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1.
Artigo em Inglês | MEDLINE | ID: mdl-32697564

RESUMO

Laser-deposited carbon aerogel is a low-density porous network of carbon clusters synthesized using a laser process. A one-step synthesis, involving deposition and annealing, results in the formation of a thin porous conductive film which can be applied as a chemiresistor. This material is sensitive to NO2 compared to ammonia and other volatile organic compounds and is able to detect ultra-low concentrations down to at least 10 parts-per-billion. The sensing mechanism, based on the solubility of NO2 in the water layer adsorbed on the aerogel, increases the usability of the sensor in practically relevant ambient environments. A heating step, achieved in tandem with a microheater, allows the recovery to the baseline, making it operable in real world environments. This, in combination with its low cost and scalable production, makes it promising for Internet-of-Things air quality monitoring.

2.
J Am Chem Soc ; 142(30): 12976-12986, 2020 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-32597176

RESUMO

Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino-s-triazine intermediates, which in turn undergo nucleophilic substitutions. This reaction was directed into two dimensions by calcium ions derived from calcium carbide and induced the formation of 2DTSs. The role of calcium ions to direct the two-dimensionality of the final structure was simulated using DFT and further proven by synthesizing molecular intermediates. The water content of the reaction medium was found to be a crucial factor that affected the structure of the products dramatically. While 2DTSs were obtained under anhydrous conditions, a mixture of graphitic material/2DTSs or only graphitic material (GM) was obtained in aqueous solutions. Due to the straightforward and gram-scale synthesis of 2DTSs, as well as their photothermal and photodynamic properties, they are promising materials for a wide range of future applications, including bacteria and virus incapacitation.

3.
ACS Nano ; 2020 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-32347713

RESUMO

We present the analysis of a family of nanotubes (NTs) based on the quaternary misfit layered compound (MLC) YxLa1-xS-TaS2. The NTs were successfully synthesized within the whole range of possible compositions via the chemical vapor transport technique. In-depth analysis of the NTs using electron microscopy and spectroscopy proves the in-phase (partial) substitution of La by Y in the (La,Y)S subsystem and reveals structural changes compared to the previously reported LaS-TaS2 MLC-NTs. The observed structure can be linked to the slightly different lattice parameters of LaS and YS. Raman spectroscopy and infrared transmission measurements reveal the tunability of the plasmonic and vibrational properties. Density-functional theory calculations showed that the YxLa1-xS-TaS2 MLCs are stable in all compositions. Moreover, the calculations indicated that substitution of La by Sc atoms is electronically not favorable, which explains our failed attempt to synthesize these MLC and NTs thereof.

4.
Chemistry ; 2020 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-32104936

RESUMO

The preparation of an MoS2 -polymer carbon nanodot (MoS2 -PCND) hybrid material was accomplished by employing an easy and fast bottom-up synthetic approach. Specifically, MoS2 -PCND was realized by the thermal decomposition of ammonium tetrathiomolybdate and the in situ complexation of Mo with carboxylic acid units present on the surface of PCNDs. The newly prepared hybrid material was comprehensively characterized by spectroscopy, thermal means, and electron microscopy. The electrocatalytic activity of MoS2 -PCND was examined in the hydrogen evolution reaction (HER) and compared with that of the corresponding hybrid material prepared by a top-down approach, namely MoS2 -PCND(exf-fun), in which MoS2 was firstly exfoliated and then covalently functionalized with PCNDs. The MoS2 -PCND hybrid material showed superior electrocatalytic activity toward the HER with low Tafel slope, excellent electrocatalytic stability, and an onset potential of -0.16 V versus RHE. The superior catalytic performance of MoS2 -PCND was rationalized by considering the catalytically active sites of MoS2 , the effective charge/energy-transfer phenomena from PCNDs to MoS2 , and the synergetic effect between MoS2 and PCNDs in the hybrid material.

5.
Angew Chem Int Ed Engl ; 59(14): 5806-5815, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-31903674

RESUMO

Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1 /CeO2 and Rh1 /CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.

6.
Angew Chem Int Ed Engl ; 59(10): 3976-3981, 2020 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-31825548

RESUMO

Molybdenum disulfide nanosheets covalently modified with porphyrin were prepared and fully characterized. Neither the porphyrin absorption nor its fluorescence was notably affected by covalent linkage to MoS2 . The use of transient absorption spectroscopy showed that a complex ping-pong energy-transfer mechanism, namely from the porphyrin to MoS2 and back to the porphyrin, operated. This study reveals the potential of transition-metal dichalcogenides in photosensitization processes.

7.
ACS Catal ; 9(12): 10626-10639, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31840008

RESUMO

Identification of active sites in heterogeneous metal catalysts is critical for understanding the reaction mechanism at the molecular level and for designing more efficient catalysts. Because of their structural flexibility, subnanometric metal catalysts, including single atoms and clusters with a few atoms, can exhibit dynamic structural evolution when interacting with substrate molecules, making it difficult to determine the catalytically active sites. In this work, Pt catalysts containing selected types of Pt entities (from single atoms to clusters and nanoparticles) have been prepared, and their evolution has been followed, while they were reacting in a variety of heterogeneous catalytic reactions, including selective hydrogenation reactions, CO oxidation, dehydrogenation of propane, and photocatalytic H2 evolution reaction. By in situ X-ray absorption spectroscopy, in situ IR spectroscopy, and high-resolution electron microscopy techniques, we will show that some characterization techniques carried out in an inadequate way can introduce confusion on the interpretation of coordination environment of highly dispersed Pt species. Finally, the combination of catalytic reactivity and in situ characterization techniques shows that, depending on the catalyst-reactant interaction and metal-support interaction, singly dispersed metal atoms can rapidly evolve into metal clusters or nanoparticles, being the working active sites for those abovementioned heterogeneous reactions.

8.
ACS Catal ; 9(12): 11530-11541, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31840009

RESUMO

The catalytic subnanometric metal clusters with a few atoms can be regarded as an intermediate state between single atoms and metal nanoparticles (>1 nm). Their molecule-like electronic structures and flexible geometric structures bring rich chemistry and also a different catalytic behavior, in comparison with the single-atom or nanoparticulate counterparts. In this work, by combination of operando IR spectroscopy techniques and electronic structure calculations, we will show a comparative study on Pt catalysts for CO + NO reaction at a very low temperature range (140-200 K). It has been found that single Pt atoms immobilized on MCM-22 zeolite are not stable under reaction conditions and agglomerate into Pt nanoclusters and particles, which are the working active sites for CO + NO reaction. In the case of the catalyst containing Pt nanoparticles (∼2 nm), the oxidation of CO to CO2 occurs in a much lower extension, and Pt nanoparticles become poisoned under reaction conditions because of a strong interaction with CO and NO. Therefore, only subnanometric Pt clusters allow NO dissociation at a low temperature and CO oxidation to occur well on the surface, while CO interaction is weak enough to avoid catalyst poisoning, resulting in a good balance to achieve enhanced catalytic performance.

9.
Nano Lett ; 19(12): 9160-9169, 2019 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-31756108

RESUMO

The one-step seed-mediated synthesis is widely used for the preparation of ferromagnetic metal nanoparticles (NPs) since it offers a good control of particle morphology. Nevertheless, this approach suffers from a lack of mechanistic studies because of the difficulties of following in real time the heterogeneous nucleation and predicting structure effects with seeds that are generated in situ. Here, we propose a complete scheme of the heteronucleation process involved in one-pot seed-mediated syntheses of cobalt nanoparticles in liquid polyols, relying on geometrical phase analysis (GPA) of high-resolution high-angle annular dark field (HAADF)-STEM images and in situ measurements of the molecular hydrogen evolution. Cobalt particles of different shapes (rods, platelets, or hourglass-like particles) were grown by reducing cobalt carboxylate in liquid polyols in the presence of iridium or ruthenium chloride as the nucleating agent. A reaction scheme was established by monitoring the H2 evolution resulting from the decomposition of metal hydrides, formed in situ by ß-elimination of metal alkoxides, and from the polyol dehydrogenation, catalytically activated by the metal particles. This is a very good probe for both the noble metal nucleation and the heterogeneous nucleation of cobalt, showing a good separation of these two steps. Ir and Ru seeds with a size in the range 1-2 nm were found exactly in the center of the cobalt particles, whatever the cobalt particle shape, and high-resolution images revealed an epitaxial growth of the hcp Co on fcc Ir or hcp Ru seeds. The microstructure analysis around the seeds made evident two different ways of relaxing the lattice mismatch between the seeds and the cobalt, with the presence of dislocations around the Ir seeds and compression zones of the cobalt lattice near the Ru seeds. The relationship between the nature of the nucleating agent, the reaction steps, and the microstructure is discussed.

10.
Nanoscale ; 11(39): 18065-18070, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31577322

RESUMO

We describe here the preparation of a novel nanohybrid comprising a two-layer cesium lead bromide nanoplatelet, [CsPbBr3]PbBr4 NPL, containing europium(ii) bromide (EuBr2) nanodots, by ultrasound/heating treatment of toluene dispersions of the CsPbBr3 nanomaterial in the presence of EuBr2 nanodots. The hybrid nanoplatelets exhibit strong excitonic and narrow emission peaks characteristic of ultrathin NPLs at 430 and 436 nm, respectively.

11.
Nanoscale ; 11(34): 16092-16102, 2019 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-31432840

RESUMO

The search for new relatively easy physicochemical methods for the structural identification of carbon nanotubes represents a key challenge. Here, analyzing the experimental data on double-walled carbon nanotubes (DWCNTs) obtained by us and taken from the literature, we have expressed the magnitude of elastic coupling between two tubular walls forming a DWCNT as a simple function dependent not only on DWCNT diameters but also on the difference between the chirality angles of the constituent nanotubes. To get this quite unexpected result, which allows us to relate more precisely the structural parameters of a DWCNT with frequencies of its radial breathing-like modes (RBLM), we have developed a new model for the RBLM dynamics that takes into account a possible deposition of water molecules from ambient air onto the DWCNT surface. The model constructed allows us to predict the higher prevalence of DWCNTs comprising two walls with identical handedness. The application of the results obtained for the identification of DWCNTs is also considered.

12.
Nanoscale ; 11(33): 15550-15560, 2019 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-31393511

RESUMO

Liquid-phase exfoliation (LPE) has been shown to be capable of producing large quantities of high-quality dispersions suitable for processing into subsequent applications. LPE typically requires surfactants for aqueous dispersions or organic solvents with high boiling point. However, they have major drawbacks such as toxicity, aggregation during solvent evaporation or the presence of residues. Here, dispersions of molybdenum disulfide in acetone are prepared and show much higher concentration and stability than predicted by Hansen parameter analysis. Aiming to understand these enhanced properties, the nanosheets were characterised using UV-visible spectroscopy, zeta potential measurements, atomic force microscopy, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and scanning transmission microscopy combined with spatially-resolved electron energy loss spectroscopy. Also, the performance of the MoS2 nanosheets exfoliated in acetone was compared to that of those exfoliated in isopropanol as a catalyst for the hydrogen evolution reaction. The conclusion from the chemical characterisation was that MoS2 nanosheets exfoliated in acetone have an oxygen edge functionalisation, in the form of molybdenum oxides, changing its interaction with solvents and explaining the observed high-quality and stability of the resulting dispersion in a low boiling point solvent. Exfoliation in acetone could potentially be applied as a pretreatment to modify the solubility of MoS2 by edge functionalisation.

13.
Nanoscale ; 11(17): 8073-8090, 2019 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-30994692

RESUMO

Advanced nanomaterials play a prominent role in nanoscience and nanotechnology developments, opening new frontiers in these areas. Among these nanomaterials, due to their unique characteristics and enhanced chemical and physical properties, inorganic nanotubes have been considered one of the most interesting nanostructures. In recent years, important progress has been achieved in the production and study of these nanomaterials, including boron nitride, transition metal dichalcogenide nanotubular structures, misfit-based nanotubes and other hybrid/doped nanotubular objects. This review is devoted to the in-depth analysis of recent studies on the synthesis, atomic structures, properties and applications of inorganic nanotubes and related nanostructures. Particular attention is paid to the growth mechanism of these nanomaterials. This is a crucial point for the challenges ahead related to the mass production of high-quality defect-free nanotubes for a variety of applications.

14.
Nano Lett ; 19(2): 1379-1386, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30645938

RESUMO

Single-crystalline FeCo nanoparticles with tunable size and shape were prepared by co-decomposing two metal-amide precursors under mild conditions. The nature of the ligands introduced in this organometallic synthesis drastically affects the reactivity of the precursors and, thus, the chemical distribution within the nanoparticles. The presence of the B2 short-range order was evidenced in FeCo nanoparticles prepared in the presence of HDAHCl ligands, combining 57Fe Mössbauer, zero-field 59Co ferromagnetic nuclear resonance (FNR), and X-ray diffraction studies. This is the first time that the B2 structure is directly formed during synthesis without the need of any annealing step. The as-prepared nanoparticles exhibit magnetic properties comparable with the ones for the bulk ( Ms = 226 Am2·kg-1). Composite magnetic materials prepared from these FeCo nanoparticles led to a successful proof-of-concept of the integration on inductor-based filters (27% enhancement of the inductance value at 100 MHz).

15.
Chem Commun (Camb) ; 55(11): 1607-1610, 2019 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-30657161

RESUMO

In this work, we will report the generation of Au clusters in a purely siliceous MCM-22 zeolite. The catalytic properties of these Au clusters have been tested for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone (KA-oil). The Au clusters encapsulated in the MCM-22 zeolite are highly active and selective for the oxidation of cyclohexane to KA-oil, which is superior to Au nanoparticles on the same support. These results suggest that Au clusters are highly active for the activation of oxygen to produce radical species.

16.
Nanoscale ; 10(48): 22730-22736, 2018 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-30500037

RESUMO

Supported nanocrystals of original shapes are highly desirable for the development of optimized catalysts; however, conventional methods for the preparation of supported catalysts do not allow shape control. In this work, we have synthesized concave platinum nanocubes exposing {110} crystallographic facets at 20 °C. In the presence of a crystallographically oriented Pt(111) support in the reaction medium, the concave nanocubes grow epitaxially on the support, producing macroscopic nanostructured surfaces. Higher reaction temperature produces a mixture of different nanostructures in solution; however, only the nanostructures growing along the 111 direction are obtained on the Pt(111) support. Therefore, the oriented surface acts as a template for a selective immobilization of specific nanostructures out of a mixture, which can be regarded as an "epitaxial resolution" of an inhomogeneous mixture of nanocrystals. Thus, a judicious choice of the support crystallographic orientation may allow the isolation of original nanostructures that cannot be obtained in a pure form.

18.
J Am Chem Soc ; 140(41): 13488-13496, 2018 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-30222336

RESUMO

Exfoliated semiconducting MoS2 and WS2 were covalently functionalized with 1,2-dithiolane-modified carbon nanodots (CNDs). The newly synthesized CND-MoS2 and CND-WS2 hybrids were characterized by spectroscopic, thermal, and electron microscopy imaging methods. Based on electronic absorption and fluorescence emission spectroscopy, modulation of the optoelectronic properties of TMDs by interfacing with CNDs was accomplished. Electrochemical studies revealed facile oxidation of MoS2 over WS2 in the examined hybrids, suggesting it to be better electron donor. Excited state events, investigated by femtosecond transient absorption spectroscopic studies, revealed ultrafast energy transfer from photoexcited CNDs to both MoS2 and WS2. Interestingly, upon MoS2 photoexcitation, charge transfer from an exciton dissociation path of MoS2 to CNDs, within CND-MoS2, was observed. However, such a process in CND-WS2 was found to be absent due to energetic reasons. The present study highlights the importance of TMD-derived donor-acceptor hybrids in light energy harvesting and optoelectronic applications. Furthermore, the fundamental information obtained from the current results will benefit design strategies and impact the development of additional TMD-based hybrid materials to efficiently manage and perform in electron-transfer processes.

19.
ACS Nano ; 12(9): 9521-9531, 2018 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-30199625

RESUMO

Despite the intensive interest in thin gold nanowires for a variety of technologically important applications, key details of the mechanism of their formation and atomic-scale structure remain unknown. Here we synthesize highly uniform, very long, and ultrathin gold nanowires in a liquid-phase environment and study their nucleation and growth using in situ high-energy synchrotron X-ray diffraction. By controlling the type of solvents, reducing agents, and gold precursor concentration, it is shown that the nucleation and growth of gold nanowires involve the emergence and self-assembly of transient linear gold complexes, respectively. In sharp contrast with the face-centered-cubic bulk gold, the evolved nanowires are found to possess a tetrahedrally close packed structure incorporating distorted icosahedra and larger size coordination polyhedra of the type observed with the room-temperature phase of bulk manganese. We relate the complexes to synergistic effects between the selected precursor and reducing agents that become appreciable over a narrow range of their molar ratios. We attribute the unusual structural state of gold nanowires to geometrical frustration effects arising from the conflicting tendencies of assemblies of metal atoms to evolve toward attaining high atomic packing density while keeping the atomic-level stresses low, ultimately favoring the growth of cylindrical nanowires with a well-defined diameter and atomically smooth surface. Our work provides a roadmap for comprehensive characterization and, hence, better understanding of 1D metallic nanostructures with an unusual atomic arrangement and may have important implications for their synthesis and performance in practical applications.

20.
Angew Chem Int Ed Engl ; 57(32): 10241-10245, 2018 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-29896878

RESUMO

Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close-packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low-index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.

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