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1.
Angew Chem Int Ed Engl ; 63(6): e202314217, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-37844013

RESUMO

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia 3 ‾ ${\bar{3}}$ d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

2.
Small ; 18(7): e2107006, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-35006648

RESUMO

A new synthetic approach for tunable mesoporous metal-organic frameworks (MeMs) is developed. In this approach, mesopores are created in the process of heat conversion of highly mosaic metal-organic framework (MOF) crystals with non-interpenetrated low-density nanocrystallites into MOF crystals with two-fold interpenetrated high-density nanocrystallites. The two-fold interpenetration reduces the volume of the nanocrystallites in the mosaic crystal, and the accompanying localized agglomeration of the nanocrystallites results in the formation of mesopores among the localized crystallite agglomerates. The pore size can be easily modulated from 7 to 90 nm by controlling the heat treatment conditions, that is, the aging temperature and aging time. Various proteins can be encapsulated in the MeM, and immobilized enzymes show catalyst activity comparable to that of the free native enzymes. Immobilized ß-galactosidase is recyclable and the enzyme activity of the immobilized catalase is maintained after exposure to high temperatures and various organic solvents.


Assuntos
Enzimas Imobilizadas , Estruturas Metalorgânicas , Catálise , Enzimas Imobilizadas/metabolismo , Estruturas Metalorgânicas/química , Temperatura
3.
Angew Chem Int Ed Engl ; 61(8): e202114539, 2022 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-34913234

RESUMO

We reported mesoporosity engineering as a general strategy to promote semihydrogenation selectivity of palladium (Pd)-based nanobundles catalysts. The best mesoporous PdP displayed full conversion, remarkable activity, excellent selectivity, and high stability in semihydrogenation of 1-phenyl-1-propyne, all of which are remarkably better than commercial Lindlar catalysts. Mechanistic investigations ascribed high semihydrogenation selectivity to the continuous crystalline framework and penetrated mesoporous channel of catalysts that weakened the adsorption and interaction capacity of alkenes and thus inhibited over-hydrogenation of alkenes to industrially unfavorable alkanes. Density functional theory calculations further demonstrated that convex crystalline mesoporosity of nanobundles catalysts electronically optimized the coordination environment of Pd active sites and energetically changed hydrogenation trends, resulting in a superior semihydrogenation selectivity to targeted alkenes.

4.
Angew Chem Int Ed Engl ; 61(41): e202210434, 2022 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-35947114

RESUMO

We report a method to prepare core-shell zeolite beta (*BEA) with an aluminous core and an epitaxial Si-rich shell. This method capitalizes on the inherent defects in *BEA crystals to simultaneously passivate acid sites on external surfaces and increase intracrystalline mesoporosity through facile post-hydrothermal synthesis modification in alkaline media. This process creates more hydrophobic materials by reducing silanol defects and enriching the shell in silica via a combination of dealumination and the relocation of silica from the core to the shell during intracrystalline mesopore formation. The catalytic consequences of *BEA core-shells relative to conventional analogues were tested using the biomass conversion of levulinic acid and n-butanol to n-butyl levulinate as a benchmark reaction. Our findings reveal that siliceous shells and intracrystalline mesopores synergistically enhance the performance of *BEA catalysts.

5.
Molecules ; 26(9)2021 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-34067110

RESUMO

A new and simple method, based entirely on a physical approach, was proposed to produce activated carbon from longan fruit seed with controlled mesoporosity. This method, referred to as the OTA, consisted of three consecutive steps of (1) air oxidation of initial microporous activated carbon of about 30% char burn-off to introduce oxygen surface functional groups, (2) the thermal destruction of the functional groups by heating the oxidized carbon in a nitrogen atmosphere at a high temperature to increase the surface reactivity due to increased surface defects by bond disruption, and (3) the final reactivation of the resulting carbon in carbon dioxide. The formation of mesopores was achieved through the enlargement of the original micropores after heat treatment via the CO2 gasification, and at the same time new micropores were also produced, resulting in a larger increase in the percentage of mesopore volume and the total specific surface area, in comparison with the production of activated carbon by the conventional two-step activation method using the same activation time and temperature. For the activation temperatures of 850 and 900 °C and the activation time of up to 240 min, it was found that the porous properties of activated carbon increased with the increase in activation time and temperature for both preparation methods. A maximum volume of mesopores of 0.474 cm3/g, which accounts for 44.1% of the total pore volume, and a maximum BET surface area of 1773 m2/g was achieved using three cycles of the OTA method at the activation temperature of 850 °C and 60 min activation time for each preparation cycle. The two-step activation method yielded activated carbon with a maximum mesopore volume of 0.270 cm3/g (33.0% of total pore volume) and surface area of 1499 m2/g when the activation temperature of 900 °C and a comparable activation time of 240 min were employed. Production of activated carbon by the OTA method is superior to the two-step activation method for better and more precise control of mesopore development.


Assuntos
Ar , Carvão Vegetal/química , Temperatura , Biomassa , Carbono/química , Dióxido de Carbono/química , Modelos Moleculares , Nitrogênio/química , Oxirredução , Porosidade , Sementes/química , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Termogravimetria
6.
Angew Chem Int Ed Engl ; 60(39): 21242-21249, 2021 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-34378296

RESUMO

Mesoporous carbon nitrides with C3 N5 and C3 N6 stoichiometries created a new momentum in the field of organic metal-free semiconductors owing to their unique band structures and high basicity. Here, we report on the preparation of a novel graphitic microporous carbon nitride with a tetrazine based chemical structure and the composition of C3 N5.4 using ultra-stable Y zeolite as the template and aminoguanidine hydrochloride, a high nitrogen-containing molecule, as the CN precursor. Spectroscopic characterization and density functional theory calculations reveal that the prepared material exhibits a new molecular structure, which comprises two tetrazines and one triazine rings in the unit cell and is thermodynamically stable. The resultant carbon nitride shows an outstanding surface area of 130.4 m2 g-1 and demonstrates excellent CO2 adsorption per unit surface area of 47.54 µmol m-2 , which is due to the existence of abundant free NH2 groups, basic sites and microporosity. The material also exhibits highly selective sensing over water molecules (151.1 mmol g-1 ) and aliphatic hydrocarbons due to its unique microporous structure with a high amount of hydrophilic nitrogen moieties and recognizing ability towards small molecules.

7.
Angew Chem Int Ed Engl ; 60(51): 26622-26629, 2021 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-34463010

RESUMO

Lithium-sulfur (Li-S) batteries are regarded as a promising next-generation system for advanced energy storage owing to a high theoretical energy density of 2600 Wh kg-1 . However, the practical implementation of Li-S batteries has been thwarted by the detrimental shuttling behavior of polysulfides, and the sluggish kinetics in electrochemical processes. Herein, a novel single atom (SA) catalyst with oversaturated Fe-N5 coordination structure (Fe-N5 -C) is precisely synthesized by an absorption-pyrolysis strategy and introduced as an effective sulfur host material. The experimental characterizations and theoretical calculations reveal synergism between atomically dispersed Fe-N5 active sites and the unique carbon support. The results exhibit that the sulfur composite cathode built on the Fe-N5 -C can not only adsorb polysulfides via chemical interaction, but also boost the redox reaction kinetics, thus mitigating the shuttle effect. Meanwhile, the robust three-dimensional nitrogen doped carbon nanofiber with large surface area, and high porosity enables strong physical confinement and fast electron/ion transfer process. Attributed to such unique features, Li-S batteries with S/Fe-N5 -C composite cathode realize outstanding cyclability and rate capability, as well as high areal capacities under raised sulfur loading, which demonstrates great potential in developing advanced Li-S batteries.

8.
Angew Chem Int Ed Engl ; 59(13): 5092-5101, 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-31886942

RESUMO

Developing superior electrocatalysts for formic acid oxidation (FAO) is the most crucial step in commercializing direct formic acid fuel cells. Herein, we electrodeposited palladium membranes with periodically ordered mesoporosity obtained by asymmetrically replicating the bicontinuous cubic phase structure of a lyotropic liquid-crystal template. The Pd membrane with the largest periodicity and highest degree of order delivered up to 90.5 m2 g-1 of electrochemical active surface area and 3.34 A mg-1 electrocatalysis capability towards FAO, 3.8 and 7.8 times the values of the commercial Pd/C catalyst, respectively. By controlling the temperature and potential of the electrodeposition procedure, the periodicity area and order degree of the mesoporosity are highly tunable. These Pd membranes gave prototype formic acid fueled cells with 4.3 and 2.4 times the maximum current and power density of the commercial Pd/C catalyst.

9.
J Cell Physiol ; 234(5): 6696-6708, 2019 05.
Artigo em Inglês | MEDLINE | ID: mdl-30341892

RESUMO

Alkaptonuria (AKU) is a disease caused by a deficient homogentisate 1,2-dioxygenase activity leading to systemic accumulation of homogentisic acid (HGA), that forms a melanin-like polymer that progressively deposits onto connective tissues causing a pigmentation called "ochronosis" and tissue degeneration. The effects of AKU and ochronotic pigment on the biomechanical properties of articular cartilage need further investigation. To this aim, AKU cartilage was studied using thermal (thermogravimetry and differential scanning calorimetry) and rheological analysis. We found that AKU cartilage had a doubled mesopore radius compared to healthy cartilage. Since the mesoporous structure is the main responsible for maintaining a correct hydrostatic pressure and tissue homoeostasis, drastic changes of thermal and rheological parameters were found in AKU. In particular, AKU tissue lost its capability to enhance chondrocytes metabolism (decreased heat capacity) and hence the production of proteoglycans. A drastic increase in stiffness and decrease in dissipative and lubricant role ensued in AKU cartilage. Multiphoton and scanning electron microscopies revealed destruction of cell-matrix microstructure and disruption of the superficial layer. Such observations on AKU specimens were confirmed in HGA-treated healthy cartilage, indicating that HGA is the toxic responsible of morphological and mechanical alterations of cartilage in AKU.


Assuntos
Alcaptonúria/tratamento farmacológico , Condrócitos/efeitos dos fármacos , Ácido Homogentísico/farmacologia , Ocronose/tratamento farmacológico , Alcaptonúria/metabolismo , Cartilagem Articular/efeitos dos fármacos , Cartilagem Articular/metabolismo , Condrócitos/metabolismo , Humanos , Oxirredução/efeitos dos fármacos , Pigmentação/efeitos dos fármacos
10.
Molecules ; 23(11)2018 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-30453620

RESUMO

The development of powerful synthetic methodologies is paramount in the design of advanced nanostructured materials. Owing to its remarkable properties and low cost, nanostructured TiO2 is widely investigated for applications such as photocatalysis, energy conversion or energy storage. In this article we report the synthesis of mesoporous TiO2 by three different non-hydrolytic sol-gel routes, and we investigate the influence of the synthetic route and of the presence and nature of the solvent on the structure, texture and morphology of the materials. The first route is the well-known ether route, based on the reaction of TiCl4 with iPr2O. The second and third routes, which have not been previously described for the synthesis of mesoporous TiO2, involve the reaction of Ti(OiPr)4 with stoichiometric amounts of acetophenone and benzoic anhydride, respectively. All materials are characterized by XRD, N2 physisorption and SEM. By playing with the non-hydrolytic route used and the reaction conditions (presence of a solvent, nature of the solvent, calcination), it is possible to tune the morphology and texture of the TiO2. Depending on the reaction conditions, a large variety of mesoporous TiO2 nanostructures could be obtained, resulting from the spontaneous aggregation of TiO2 nanoparticles, either rounded nanoparticles, platelets or nanorods. These nanoparticle networks exhibited a specific surface area up to 250 m² g-1 before calcination, or up to 110 m² g-1 after calcination.


Assuntos
Géis/química , Nanopartículas/química , Titânio/química , Catálise , Nanopartículas/ultraestrutura , Nitrogênio , Porosidade , Difração de Raios X
11.
Nano Lett ; 16(4): 2159-67, 2016 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-26918518

RESUMO

In the past decade, nanomaterials have made their way into a variety of technologies in solar energy, enhancing the performance by taking advantage of the phenomena inherent to the nanoscale. Recent examples exploit plasmonic core/shell nanoparticles to achieve efficient direct steam generation, showing great promise of such nanoparticles as a useful material for solar applications. In this paper, we demonstrate a novel technique for fabricating bimetallic hollow mesoporous plasmonic nanoshells that yield a higher solar vapor generation rate compared with their solid-core counterparts. On the basis of a combination of nanomasking and incomplete galvanic replacement, the hollow plasmonic nanoshells can be fabricated with tunable absorption and minimized scattering. When exposed to sun light, each hollow nanoshell generates vapor bubbles simultaneously from the interior and exterior. The vapor nucleating from the interior expands and diffuses through the pores and combines with the bubbles formed on the outer wall. The lack of a solid core significantly accelerates the initial vapor nucleation and the overall steam generation dynamics. More importantly, because the density of the hollow porous nanoshells is essentially equal to the surrounding host medium these particles are much less prone to sedimentation, a problem that greatly limits the performance and implementation of standard nanoparticle dispersions.

12.
J Anal Appl Pyrolysis ; 121: 62-66, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27695151

RESUMO

The effect of pyrolysis rate on the properties of alginic acid-derived carbonaceous materials, termed Starbon®, was investigated. Thermal Gravimetry-IR was used to prepare porous carbons up to 800 °C at several rates and highlighted increased CO2 production at higher pyrolysis rates. N2 porosimetry of the resultant carbons shows how pyrolysis rate affects both the mesopore structure and thus surface area and surface energy. Surface capacity of these carbons was analysed by methylene blue dye adsorption. In general, as the rate of pyrolysis increased, the mesopore content and adsorbent capacity decreased. It is considered here that the rapid production of volatiles at these higher rates causes structural collapse of the non-templated pore network. The work here demonstrates that pyrolysis rate is a key variable which needs to be controlled to maximise the textural properties of Starbon® required for adsorption applications.

13.
New Phytol ; 205(3): 1277-1287, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25377686

RESUMO

In order to progress in the understanding of mechanical stress generation, the mesoporosity of the cell wall and its changes during maturation of poplar (Populus deltoides × P. nigra) tension wood (TW) and opposite wood (OW) were measured by nitrogen adsorption-desorption. Variations in the thickness of the gelatinous layer (G-layer) were also measured to clarify whether the mesoporosity change simultaneously with the deposition of the G-layer in TW. Results show that mesoporous structures of TW and OW were very similar in early development stages before the deposition of G-layers. With the formation of the S2 layer in OW and the G-layer in TW, the mesopore volume decreased steeply before lignification. However, in TW only, the decrease in mesopore volume occurred together with the pore shape change and a progressive increase in pore size. The different patterns observed in TW revealed that pores from G-layers appear with a different shape compared to those of the compound middle lamella, and their size increases during the maturation process until stabilising in mature wood. This observation strongly supports the hypothesis of the swelling of the G-layer matrix during maturation as the origin of maturation stress in poplar tension wood.


Assuntos
Câmbio/fisiologia , Estresse Mecânico , Árvores/fisiologia , Madeira/fisiologia , Parede Celular/fisiologia , Cruzamentos Genéticos , Modelos Biológicos , Populus , Porosidade
14.
Angew Chem Int Ed Engl ; 54(10): 2888-910, 2015 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-25521805

RESUMO

Cellulose nanocrystals (CNCs), known for more than 50 years, have attracted attention because of their unique properties such as high specific strength and modulus, high surface area, and fascinating optical properties. Just recently, however, their potential in supramolecular templating was identified by making use of their self-assembly behavior in aqueous dispersions in the presence of compatible precursors. The combination of the mesoporosity, photonic properties, and chiral nematic order of the materials, which are available as freestanding films, has led to a significant number of interesting and promising discoveries towards new functional materials. This Review summarizes the use of cellulose derivatives, especially CNCs, as novel templates and gives an overview of the recent developments toward new functional materials.

15.
Pharmaceutics ; 15(2)2023 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-36839857

RESUMO

Hierarchical zeolites are aluminosilicates with a crystal structure, which next to the micropores possess secondary porosity in the range of mesopores and/or small macropores. Due to their ordered structure and additional secondary porosity, they have aroused great interest among scientists in recent years. Therefore, the present work concerns the synthesis and characterization of hierarchical zeolites with secondary mesoporosity, based on commercial zeolites such as MFI (ZSM-5), BEA (ß) and FAU (Y), and modified with polysaccharides such as inulin, hyaluronic acid, and heparin. All materials were characterized by various analytical techniques and applied as a platform for delivery of selected drug molecules. On the basis of X-ray diffraction (presence of reflections in the 2θ angle range of 1.5-2.5°) and low-temperature nitrogen sorption isotherms (mixture of isotherms of I and IV type) additional secondary porosity was found in the mesopore range. Additional tests were also conducted to determine the possibility of loading selected molecules with biological activity into the aforementioned materials and then releasing them in the therapeutic process. Molecules with different therapeutic options were selected for testing, namely ibuprofen, curcumin, and ferulic acid with anti-inflammatory, potentially anticancer, antioxidant, and skin discoloration activities, respectively. Preliminary studies have confirmed the possibility of using hierarchical zeolites as potential carriers for bioactive molecules, as the loading percentage of active substances ranged from 39-79% and cumulative release for ibuprofen reached almost 100% after 8 h of testing.

16.
Heliyon ; 9(2): e13500, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36846672

RESUMO

Formation of activated carbon from petroleum coke by KOH, results in high specific surface area materials that are predominantly microporous. This initial microporosity means that the adsorption kinetics of target species are not as rapid as they could be, thus limiting environmental remediation applications for the material. To address this problem a series of additional heat cycles with no additional chemical inputs were applied after activation but prior to the removal of activating agents. This process resulted in the oxidation of residual potassium metal from the initial activation which allows it to function again as an activating agent for the subsequent cycles. The heat cycling resulted in an increase in mesoporosity by 10-25% with each successive cycle independent of the KOH to feedstock ratio. This was shown to be demonstrably different than equivalently extended heating times, thus identifying the importance of thermal cycling. Adsorption kinetics of three model naphthenic acids showed faster kinetics for the pore widened activated carbon. The t1/2 times dropped from 20 to 6.6 min for diphenyl acetic acid, 34.3 to 4.5 min for cyclohexane acetic acid, and 51.4 to 12.0 min for heptanoic acid.

17.
Polymers (Basel) ; 15(13)2023 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-37447451

RESUMO

Up to now, the use of TiO2 has been considered a promising advanced technology for organic pollutants removal from air or water, since it has high biological and chemical stability, high photoactivity, low toxicity, and low-cost production. However, there are issues to be addressed in enhancing TiO2 performance, and one of the current key issues is redesigning UV-active photocatalysts and making them active in the visible region of the electromagnetic spectrum. This way, solar light absorption will be insured, and thus, a more efficient photocatalyst could be obtained. For this reason, conjugated polymers and their derivatives are considered to act as photosensitizers, being able to shift the TiO2 activity from the UV to the visible region. Therefore, this study focuses on the synthesis of TiO2/conjugated polymer systems, which was accomplished by the deposition of poly-3,4-ethylene-dioxy-thiophene (PEDOT [-C6H4O2S-]n), a low-band semiconductor with an excellent stability due to its extending π-conjugated electron system, on titania nanoarchitecture. First of all, a TiO2 nanoarchitecture was synthesized by an ultrasound-assisted sol-gel method. Then, TiO2/PEDOT systems were obtained and characterized by using different techniques such as X-ray diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, UV-Vis diffuse reflectance, and N2 sorption measurements. The synthesized composites confirmed their mesoporosity and lower band gap values compared to bare titania, which clearly shows the ability to work as photocatalysts under visible-light activity. Further, we demonstrated that an organic pollutant, Congo Red dye, used as a model molecule could be photodegraded with the synthesized TiO2/PEDOT systems, with efficiencies of up to 95% in the case of TconvPEDOT under UV light and up to 99% for TconvPEDOT under visible-light irradiation, accomplishing in this way a successful synthesis of visible-light-activated titania photocatalyst.

18.
Appl Biochem Biotechnol ; 195(5): 3456-3476, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36598642

RESUMO

Boronate affinity ligands (BALs) have gained attention for glycoproteins capture and recognition due to their unique affinity interaction with glycans. In this paper, the effect of azo immobilization of phenylboronic acid on the reduction of adsorption pH of a recombinant glycoprotein (i.e., rhEPO) on hydrogel microparticles was investigated. To evaluate the influence of intraparticle porosity on protein adsorption, microporous (MicroBead) and mesoporous (MesoBead) agarose beads carrying two levels of amine densities were functionalized with azoboronate ligand. Affinity adsorption of the glycoprotein during static and dynamic adsorptions at relatively low pHs of 8 and 7 was studied. Results revealed successful adsorption of rhEPO at pH = 8 through affinity capture of glycans by azoboronate ligands. Increased amine density provided 1.1 and 1.5 times higher static adsorption capacities and dynamic performance efficiencies, respectively. In addition, adsorption capacities and initial adsorption rates of rhEPO on MesoBeads were respectively 1.4 and 2.5-2.8 times of MicroBeads. Also, at pH = 8, MesoBeads recorded higher dynamic recoveries (59 and 91%) compared with microporous ones (46 and 69%) since mesoporosity facilitates intraparticle mass transfer. Reduction of binding pH from 8 to 7 resulted in a sharp decrease in dynamic recovery (14%), indicating the appropriate binding pH of azoPBA to be above 7. The azoboronate affinity ligand is a leading candidate for capturing glycoproteins at relatively low pH. Also, mesoporous microparticles are appropriate tools in more efficient medium-sized protein binding applications.


Assuntos
Eritropoetina , Hidrogéis , Humanos , Adsorção , Aminas , Glicoproteínas , Ligantes , Proteínas Recombinantes , Sefarose , Compostos Azo/química , Porosidade , Compostos de Boro/química
19.
Nanomaterials (Basel) ; 13(4)2023 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-36839054

RESUMO

TiO2/montmorillonite composites were synthesized using inverse micellar route for the preparation of titania nanoparticles (4-6 nm diameter) in 1-hexanol and for the dispersion of one of the clay components. Two series of composites were obtained: one derived from cetyltrimethylammonium organomontmorillonite (CTA-Mt), exfoliated in 1-hexanol, and the other from sodium form of montmorillonite (Na-Mt) dispersed by formation of an inverse microemulsion in 1-hexanol. The TiO2 content ranged from 16 to 64 wt.%. The composites were characterized with X-ray diffraction, scanning/transmission electron microscopy/energy dispersive X-ray spectroscopy, thermal analysis, and N2 adsorption-desorption isotherms. The Na-Mt-derived component was shown to undergo transformation to CTA-Mt, as indicated by basal spacing of 17.5 nm, due to the interaction with the CTABr surfactant in inverse microemulsion. It was also better dispersed and intermixed with TiO2 nanoparticles. As a result, the TiO2/Na-Mt series displayed superior textural properties, with specific surface area up to 256 m2g-1 and pore volume up to 0.247 cm3g-1 compared with 208 m2g-1 and 0.231 cm3g-1, respectively, for the TiO2/CTA-Mt counterpart. Members of both series were uniformly mesoporous, with the dominant pore size around 5 nm, i.e., comparable with the dimensions of titania nanoparticles. The advantage of the adopted synthesis method is discussed in the context of other preparative procedures used for manufacturing of titania-clay composites.

20.
Nanomaterials (Basel) ; 12(11)2022 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-35683760

RESUMO

Nanocrystalline layer-structured monoclinic Na2Ti3O7 is currently under consideration for usage in solid state electrolyte applications or electrochemical devices, including sodium-ion batteries, fuel cells, and sensors. Herein, a facile one-pot hydrothermal synthetic procedure is developed to prepare self-assembled moss-like hierarchical porous structure constructed by ultrathin Na2Ti3O7 nanotubes with an outer diameter of 6-9 nm, a wall thickness of 2-3 nm, and a length of several hundred nanometers. The phase and chemical transformations, optoelectronic, conductive, and electrochemical properties of as-prepared hierarchically-organized Na2Ti3O7 nanotubes have been studied. It is established that the obtained substance possesses an electrical conductivity of 3.34 × 10-4 S/cm at room temperature allowing faster motion of charge carriers. Besides, the unique hierarchical Na2Ti3O7 architecture exhibits promising cycling and rate performance as an anode material for sodium-ion batteries. In particular, after 50 charge/discharge cycles at the current loads of 50, 150, 350, and 800 mA/g, the reversible capacities of about 145, 120, 100, and 80 mA∙h/g, respectively, were achieved. Upon prolonged cycling at 350 mA/g, the capacity of approximately 95 mA∙h/g at the 200th cycle was observed with a Coulombic efficiency of almost 100% showing the retention as high as 95.0% initial storage. At last, it is found that residual water in the un-annealed nanotubular Na2Ti3O7 affects its electrochemical properties.

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