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1.
ACS Biomater Sci Eng ; 9(5): 2170-2180, 2023 05 08.
Artigo em Inglês | MEDLINE | ID: mdl-36149264

RESUMO

Obesity is a complex disorder associated with immense health consequences including high risk of cardiovascular diseases, diabetes, and cancer. Abnormality in the thyroid gland, genetics, less physical activity, uptake of excessive diet, and leptin resistance are critical factors in the development of obesity. To determine the treatment strategy, understanding the pathophysiology of obesity is crucial. For instances, leptin resistance mediated obesity defined by the presence of excessive leptin hormone (Lep) in the systemic circulation is very common in diet induced obesity. Therefore, our hypothesis is that quantitative measurement of Lep from blood can help to identify individuals with Lep resistant mediated obesity and thereby guide toward a proper treatment strategy. In this work, we aim to utilize an electrochemical immunosensing platform for diagnosis of obesity by measuring the Lep content in systemic circulation. A porous carbon confined FeNi bimetallic system was synthesized with three different ratios of Fe and Ni ions using high temperature pyrolysis technique. The suitability of the sensor for detecting Lep was studied using both CV and EIS techniques. The limit of detection (LOD) for GCE was recorded as 157.4 fg/mL with a wide linear concentration range of 500 fg/mL to 80 ng/mL, while for SPCE the LOD was 184.9 fg/mL with a linear range of 500 fg/mL to 50 ng/mL. Finally, the feasibility and applicability of the sensor for Lep detection was tested with serum collected from high fat diet induced obese rats. The selectivity, sensitivity, storage, and experimental stability and reproducibility tests showed potential for this biosensor platform as a point-of-care Lep detection device.


Assuntos
Leptina , Obesidade , Ratos , Animais , Reprodutibilidade dos Testes , Obesidade/diagnóstico , Obesidade/terapia
2.
ACS Appl Mater Interfaces ; 14(3): 3919-3929, 2022 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-35014264

RESUMO

The design of alternative earth-abundant van der Waals (vdW) nanoheterostructures for bifunctional oxygen evolution/reduction (OER/ORR) electrocatalysis is of paramount importance to fabricate energy-related devices. Herein, we report a simple metal-organic framework (MOF)-derived synthetic strategy to fabricate low-dimensional (LD) nanohybrids formed by zero-dimensional (0D) ZrO2 nanoparticles (NPs) and heteroatom-doped two-dimensional (2D) carbon nanostructures. The 2D platforms controlled the electronic structures of interfacial Zr atoms, thus producing optimized electron polarization for boron and nitrogen-doped carbon (BCN)/ZrO2 nanohybrids. X-ray photoelectron spectroscopy (XPS) and theoretical studies revealed the key role of the synergistic couple effect of boron (B) and nitrogen (N) in interfacial electronic polarization. The BCN/ZrO2 nanohybrid showed excellent bifunctional electrocatalytic activity, delivering an overpotential (η10) of 301 mV to reach a current density of 10 mA-cm-2 for the OER process and a half-wave potential (E1/2) of 0.85 V vs reversible hydrogen electrode (RHE) for the ORR process, which are comparable to the state-of-the-art LD nanohybrids. Furthermore, BCN/ZrO2 also showed competitive performances for water-splitting and zinc-air battery devices. This work establishes a new route to fabricate highly efficient multifunctional electrocatalysts by tuning the electronic polarization properties of 0D-2D electrochemical interfaces.

3.
Chem Soc Rev ; 51(3): 812-828, 2022 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-35022644

RESUMO

Low dimensional electrocatalytic heterostructures have recently attracted significant attention in the catalysis community due to their highly tuneable interfaces and exciting electronic features, opening up new possibilities for effective nanometric control of both the charge carriers and energetic states of several intermediate catalytic species. In-depth understanding of electrocatalytic routes at the interface between two or more low-dimensional nanostructures has triggered the development of heterostructure nanocatalysts with extraordinary properties for water splitting reactions, NRR and CO2RR. This tutorial review provides an overview of the most recent advances in synthetic strategies for 0D-1D, 0D-2D, and 2D-2D nanoheterostructures, discussing key aspects of their electrocatalytic performances from experimental and computational perspectives as well as their applications towards the development of overall water splitting and Zn-air battery devices.

5.
Langmuir ; 37(18): 5699-5706, 2021 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-33900778

RESUMO

Blending TiO2 and cement to create photocatalytic composites holds promise for low-cost, durable water treatment. However, the efficiency of such composites hinges on cross-effects of several parameters such as cement composition, type of photocatalyst, and microstructure, which are poorly understood and require extensive combinatorial tests to discern. Here, we report a new combinatorial data science approach to understand the influence of various photocatalytic cement composites based on limited datasets. Using P25 nanoparticles and submicron-sized anatase as representative TiO2 photocatalysts and methyl orange and 1,4-dioxane as target organic pollutants, we demonstrate that the cement composition is a more influential factor on photocatalytic activity than the cement microstructure and TiO2 type and particle size. Among the various cement constituents, belite and ferrite had strong inverse correlation with photocatalytic activity, while natural rutile had a positive correlation, which suggests optimization opportunities by manipulating the cement composition. These results were discerned by screening 7806 combinatorial functions that capture cross-effects of multiple compositional phases and obtaining correlation scores. We also report •OH radical generation, cement aging effects, TiO2 leaching, and strategies to regenerate photocatalytic surfaces for reuse. This work provides several nonintuitive correlations and insights on the effect of cement composition and structure on performance, thus advancing our knowledge on development of scalable photocatalytic materials for drinking water treatment in rural and resource-limited areas.

6.
Chem Soc Rev ; 50(8): 4856-4871, 2021 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-33704291

RESUMO

Nature-inspired hierarchical architectures have recently drawn enormous interest in the materials science community, being considered as promising materials for the development of high-performance wearable electronic devices. Their highly dynamic interfacial interactions have opened new horizons towards the fabrication of sustainable sensing and energy storage materials with multifunctional properties. Nature-inspired assemblies can exhibit impressive properties including ultrahigh sensitivity, excellent energy density and coulombic efficiency behaviors as well as ultralong cycling stability and durability, which can be finely tuned and enhanced by controlling synergistic interfacial interactions between their individual components. This tutorial review article aims to address recent breakthroughs in the development of advanced Nature-inspired sensing and energy storage materials, with special emphasis on the influence of interfacial interactions over their improved properties.

7.
J Am Chem Soc ; 143(2): 1203-1215, 2021 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-33401899

RESUMO

The development of low-dimensional (LD) supramolecular materials with multifunctional electrocatalytic properties has sparked the attention of the catalysis community. Herein, we report the synthesis of a new class of 0D-2D heterostructures composed of boron carbon nitride nanosheets (BCN NSs) and fullerene molecules (C60/F) that exhibit multifunctional electrocatalytic properties for the hydrogen evolution/oxidation reactions (HER/HOR) and the oxygen evolution/reduction reactions (OER/ORR). The electrocatalytic properties were studied with varying F:BCN weight ratios to optimize the intermolecular electron transfer (ET) from the BCN NSs to the electron-accepting C60 molecules. The nanohybrid supramolecular material with 10 wt % F in BCN NSs (10% F/BCN) exhibited the largest Raman and C 1s binding energy shifts, which were associated with greater cooperativity interactions and enhanced ET processes at the F/BCN interface. This synergistic interfacial phenomenon resulted in highly active catalytic sites that markedly boosted electrocatalytic activity of the material. The 10% F/BCN showed the highest tetrafunctional catalytic performance, outperforming the OER catalytic activity of commercial RuO2 catalysts with a η10 of 390 mV and very competitive onset potential values of -0.042 and 0.92 V vs RHE for HER and ORR, respectively, and a current density value of 1.47 mA cm-2 at 0.1 V vs RHE with an ultralow ΔGH* value of -0.03 eV toward the HOR process. Additionally, the 10% F/BCN catalyst was also used as both cathode and anode in a water splitting device, delivering a cell potential of 1.61 V to reach a current density of 10 mA cm-2.

8.
J Colloid Interface Sci ; 581(Pt B): 905-918, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32956910

RESUMO

Porous carbon encapsulated non-precious metal nanocatalysts have recently opened the ways towards the development of high-performance water remediation and energy conversion technologies. Herein, we report a facile, scalable and green synthetic methodology to fabricate porous carbon encapsulated transition metal nanocatalysts (M@TP: M = Cu, Ni, Fe and Co) using commercial tissue paper. The morphology, crystalline structure, chemical composition and textural properties of the M@TP nanocatalysts were thoroughly characterized. The catalytic activity of the M@TP nanocatalysts was investigated for the degradation of Congo red (CR) via peroxymonosulfate activation. Co@TP-6 was found to be the most active catalyst allowing 97.68% degradation in 30 min with a higher rate constant of 0.109 min-1. The nanocatalysts also displayed a carbon shell thickness-dependent electrocatalytic hydrogen evolution reaction (HER) activity, most likely due to the shielding effect of the carbon layers over the electron transfer (ET) processes at the metal core/carbon interfaces. Remarkably, the Ni@TP-6 electrocatalyst, with the smaller carbon shell thickness, showed the best electrocatalytic performance. They delivered an ultralow onset potential of -30 mV vs RHE, an overpotential of 105 mV at a current density of 10 mA·cm-2 and an excellent electrochemical stability to keep the 92% of the initial current applied after 25000 s, which is comparable with the HER activity of the state-of-the-art Ni-based catalysts.

9.
Water Sci Technol ; 82(7): 1370-1379, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33079716

RESUMO

While extensive work has been done on the generation of adsorbents by carbonization of large polymeric structures, few works are currently available for the use of monomeric carbon molecules as precursors during carbonization. In this work we report the formation of a carbon adsorbent material from the carbonization of glucose in the presence of zinc oxide (ZnO) nanoparticle templates. Carbonization at 1,000 °C under inert atmosphere yields a product with Brunauer-Emmett-Teller (BET) surface area of 1,228.19 m2/g and 14.77 nm average pore diameter. Adsorption capacities against methylene blue, 2-naphthol and bisphenol-A at pH 7 were found to be 539 mg/g, 737 mg/g and 563 mg/g, respectively. Our material demonstrates a strong fit with the Langmuir isotherm, and adsorption kinetics show regression values near unity for the pseudo-second order kinetic model. A flow adsorption column was implemented for the remediation of tap water containing 20 mg/L methylene blue and found to quantitatively purify 11.5 L of contaminated water.


Assuntos
Poluentes Ambientais , Nanopartículas , Poluentes Químicos da Água , Glucose , Água
11.
J Am Chem Soc ; 142(34): 14688-14701, 2020 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-32786805

RESUMO

The rational design of multifunctional catalysts that use non-noble metals to facilitate the interconversion between H2, O2, and H2O is an intense area of investigation. Bimetallic nanosystems with highly tunable electronic, structural, and catalytic properties that depend on their composition, structure, and size have attracted considerable attention. Herein, we report the synthesis of bimetallic nickel-copper (NiCu) alloy nanoparticles confined in a sp2 carbon framework that exhibits trifunctional catalytic properties toward hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER) reactions. The electrocatalytic functions of the NiCu nanoalloys were experimentally and theoretically correlated with the composition-dependent local structural distortion of the bimetallic lattice at the nanoparticle surfaces. Our study demonstrated a downshift of the d-band of the catalysts that adjusts the binding energies of the intermediate catalytic species. XPS analysis revealed that the binding energy for Ni 2p3/2 band of the Ni0.25Cu0.75/C nanoparticles was shifted ∼3 times compared to other bimetallic systems, and this was correlated to the high electrocatalytic activity observed. Interestingly, the bimetallic Ni0.25Cu0.75/C catalyst surpassed the OER performance of RuO2 benchmark catalyst exhibiting a small onset potential of 1.44 V vs RHE and an overpotential of 400 mV at 10 mA·cm-2 as well as the electrochemical long-term stability of commercial RuO2 and Pt catalysts and kept at least 90% of the initial current applied after 20 000 s for the OER/ORR/HER reactions. This study reveals significant insight about the structure-function relationship for non-noble bimetallic nanostructures with multifunctional electrocatalytic properties.

12.
Int J Nanomedicine ; 15: 5097-5111, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32764939

RESUMO

INTRODUCTION: In this in-vitro study, we designed a 3D printed composite of zinc oxide (ZnO) nanoparticles (NPs) with photocatalytic activities encapsulated within hydrogel (alginate) constructs, for antibacterial purposes applicable towards wound healing. We primarily sought to confirm the mechanical properties and cell compatibility of these ZnO NP infused scaffolds. METHODS: The antibacterial property of the ZnO NPs was confirmed by hydroxyl radical generation using ultraviolet (U.V.) photocatalysis. Titanium dioxide (TiO2), a well-known antibacterial compound, was used as a positive control (1% w/v) for the ZnO NP-based alginate constructs and their antibacterial efficacies compared. Among the ZnO group, 3D printed gels containing 0.5% and 1% w/v of ZnO were analyzed and compared with manually casted samples via SEM, swelling evaluation, and rheological analysis. Envisioning an in-vivo application for the 3D printed ZnO NP-based alginates, we studied their antibacterial properties by bacterial broth testing, cytocompatibility via live/dead assay, and moisture retention capabilities utilizing a humidity sensor. RESULTS: 3D printed constructs revealed significantly greater pore sizes and enhanced structural stability compared to manually casted samples. For all samples, the addition of ZnO or TiO2 resulted in significantly stiffer gels in comparison with the alginate control. Bacterial resistance testing on Staphylococcus epidermidis indicated the addition of ZnO NPs to the gels decreased bacterial growth when compared to the alginate only gels. Cell viability of STO-fibroblasts was not adversely affected by the addition of ZnO NPs to the alginate gels. Furthermore, the addition of increasing doses of ZnO NPs to the alginate demonstrated increased humidity retention in gels. DISCUSSION: The customization of 3D printed alginates containing antibacterial ZnO NPs leads to an alternative that allows accessible mobility of molecular exchange required for improving chronic wound healing. This scaffold can provide a cost-effective and durable antibacterial treatment option.


Assuntos
Alginatos/química , Alginatos/farmacologia , Hidrogéis/química , Nanopartículas/química , Cicatrização/efeitos dos fármacos , Óxido de Zinco/química , Sobrevivência Celular/efeitos dos fármacos , Fibroblastos/citologia
13.
Sci Total Environ ; 704: 135406, 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-31896226

RESUMO

While the use of TiO2 nanoparticles in the form of slurry/suspension requires energy-intensive separation processes, its immobilization in solid support may open new opportunities in the area of sustainable water treatment technologies. In this study, a novel method for the development of photocatalytic paint based on TiO2 nanoparticles and acrylate-based photopolymer resin is reported. The paint (TiO2@polymer) was applied on substrates such as plastic petri dish and glass jar, which was polymerized/solidified by ultraviolet light irradiation. The painted petri dish and glass jar were used for the photocatalytic degradation of model organic pollutants viz. methyl orange (MO), methylene blue (MB), and indole in deionized water, simulated fresh drinking water, and tap water matrices. The photocatalytic degradation studies were performed under sunlight and UV-B light were used for. The sunlight-assisted photocatalytic degradation of MO and MB was found to be faster and more efficient than the UV-B light-assisted ones. Under UV-B light irradiation, it took 120 min to degrade about 80% of 6 ppm MB solution, whereas under sunlight irradiation it took 60 min to degrade about 90% of the same MB solution. The photocatalytic paint generated hydroxyl radical (·OH) under the UV-B and sunlight irradiation, which was studied by the terephthalic acid fluorescence tests. Further, the potential release of TiO2 during the exposure to UV irradiation was studied by single particle ICP-MS analysis.

14.
Sci Total Environ ; 698: 134214, 2020 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-31514030

RESUMO

In this report, highly crystalline and well-dispersed nano-sized nickel metal organic framework (MOFs) was decorated over graphene oxide (GO) and carbon nanotubes (CNTs) platforms to form hybrid nanocomposites. These as-synthesized hybrid nanocomposites were synthesized through a one-pot green solvothermal method. The prepared nanocomposites were characterized by SEM, TEM, EDS, XRD, FT-IR, Raman and TGA techniques. XRD analysis revealed the crystalline structure of the hybrid nanocomposites. Morphological and elemental studies also verified successful decoration of nickel-benzene dicarboxylate (Ni-BDC) MOFs over GO and CNT platforms. Chemical analysis collected through IR, and thermal analysis collected through TGA technique, illustrated the presence of all the components in the hybrid nanomaterials. Methylene blue (MB) was used as a model organic pollutant to analyze the adsorption capacity of the prepared nanocomposites. According to the findings, a strong interaction exists between the MB molecule and the developed adsorbents at which due to the synergistic effect, the hybrid nanocomposites show several times higher adsorption capacity compared to that of parent materials. This improvement can be due to several reasons: high surface area of the MOFs in the composites resulting from the smaller size of MOFs, presence of the pores formed between the MOFs and the platforms and different morphological characteristic of Ni-BDC MOFs in hybrid nanocomposites, compared to bare Ni-BDC MOFs. Furthermore, the isotherm and kinetic studies revealed that the adsorption of MB onto the newly prepared adsorbents could best be explained by the Langmuir and Pseudo-second order kinetic models. A regeneration study demonstrated the highly stable nature of the hybrid nanocomposites.

15.
ACS Omega ; 4(4): 6560-6572, 2019 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-31459786

RESUMO

We report a facile method for the synthesis of zinc oxide nanoparticles (nZnOs) by rapidly heating a paste of zinc nitrate and sucrose on the hot plate at 500 °C. The transmission electron microscopy images revealed the spherical shape of the nZnO with an average size of 35 nm. The band gap and the specific surface area of the nZnO were measured to be about 3.32 eV and 80.11 m2/g, respectively. The nZnO was utilized for the photocatalytic degradation of methyl orange (MO) and methylene blue (MB) in water under the ultraviolet (UV-B) light and sunlight irradiation. Photocatalysis was performed in two types of water matrices, viz., the deionized water and the simulated fresh drinking water. Almost a complete degradation of MO and MB was obtained within 30 min of UV-B light irradiation. Under sunlight irradiation, more than 95% of the MO solution underwent degradation within 30 min. The photocatalytic stability of the nZnO was examined for five cycles, and a similar activity was found throughout the cycles. The photocatalytic generation of the hydroxyl radical (•OH) was confirmed by the terephthalic acid photoluminescence tests. Moreover, the synthesis methodology was validated by triplicating the nZnO synthesis. Every time, the nZnO demonstrated a similar photocatalytic activity, which confirmed the robustness of the synthesis procedure.

16.
Sci Total Environ ; 673: 306-317, 2019 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-30991320

RESUMO

A series of novel absorbents based on Cu-BDC MOFs decorated over graphene oxide (GrO) and carbon nanotubes (CNTs) hybrid nanocomposites, namely Cu-BDC@GrO and Cu-BDC@CNT, are synthesized via a facile and one-pot green solvothermal method for water remediation. The nanocomposites were characterized by XRD, TEM, SEM, EDS, Raman, FTIR, TGA, XPS, Zetasizer and ICP-OES instruments. XRD results confirmed the high crystalline structure of the synthesized hybrid nanocomposites. Morphological analysis by SEM and TEM verified the successful decoration of nano-sized Cu-BDC MOFs over GrO and CNT platforms; whereas, EDS and XPS analysis confirmed the presence of all components in the hybrid nanocomposites. Bisphenol A was used in this study as a model organic pollutant that is sometimes present in the industrial wastewater to test the adsorption capacity of the prepared hybrid nanomaterials toward their removal from water. The hybrid nanomaterials showed remarkable adsorption capacity of 182.2 and 164.1 mg/g toward the removal of BPA, which was several times higher than that of 60.2 mg/g for Cu-BDC MOF itself. The Langmuir, Freundlich, Temkin and D-R isotherm models were applied to analyze the experimental data and the results revealed that the Freundlich model describes the experimental data best. A kinetic study was carried out and it showed that the prepared nanomaterials could remove maximum amount of BPA from water in 30 min. The pseudo-first order, pseudo-second order and intra-particle diffusion models were applied to evaluate the kinetic data and the results suggested that the kinetics data could be well fitted to the pseudo-second order kinetic model. Additionally, the BAP adsorption process onto the hybrid nanocomposites was spontaneous and exothermic. The π-π interactions between the BPA and hybrid nanomaterials played a vital role during the BPA adsorption process. The higher adsorption capacity and water stability makes them a good candidate for water remediation applications.

17.
Nanoscale Adv ; 1(8): 2953-2964, 2019 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-36133620

RESUMO

Herein, we report a facile method for the synthesis of platinum nanoparticles (PtNPs) about 2.25 nm in size by heating a solution of chloroplatinic acid and sodium rhodizonate. The PtNPs were synthesized in about 5 min. The PtNPs were supported on macroporous cellulose fibers that were obtained from Kimwipe paper (KWP). The cellulose fiber-supported PtNPs (PtNPs@KWP) exhibited excellent catalytic activity towards the reduction of organic pollutants [e.g. methyl orange (MO)] in the presence of hydrogen (H2) gas and formic acid (FA). FA and H2 gas were utilized as clean and alternative reducing agents. The reduction of MO was performed in two different types of water matrices viz. deionized water (DIW) and simulated fresh drinking water (FDW). In both water matrices, the FA mediated reduction of MO was found to be faster than the H2 gas-bubbled one. The PtNPs@KWP demonstrated excellent cycling stability without leaching the PtNPs or platinum ions into the solution for at least five cycles.

18.
J Drug Deliv ; 2018: 2851579, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30534433

RESUMO

Cationic liposomes with DNA-transportation properties have attracted considerable attention for their ability to deliver medicinal oligonucleotides to mammalian cells. Amongst these are metalloliposomes that use transition metal ions to confer the lipid molecules cationic charge and unique advantages such as redox- and ligand-exchange triggered DNA-release properties. In this study, lipophilic copper (II) and zinc (II) complexes of 1-alkyl-1,4,7-triazacyclononane were prepared to investigate their ability to bind and transfect double stranded DNA with mammalian cells in vitro and in vivo. The copper(II)-surfactant complexes Cu(TACN-C8)2 (1), Cu(TACN-C10)2 (2), Cu(TACN-C12)2 (3), Cu(TACN-C14)2 (4), Cu(TACN-C16)2 (5), and Cu(TACN-C18)2 (6) that comprise ligands that vary in the length of the alkyl group and the zinc (II)-surfactant complex of Zn(TACN-C12)2 (7) were synthesized. The critical micelle concentration (CMC) for 1-7 was measured using fluorescence spectroscopy and an evaluation of the transfection efficiency of the complexes was assessed using the pEGFP-N1 plasmid and HEK 293-T cells. An inverse relationship between DNA transfection efficiency and CMC of the Cu(II) metallosurfactants was observed. The highest transfection efficiency of 38% was observed for Cu(TACN-C12)2 corresponding to the surfactant with dodecyl alkyl chain having a CMC of 50 µM. Further, an in vivo experiment using mice models was conducted to test the Cu(TACN-C12)2 (3) and Zn(TACN-C12)2 (7) metallosurfactants delivering a DNA vaccine designed for protection against leishmaniasis disease and the study revealed that the Cu-lipoplex elicited the production of significantly more T cells than the Zn-lipoplex and the control group in vivo.

19.
Materials (Basel) ; 11(9)2018 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-30205605

RESUMO

Organic semiconductor materials composed of π⁻π stacking aromatic compounds have been under intense investigation for their potential uses in flexible electronics and other advanced technologies. Herein we report a new family of seven π⁻π stacking compounds of silver(I) bis-N-(4-pyridyl) benzamide with varying counterions, namely [Ag(NPBA)2]X, where NPBA is N-(4-pyridyl) benzamine, X = NO3- (1), ClO4- (2), CF3SO3- (3), PF6- (4), BF4- (5), CH3PhSO3- (6), and PhSO3- (7), which form extended π-π stacking networks in one-dimensional (1D), 2D and 3D directions in the crystalline solid-state via the phenyl moiety, with average inter-ring distances of 3.823 Å. Interestingly, the counterions that contain π⁻π stacking-capable groups, such as in 6 and 7, can induce the formation of mesomorphic phases at 130 °C in dimethylformamide (DMF), and can generate highly branched networks at the mesoscale. Atomic force microscopy studies showed that 2D interconnected fibers form right after nucleation, and they extend from ~30 nm in diameter grow to reach the micron scale, which suggests that it may be possible to stop the process in order to obtain nanofibers. Differential scanning calorimetry studies showed no remarkable thermal behavior in the complexes in the solid state, which suggests that the mesomorphic phases originate from the mechanisms that occur in the DMF solution at high temperatures. An all-electron level simulation of the band gaps using NRLMOL (Naval Research Laboratory Molecular Research Library) on the crystals gave 3.25 eV for (1), 3.68 eV for (2), 1.48 eV for (3), 5.08 eV for (4), 1.53 eV for (5), and 3.55 eV for (6). Mesomorphic behavior in materials containing π⁻π stacking aromatic interactions that also exhibit low-band gap properties may pave the way to a new generation of highly branched organic semiconductors.

20.
ACS Omega ; 3(8): 10243-10249, 2018 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-31459153

RESUMO

Our work reports the hydrothermal synthesis of a bimetallic composite CoMoS, followed by the addition of cellulose fibers and its subsequent carbonization under Ar atmosphere (CoMoS@C). For comparison, CoMoS was heat-treated under the same conditions and referred as bare-CoMoS. X-ray diffraction analysis indicates that CoMoS@C composite matches with the CoMoS4 phase with additional peaks corresponding to MoO3 and CoMoO4 phases, which probably arise from air exposure during the carbonization process. Scanning electron microscopy images of CoMoS@C exhibit how the CoMoS material is anchored to the surface of carbonized cellulose fibers. As anode material, CoMoS@C shows a superior performance than bare-CoMoS. The CoMoS@C composite presents an initial high discharge capacity of ∼1164 mA h/g and retains a high specific discharge capacity of ∼715 mA h/g after 200 cycles at a current density of 500 mA/g compared to that of bare-CoMoS of 102 mA h/g. The high specific capacity and good cycling stability could be attributed to the synergistic effects of CoMoS and carbonized cellulose fibers. The use of biomass in the anode material represents a very easy and cost-effective way to improve the electrochemical Li-ion battery performance.

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