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Amine intercalated titanates were synthesized by direct exchange of potassium ions of K2Ti4O9 by alkyl ammonium ions of various alkyl chain lengths. These intercalated solids exfoliate well in alcohols of different alkyl chain lengths and non-polar solvents such as toluene and hexane to yield colloidal dispersions of titanate nanosheets. The longer the alkyl chain of the intercalated amine the better the exfoliation of the intercalated titanate in long chain alcohols and non-polar solvents. While non-uniform rectangular nanosheets were obtained when aggressive sonication was employed for exfoliating the solids, nanoribbons were obtained when the exfoliation was carried out by gently stirring the solids in the solvent.
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Porous hexagonal nanoplatelets of mixed metal oxide (MMO) derived from the calcination of MgAl layered double hydroxide exhibits a CO2 sorption capacity of 1.99 mmol g-1 at 30 °C, with a retention of 87% sorption capacity over 10 carbonation-decarbonation cycles and a CO2 sorption capacity of 1 mmol g-1 at 200 °C with a 40% increase in capacity over 10 cycles. The high sorption capacity is attributed to the porous nanoplatelet structure of the MMO with a BET surface area of 115 m2 g-1, which enables increased CO2 diffusion. Upon partially replacing magnesium with calcium (33, 50 and 66 mol%), the CO2 sorption capacity of the MMO increases with an increase in temperature. MMO derived from LDH, in which 66% of magnesium is replaced by calcium (MgCaAl-66), delivers CO2 sorption capacities of 1.38, 1.31, 2.50, 4.85 and 7.75 mmol g-1 at 200, 300, 350, 400 and 600 °C, respectively, which is significant for application in the sorption-enhanced water gas shift (SEWGS) process. MgCaAl-66 MMO exhibits a sorption capacity of 1 mmol g-1, which is stable over 10 cycles at 200 °C, and a sorption capacity of 3.68 mmol g-1 at 400 °C with 85% capture efficiency retention over 10 cycles. While the incorporation of Ca2+ serves multiple purposes such as increasing basic defect sorption sites and improving stability to repress the sintering-induced limitation of MMO over sorption cycles, the porous nanoplatelets act as individual sorbent units resisting volume changes through carbonation-decarbonation cycles.
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Anion exchange reactions with several monovalent anions and a divalent sulfate anion could be successfully carried out on 3R2 polytype of magnesium aluminum LDH containing interlayer carbonate ions by refluxing the carbonate-LDH in 1-butanol with ammonium salt of the desired anion. The reaction was similar to what was observed in the case of 3R1 polytype (Bhojaraj et al., ACS Omega 2019, 4, 20072-20079) in that here too the reaction occurs topotactically resulting in 3R2 polytypes of LDHs in the cases of chloride and bromide anions. However, the reaction is much slower here demanding longer reaction times and/or higher amounts of ammonium salt of the anion. These exchange reactions pave the way for the synthesis of well-defined, hitherto unknown, 3R2 polytypes of magnesium aluminum LDH with chloride and bromide as interlayer anions.
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Mg-Al layered double hydroxide (MgAl-LDH) exhibits selectivity in the intercalation of amino acids (AAs). When the MgAl-LDH derived mixed metal oxide was treated with different mixtures of AAs, preferential sorption of one AA over the other(s) was observed as indicated by XRD analysis of the products and HPLC analysis of the interlayer AA contents in the products. The order of preference was aspartic acid, glutamic acid (acidic AAs) > glycine, alanine (neutral AAs) > hystidine, and arginine (basic AAs). Among the acidic AAs, aspartic acid was preferred over glutamic acid and among the basic AAs, histidine was preferred over arginine. LDH shows equal preference for glycine and alanine. The selectivity can be explained on the basis of the isoelectric pH (pI) of the AA. A similar selectivity order was obtained when the mixtures of AAs were treated with nitrate-intercalated LDH (direct anion exchange) although the net AA intercalated is much lower due to competition with carbonate derived from atmospheric CO2. The high selectivity observed in some cases (such as aspartic acid and glycine) would result in the quantitative separation of the individual AAs from their mixture.
Assuntos
Aminoácidos , Ácido Aspártico , Alanina , Arginina , Glutamatos , Glicina , Hidróxidos/química , MagnésioRESUMO
Macroporous TiO2 monoliths were synthesized by self-sustained combustion reactions of molded pellets made up of a mixture of TiCl4 as a precursor, urea as a fuel, ammonium nitrate as an oxidizer, and starch as a binder. The porous TiO2 monoliths were found to be a heterostructure of anatase and rutile phases, in addition to being doped with carbon. Variation in the amount of starch yielded porous monoliths of different anatase-rutile ratios (increasing rutile component from 0 to 40%) but comparable Brunauer-Emmett-Teller (BET) surface area (â¼30 m2 g-1). The porous monoliths obtained, where the TiCl4/starch mass ratio was 2.17, exhibit exceptional photocatalytic activity in the degradation of dyes (methylene blue and methyl orange) and selective oxidation of benzyl alcohol to benzaldehyde under natural sunlight. The synergistic combination of high surface area, porous network, lowered band gap due to heterostructured anatase-rutile polymorphs, and the presence of doped carbon renders the macroporous TiO2 an efficient photocatalyst.
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Pristine and Co-doped MoS2 nanosheets, containing a dominant 1T phase, have been densified by spark plasma sintering (SPS) to produce a nanostructured arrangement. The structural analysis by X-ray powder diffraction revealed that the reactive sintering process transforms the 1T-MoS2 nanosheets into their stable 2H form despite a significantly reduced sintering temperature and time testifying to the fast kinetics of phase change. Together with the phase conversion, the SPS process promoted a strong texturing of the nanosheets, which drives additional scattering processes and alters the electronic and thermal transport properties. In the pristine sample, it produced one of the lowest thermal conductivities ever reported on MoS2 with a minimal value of 0.66 W/m·K at room temperature. The effect of Co substitution in the final sintered samples is not significant, compared to the pristine MoS2 sample, except for a non-negligible improvement of the electrical conductivity by a factor of 100 in the high-Co content (6% by mass) sample.
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In this work, a series of Bi2Te3/X mol% MoS2 (X = 0, 25, 50, 75) bulk nanocomposites were prepared by hydrothermal reaction followed by reactive spark plasma sintering (SPS). X-ray diffraction analysis (XRD) indicates that the native nanopowders, comprising of Bi2Te3/MoS2 heterostructure, are highly reactive during the electric field-assisted sintering by SPS. The nano-sized MoS2 particles react with the Bi2Te3 plates matrix forming a mixed-anion compound, Bi2Te2S, at the interface between the nanoplates. The transport properties characterizations revealed a significant influence of the nanocomposite structure formation on the native electrical conductivity, Seebeck coefficient, and thermal conductivity of the initial Bi2Te3 matrix. As a result, enhanced ZT values have been obtained in Bi2Te3/25 mol% MoS2 over the temperature range of 300-475 K induced mainly by a significant increase in the electrical conductivity.
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A layered titanate, K2Ti4O9, is intercalated with various n-alkylamines through ion-exchange reaction in aqueous medium. On heating, the intercalated amine is partially deintercalated, yielding nitrogen-doped amine-intercalated titanates. The modified titanates are studied as catalysts in methylene blue degradation under UV irradiation. Heat-treated long-chain amine titanates exhibit better photocatalytic activity in comparison to short chain amine titanates. The improved catalytic activity could be attributed to two factors: (i) increased surface access as the titanate layers are well separated, pillared by the alkylamine chains and (ii) nitrogen doping.
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Deintercalation of carbonate from layered double hydroxides (LDH) followed by intercalation of another anion (decarbonative intercalation) is a good method for the synthesis of crystalline LDH with different intercalated anions. We have carried out decarbonative intercalation of halides, nitrate, acetate, and sulfate by refluxing the carbonate-LDH with the corresponding ammonium salt in 1-butanol to obtain ordered LDH incorporating the desired anion. The crystallinity of the precursor LDH is retained in the anion-exchanged products, making this reaction a useful tool to prepare ordered LDH containing various anions. In addition, the morphology of the LDH is also retained after the exchange, making the reaction morphotactic. As the reaction is facilitated by the weak acidity of the ammonium salt, just grinding the carbonate-LDH with the ammonium salt of the desired anion also results in anion exchange. However, while the crystallinity of the LDH is retained, the morphology changes possibly due to breaking up of the crystals during the reaction.
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Solvated two-dimensional nanosheets of copper hydroxy dodecylsulfate in 1-butanol react with thiourea under microwave irradiation to yield surfactant-free porous aggregates of CuS nanoparticles. These aggregates exhibit excellent photocatalytic activity toward degradation of methylene blue, methyl orange, and 4-chlorophenol in natural sunlight. While the high surface area (14.74 m2 g-1) and porosity increase the active reaction centers for adsorption and degradation of organic molecules, quantum confinement results in a low recombination of photogenerated electrons and holes. Chemical and photogenerated hydroxyl radicals cause the oxidation of the dyes and 4-chlorophenol.
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Co-doped MoS2 nanosheets have been synthesized through the hydrothermal reaction of ammonium tetrathiomolybdate and hydrazine in the presence of cobalt acetate. These nanosheets exhibit a dominant metallic 1T phase with cobalt ion-activated defective basal planes and S-edges. In addition, the nanosheets are dispersible in polar solvents like water and methanol. With increased active sites, Co-doped MoS2 nanosheets exhibit exceptional catalytic activity in the reduction of nitroarenes by NaBH4 with impressive turnover frequencies of 8.4, 3.2, and 20.2 min-1 for 4-nitrophenol, 4-nitroaniline, and nitrobenzene, respectively. The catalyst is magnetic, enabling its easy separation from the reaction mixture, thus making its recycling and reusability simple and efficient. The enhanced catalytic activity of the Co-doped 1T MoS2 nanosheets in comparison to that of undoped 1T MoS2 nanosheets suggests that incorporation of cobalt ions in the MoS2 lattice is the major reason for the efficiency of the catalyst. The dopant, Co, plays a dual role. In addition to providing active sites where electron transfer is assisted through redox cycling, it renders the nanosheets magnetic, enabling their easy removal from the reaction mixture.
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Layered double hydroxide (LDH)-monodispersed 4-nm CdSe nanoparticle composites were prepared through restacking of layers of colloidally dispersed delaminated LDH in the presence of CdSe nanoparticles in 1-butanol. The composites exhibit a blue shift for CdSe absorption, which increases with a decrease in nanoparticle content. The observed blue shift is due to the interaction of the quantum dots with the LDH layers, which leads to surface modification of the nanoparticles.
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The delamination-restacking behavior of a number of layered double hydroxides (LDHs) differing in [M(II)]/[M(III)] ratio, constituent metal ions and intercalated surfactant anions in different organic solvents has been studied. Colloidal dispersion due to delamination and the stability of the colloid obtained have been found to be not affected much by the nature of the constituent metal ions but increase with increase in the size of the surfactant anion. LDHs with low [M(II)]/[M(III)] ratio delaminate better than the ones with high [M(II)]/[M(III)] ratio. Delamination is best in alcohols such as 1-butanol, 1-hexanol, 1-octanol and 1-decanol, while a little delamination occurs in nonpolar solvents such as hexane. In all the cases, the original layered solid could be obtained through restacking of layers from the colloidal dispersion.
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Co3O4 nanoparticles of 35 nm with a cauliflower-like morphology were obtained when a monolayer colloidal dispersion of dodecyl sulfate intercalated alpha-cobalt hydroxide in butanol was subjected to solvothermal hydrolytic decomposition. The nanogranular particles exhibit weakly ferromagnetic properties in contrast with both bulk and dispersed nanoparticulate Co3O4.
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gamma-Fe2O3 nanocrystals capped with citrate and octylamine have been chemically prepared. The octylamine-capped nanocrystals exhibit a tendency to form ordered lattices. Films of nanocrystals of varying thickness (454, 720, and 1400 microg/cm2 in the case of citrate-capped nanocrystals and 300 microg/cm2 in the case of octylamine-capped nanocrystals) have been prepared on Si(100) substrates by drop casting and have been characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. Magnetic measurements have been carried out on the films as well as on nanocrystal powders. The films of citrate-capped gamma-Fe2O3 nanocrystals exhibit enhanced perpendicular magnetization, with the anisotropy depending on the film thickness.
Assuntos
Compostos Férricos/química , Magnetismo , Nanotecnologia/métodos , Silício/química , Aminas/química , Anisotropia , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Nanotecnologia/instrumentação , Dióxido de Silício/química , Difração de Raios XRESUMO
Dodecyl sulfate and dodecylbenzene sulfonate intercalated alpha-hydroxides of nickel and cobalt were synthesized by ammonia precipitation. These solids delaminate to give a colloidal dispersion of layers in organic solvents such as 1-butanol. The dispersed layers could be reassembled either by evaporation of the colloid or by coagulation by the addition of a polar solvent.
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The preparation of capped metal oxide nanoparticles through the hydrolysis of metal salts is made arduous by the difficulty of dissolving long organic chain capping agents in water; by performing the reaction in propylene glycol under reflux, instead of water, we are able to hydrolyse FeCl3 in the presence of n-octylamine to obtain (repeatedly) soluble, monodisperse approximately 5 nm gamma-Fe2O3 particles that display a tendency to aggregate into superlattices.
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The reaction of ß-Co(OH)2 hexagonal platelets with graphite oxide in an aqueous colloidal dispersion results in the formation of ß-Co(OH)2 hexagonal rings anchored to graphene oxide layers. The interaction between the basic hydroxide layers and the acidic groups on graphene oxide induces chemical etching of the hexagonal platelets, forming ß-Co(OH)2 hexagonal rings. On heating in air or N2, the hydroxide hybrid is morphotactically converted to porous Co3O4/CoO hexagonal ring-graphene hybrids. Porous NiCo2O4 hexagonal ring-graphene hybrid is also obtained through a similar process starting from ß-Ni0.33Co0.67(OH)2 platelets. As electrode materials for supercapacitors or lithium-ion batteries, these materials exhibit a large capacity, high rate capability, and excellent cycling stability.
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WS2 nanoribbons have been synthesized by chemical unzipping of WS2 nanotubes. Lithium atoms are intercalated in WS2 nanotubes by a solvothermal reaction with n-butyllithium in hexane. The lithiated WS2 nanotubes are then reacted with various solvents--water, ethanol, and long chain thiols. While the tubes break into pieces when treated with water and ethanol, they unzip through longitudinal cutting along the axes to yield nanoribbons when treated with long chain thiols, 1-octanethiol and 1-dodecanethiol. The slow diffusion of the long chain thiols reduces the aggression of the reaction, leading to controlled opening of the tubes.
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Recently, we have shown that the graphene-VO2(B) nanotube hybrid is a promising lithium ion battery cathode material (Nethravathi et al. Carbon, 2012, 50, 4839-4846). Though the observed capacity of this material was quite satisfactory, the rate capability was not. To improve the rate capability we wanted to prepare a graphene-VO2(B) hybrid in which the VO2(B) would be built on 2D nanosheets that would enable better electrode-electrolyte contact. Such a material, a N-doped graphene-VO2(B) nanosheet-built 3D flower hybrid, is fabricated by a single-step hydrothermal reaction within a mixture of ammonium vanadate and colloidal dispersion of graphite oxide. The 3D VO2(B) flowers which are uniformly distributed on N-doped graphene are composed of ultrathin 2D nanosheets. When used in lithium ion batteries, this material exhibits a large capacity, high rate capability, and excellent cycling stability. The enhanced performance results from its unique features: excellent electronic conductivity associated with the N-doped graphene, short transportation length for lithium ions related to ultrathin nanosheets, and improved charge transfer due to the anchoring of the VO2(B) flowers to N-doped graphene.