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1.
Artigo em Inglês | MEDLINE | ID: mdl-32687305

RESUMO

Lithium ion batteries (LIBs) are nowadays widely used in many energy storage devices, which have certain requirements on size, weight and performance. State-of-the-art LIBs operate very reliably and with good performance under restricted and controlled conditions, but lack in efficiency and safety when these conditions are exceeded. In this work, the influence of outranging conditions in terms of charging rate and operating temperature on electrochemical characteristics was studied on the example of lithium titanate (Li4Ti5O12, LTO) electrodes. Structural processes in the electrode, cycled with ultrafast charge and discharge, were evaluated by operando synchrotron powder diffraction and ex situ X-ray absorption spectroscopy. Based on the Rietveld refinement, it was shown, that the electrochemical storage mechanism is based on the Li-intercalation process at least up to current rates of 5C, meaning full battery charge within 12 min. For applications at temperatures between -30 and 60 °C, four carbonate-based electrolyte systems with different additives were tested for cycling performance in half-cells with LTO and metallic lithium as electrodes. It was shown, that the addition of 30 wt.% [PYR14][PF6] to the conventional LP30 electrolyte, usually used in LIBs, significantly decreases its melting point, which enables the successful low-temperature application at least down to -30 °C, in contrast to LP30, which freezes below -10 °C, making battery operation impossible. Moreover, at elevated temperatures up to 60 °C, batteries with the LP30/[PYR14][PF6] electrolyte exhibit stable long-term cycling behavior very close to LP30. Our findings provide a guideline for the application of LTO in LIBs beyond conventional conditions and show how to overcome limitations by designing appropriate electrolytes.

2.
Angew Chem Int Ed Engl ; 59(29): 12048-12054, 2020 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-32315501

RESUMO

As there is a great demand of 2D metal networks, especially out of gold for a plethora of applications we show a universal synthetic method via phase boundary gelation which allows the fabrication of networks displaying areas of up to 2 cm2 . They are transferred to many different substrates: glass, glassy carbon, silicon, or polymers such as PDMS. In addition to the standardly used web thickness, the networks are parametrized by their fractal dimension. By variation of experimental conditions, we produced web thicknesses between 4.1 nm and 14.7 nm and fractal dimensions in the span of 1.56 to 1.76 which allows to tailor the structures to fit for various applications. Furthermore, the morphology can be tailored by stacking sheets of the networks. For each different metal network, we determined its optical transmission and sheet resistance. The obtained values of up to 97 % transparency and sheet resistances as low as 55.9 Ω/sq highlight the great potential of the obtained materials.

3.
ChemSusChem ; 2020 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-32243702

RESUMO

The synthesis of porous electrode materials is often linked with the generation of waste that results from extensive purification steps and low mass yield. In contrast to porous carbons, covalent triazine frameworks (CTFs) display modular properties on a molecular basis through appropriate choice of the monomer. Herein, the synthesis of a new pyridine-based CTF material is showcased. The porosity and nitrogen-doping are tuned by a careful choice of the reaction temperature. An in-depth structural characterization by using Ar physisorption, X-ray photoelectron spectroscopy, and Raman spectroscopy was conducted to give a rational explanation of the material properties. Without any purification, the samples were applied as symmetrical supercapacitors and showed a specific capacitance of 141 F g-1 . Residual ZnCl2 , which acted formerly as the porogen, was used directly as the electrolyte salt. Upon the addition of water, ZnCl2 was dissolved to form the aqueous electrolyte in situ. Thereby, extensive and time-consuming washing steps could be circumvented.

4.
Nat Commun ; 11(1): 1590, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-32221287

RESUMO

Amongst various porous materials, noble metal aerogels attract wide attention due to their concurrently featured catalytic properties and large surface areas. However, insufficient understanding and investigation of key factors (e.g. reductants and ligands) in the fabrication process limits on-target design, impeding material diversity and available applications. Herein, unveiling multiple roles of reductants, we develop an efficient method, i.e. the excessive-reductant-directed gelation strategy. It enables to integrate ligand chemistry for creating gold aerogels with a record-high specific surface area (59.8 m2 g-1), and to expand the composition to all common noble metals. Moreover, we demonstrate impressive electrocatalytic performance of these aerogels for the ethanol oxidation and oxygen evolution reaction, and discover an unconventional organic-ligand-enhancing effect. The present work not only enriches the composition and structural diversity of noble metal aerogels, but also opens up new dimensions for devising efficient electrocatalysts for broad material systems.

5.
Artigo em Inglês | MEDLINE | ID: mdl-32187791

RESUMO

Noble-metal aerogels (NMAs) have drawn increasing attention because of their self-supported conductive networks, high surface areas, and numerous optically/catalytically active sites, enabling their impressive performance in diverse fields. However, the fabrication methods suffer from tedious procedures, long preparation times, unavoidable impurities, and uncontrolled multiscale structures, discouraging their developments. By utilizing the self-healing properties of noble-metal aggregates, the freezing-promoted salting-out behavior, and the ice-templating effect, a freeze-thaw method is crafted that is capable of preparing various hierarchically structured noble-metal gels within one day without extra additives. In light of their cleanliness, the multi-scale structures, and combined catalytic/optical properties, the electrocatalytic and photoelectrocatalytic performance of NMAs are demonstrated, which surpasses that of commercial noble-metal catalysts.

6.
Artigo em Inglês | MEDLINE | ID: mdl-32100543

RESUMO

The material-efficient monolayers of transition-metal dichalcogenides (TMDs) are a promising class of ultrathin nanomaterials with properties ranging from insulating through semiconducting to metallic, opening a wide variety of their potential applications from catalysis and energy storage to optoelectronics, spintronics, and valleytronics. In particular, TMDs have a great potential as emerging inexpensive alternatives to noble metal-based catalysts in electrochemical hydrogen evolution. Herein, we report a straightforward, low-cost, and general colloidal synthesis of various 2D transition-metal disulfide nanomaterials, such as MoS2, WS2, NiSx, FeSx, and VS2, in the absence of organic ligands. This new preparation route provides many benefits including relatively mild reaction conditions, high reproducibility, high yields, easy upscaling, no post-thermal annealing/treatment steps to enhance the catalytic activity, and, finally, especially for molybdenum disulfide nanosheets, high activity in the hydrogen evolution reaction. To underline the universal application of the synthesis, we prepared mixed CoxMo1-xS2 nanosheets in one step to optimize the catalytic activity of pure undoped MoS2, which resulted in an enhanced hydrogen evolution reaction performance characterized by onset potentials as low as 134 mV and small Tafel slopes of 55 mV/dec.

7.
Angew Chem Int Ed Engl ; 59(14): 5706-5711, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-31990450

RESUMO

Noble metal aerogels (NMAs) are an emerging class of porous materials. Embracing nano-sized highly-active noble metals and porous structures, they display unprecedented performance in diverse electrocatalytic processes. However, various impurities, particularly organic ligands, are often involved in the synthesis and remain in the corresponding products, hindering the investigation of the intrinsic electrocatalytic properties of NMAs. Here, starting from laser-generated inorganic-salt-stabilized metal nanoparticles, various impurity-free NMAs (Au, Pd, and Au-Pd aerogels) were fabricated. In this light, we demonstrate not only the intrinsic electrocatalytic properties of NMAs, but also the prominent roles played by ligands in tuning electrocatalysis through modulating the electron density of catalysts. These findings may offer a new dimension to engineer and optimize the electrocatalytic performance for various NMAs and beyond.

8.
Angew Chem Int Ed Engl ; 59(4): 1696-1702, 2020 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-31638732

RESUMO

Solar radiation is a versatile source of energy, convertible to different forms of power. A direct path to exploit it is the generation of heat, for applications including passive building heating, but it can also drive secondary energy-conversion steps. We present a novel concept for a hybrid material which is both strongly photo-absorbing and with superior characteristics for the insulation of heat. The combination of that two properties is rather unique, and make this material an optical superheater. To realize such a material, we are combining plasmonic nanoheaters with alumina aerogel. The aerogel has the double function of providing structural support for plasmonic nanocrystals, which serve as nanoheaters, and reducing the diffusion rate of the heat generated by them, resulting in large local temperature increases under a relatively low radiation intensity. This work includes theoretical discussion on the physical mechanisms impacting the system's balanced thermal equilibrium.

9.
J Chem Phys ; 151(14): 144701, 2019 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-31615238

RESUMO

A general synthesis approach of aqueous glutathione-capped ternary Ag-In-S, Cu-In-S, and Hg-In-S nanocrystals (NCs) is introduced, allowing the NC composition to be varied in a broad range. Ternary Hg-In-S (HIS) NCs are reported for the first time and found to have the same tetragonal chalcopyrite motif as Cu-In-S and Ag-In-S NCs, corroborated by phonon spectra, while X-ray photoelectron spectroscopic data indicate mercury to be present as Hg+ in the Hg-In-S NCs. Colloidal HIS and Hg-In-S/ZnS NCs showed little or no variations of the spectral width of the photoluminescence band upon NC size selection, temperature variation in a broad range of 10-350 K, deposition of a ZnS shell, or postsynthesis annealing. All these observations are similar to those reported earlier for Ag-In-S and Ag-In-S/ZnS NCs and allowed us to assume a general photoluminescence mechanism for all three ternary compounds, based on the model of radiative self-trapped exciton recombination.

10.
ACS Nano ; 13(9): 10386-10396, 2019 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-31430122

RESUMO

All inorganic lead halide perovskite nanocrystals (PNCs) typically suffer from poor stability against moisture and UV radiation as well as degradation during thermal treatment. The stability of PNCs can be significantly enhanced through polymer encapsulation, often accompanied by a decrease of photoluminescence quantum yield (PLQY) due to the loss of highly dynamic oleylamine/oleic acid (OLA/OA) ligands. Herein, we propose a solution for this problem by utilizing partially hydrolyzed poly(methyl methacrylate) (h-PMMA) and highly branched poly(ethylenimine) (b-PEI) as double ligands stabilizing the PNCs already during the mechanochemical synthesis (grinding). The hydrophobic polymer of h-PMMA imparts excellent film-forming properties and water stability to the resulting NC-polymer composite. In its own turn, the b-PEI forms an amino-rich, strongly binding ligand layer on the surface of the PNCs being responsible for the significant improvement of the PLQY and the stability of the resulting material. Moreover, the introduction of b-PEI promotes a partial phase conversion from CsPbBr3 to CsPb2Br5 to obtain CsPbBr3/CsPb2Br5 nanocrystals with a core-shell-like structure. As-prepared PNCs solutions are directly processable as inks, while their PLQY drops only slightly from 75% in colloidal solution to 65% in films. Moreover, the final PNC-polymer film exhibits excellent stability against water, heat, and ultraviolet light irradiation. These superior properties allowed us to fabricate a proof of concept thin film OLED with h-PMMA/b-PEI-stabilized PNCs as an easily processable, narrowly emitting color conversion composite material.

11.
J Phys Chem Lett ; 10(14): 4025-4031, 2019 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-31259561

RESUMO

We demonstrate high-mobility solution-processed inorganic field-effect transistors (FETs) with ultra-short channel (USC) length using semiconductor CdSe nanocrystals (NCs). Capping of the NCs with hybrid inorganic-organic CdCl3--butylamine ligands enables coarsening of the NCs during annealing at a moderate temperature, resulting in the devices having good transport characteristics with electron mobilities in the saturation regime reaching 8 cm2 V-1 s-1. Solution-based processing of the NCs and fabrication of thin films involve neither harsh conditions nor the use of hydrazine. Employing photolithographic methods, we fabricated FETs with a vertical overlap of source and drain electrodes to achieve a submicrometer channel length. To the best of our knowledge, this is the first report on an USC FET based on colloidal semiconductor NCs. Because of a short channel length, the FETs show a normalized transconductance of 4.2 m V-1 s-1 with a high on/off ratio of 105.

12.
Nanoscale ; 11(41): 19370-19379, 2019 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-31173035

RESUMO

In this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 V-1 s-1.

13.
Sci Adv ; 5(5): eaaw4590, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31139750

RESUMO

Noble metal foams (NMFs) are a new class of functional materials featuring properties of both noble metals and monolithic porous materials, providing impressive prospects in diverse fields. Among reported synthetic methods, the sol-gel approach manifests overwhelming advantages for versatile synthesis of nanostructured NMFs (i.e., noble metal aerogels) under mild conditions. However, limited gelation methods and elusive formation mechanisms retard structure/composition manipulation, hampering on-demand design for practical applications. Here, highly tunable NMFs are fabricated by activating specific ion effects, enabling various single/alloy aerogels with adjustable composition (Au, Ag, Pd, and Pt), ligament sizes (3.1 to 142.0 nm), and special morphologies. Their superior performance in programmable self-propulsion devices and electrocatalytic alcohol oxidation is also demonstrated. This study provides a conceptually new approach to fabricate and manipulate NMFs and an overall framework for understanding the gelation mechanism, paving the way for on-target design of NMFs and investigating structure-performance relationships for versatile applications.

14.
Chemistry ; 25(38): 9012-9016, 2019 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-31081977

RESUMO

DNA nanostructures provide a powerful platform for the programmable assembly of nanomaterials. Here, this approach is extended to semiconductor nanorods that possess interesting electrical properties and could be utilized for the bottom-up fabrication of nanoelectronic building blocks. The assembly scheme is based on an efficient DNA functionalization of the nanorods. A complete coverage of the rod surface with DNA ensures a high colloidal stability while maintaining the rod size and shape. It furthermore supports the assembly of the nanorods at defined docking positions of a DNA origami platform with binding efficiencies of up to 90 % as well as the formation of nanorod dimers with defined relative orientations. By incorporating orthogonal binding sites for gold nanoparticles, defined metal-semiconductor heterostructures can be fabricated. Subsequent application of a seeded growth procedure onto the gold nanoparticles (AuNPs) allows for to establish a direct metal-semiconductor interface as a crucial basis for the integration of semiconductors in self-assembled nanoelectronic devices.

15.
J Chem Phys ; 150(14): 144902, 2019 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-30981224

RESUMO

Electrochemistry is a highly versatile part of chemical research which is involved in many of the processes in the field of micromotion. Its input has been crucial from the synthesis of microstructures to the explanation of phoretic mechanisms. However, using electrochemical effects to propel artificial micromotors is still to be achieved. Here, we show that the forces generated by electrochemical reactions can not only create active motion, but they are also strong enough to overcome the adhesion to the substrate, caused by the increased ionic strength of the solutions containing the ions of more noble metals themselves. The galvanic replacement of copper by platinum ions is a spontaneous process, which not only provides a sufficiently strong electromotive force to propel the Janus structures but also results in asymmetric Pt-hatted structures, which can be further used as catalytic micromotors.

16.
Phys Chem Chem Phys ; 21(18): 9036-9043, 2019 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-30900709

RESUMO

We investigate the influence of the average molar mass (Mw) of the capping agent poly(N-vinylpyrrolidone) (PVP) on the conductivity of a silver nanowire (AgNW) network. During the polyol process, the chain length of PVP is known to influence the AgNW diameters and lengths. By altering the reaction temperature and time and using PVP of different chain lengths, we synthesized AgNWs with varying diameters, lengths and PVP coverage. The obtained plethora of AgNWs is the basis for conductivity investigations of networks made of AgNWs with a diameter of either 60 nm or 80 nm. The results show a negative influence of long-chain PVP on the conductivity of the subsequent network if 60 nm thick AgNWs are employed. Overall, we obtain well performing AgNW transparent electrodes on glass with RS = 24.4 Ω sq-1 at 85.5%T550nm.

17.
Phys Chem Chem Phys ; 21(10): 5723-5729, 2019 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-30801102

RESUMO

We simulated irreversible aggregation of non-interacting particles and of particles interacting via repulsive and attractive potentials explicitly implementing the rotational diffusion of aggregating clusters. Our study confirms that the attraction between particles influences neither the aggregation mechanism nor the structure of the aggregates, which are identical to those of non-interacting particles. In contrast, repulsive particles form more compact aggregates and their fractal dimension and aggregation times increase with the decrease of the temperature. A comparison of the fractal dimensions obtained for non-rotating clusters of non-interacting particles and for rotating clusters of repulsive particles provides an explanation for the conformity of the respective values obtained earlier in the well established model of diffusion-limited cluster aggregation neglecting rotational diffusion and in experiments on colloidal particles.

18.
Adv Mater ; 31(31): e1804881, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30536681

RESUMO

Electrocatalysis plays a prominent role in renewable energy conversion and storage, enabling a number of sustainable processes for future technologies. There are generally three strategies to improve the efficiency (or activity) of the electrocatalysts: i) increasing the intrinsic activity of the catalyst itself, ii) improving the exposure of active sites, and iii) accelerating mass transfer during catalysis (both reactants and products). These strategies are not mutually exclusive and can ideally be addressed simultaneously, leading to the largest improvements in activity. Aerogels, as featured by large surface area, high porosity, and self-supportability, provide a platform that matches all the aforementioned criteria for the design of efficient electrocatalysts. The field of aerogel synthesis has seen much progress in recent years, mainly thanks to the rapid development of nanotechnology. Employing precursors with different properties enables the resulting aerogel with targeted catalytic properties and improved performances. Here, the design strategies of aerogel catalysts are demonstrated, and their performance for several electrochemical reactions is reviewed. The common principles that govern electrocatalysis are further discussed for each category of reactions, thus serving as a guide to the development of future aerogel electrocatalysts.

19.
Sci Rep ; 8(1): 13677, 2018 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-30209288

RESUMO

Structure, composition, and optical properties of colloidal mercaptoacetate-stabilized Cu2ZnSnS4 (CZTS) nanocrystal inks produced by a "green" method directly in aqueous solutions were characterized. A size-selective precipitation procedure using 2-propanol as a non-solvent allows separating a series of fractions of CZTS nanocrystals with an average size (bandgap) varying from 3 nm (1.72 eV) to 2 nm (2.04 eV). The size-selected CZTS nanocrystals revealed also phonon confinement, with the main phonon mode frequency varying by about 4 cm-1 between 2 nm and 3 nm NCs.

20.
Nat Mater ; 17(9): 827-833, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-30013055

RESUMO

Tuning the surface structure at the atomic level is of primary importance to simultaneously meet the electrocatalytic performance and stability criteria required for the development of low-temperature proton-exchange membrane fuel cells (PEMFCs). However, transposing the knowledge acquired on extended, model surfaces to practical nanomaterials remains highly challenging. Here, we propose 'surface distortion' as a novel structural descriptor, which is able to reconciliate and unify seemingly opposing notions and contradictory experimental observations in regards to the electrocatalytic oxygen reduction reaction (ORR) reactivity. Beyond its unifying character, we show that surface distortion is pivotal to rationalize the electrocatalytic properties of state-of-the-art of PtNi/C nanocatalysts with distinct atomic composition, size, shape and degree of surface defectiveness under a simulated PEMFC cathode environment. Our study brings fundamental and practical insights into the role of surface defects in electrocatalysis and highlights strategies to design more durable ORR nanocatalysts.

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