.0%, voltage efficiency between 90.2 and 73.2% and energy efficiency between 89.3 and 72.8% within the current density range of 100-300 mA cm-2, delivering a maximum power density of 0.83 W cm-2 at a current density of 870 mA cm-2. The SPEEK:2.5% S-NbS2 membrane-based VRFBs show a stable behavior over 200 cycles at 200 mA cm-2. This study opens up an effective avenue for the production of advanced SPEEK-based membranes for VRFBs.

19.
ACS Appl Energy Mater ; 5(2): 1378-1384, 2022 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-35252771

RESUMO

Perovskite solar cells have reached certified power conversion efficiency over 25%, enabling the realization of efficient large-area modules and even solar farms. It is therefore essential to deal with technical aspects, including the reverse-bias operation and hot-spot effects, which are crucial for the practical implementation of any photovoltaic technology. Here, we analyze the reverse bias (from 2.5 to 30 V) and temperature behavior of mesoscopic cells through infrared thermal imaging coupled with current density measurements. We show that the occurrence of local heating (hot-spots) and arc faults, caused by local shunts, must be considered during cell and module designing.

20.
Inorg Chem ; 61(11): 4598-4608, 2022 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-35254806

RESUMO

This work reports a method to obtain stable dispersions of nickel-iron layered double hydroxide (NiFe-LDH) nanosheets in ethanol by exposing the as-synthetized bulk NiFe-LDH to a sodium acetate solution or by adding acetate and citrate anions inside the reaction mixture. In the case of citrate-containing NiFe-LDH, the formation of single-layer nanosheets is confirmed by X-ray diffraction and atomic force microscopy measurements. Lastly, the effect of acetate ions on the electrocatalytic activity of NiFe-LDH is discussed for the oxygen evolution reaction. Our results provide useful information to improve the existing LDH exfoliation routes based on the use of green solvent alternatives to the mostly used formamide.

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