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1.
ACS Appl Mater Interfaces ; 11(28): 25155-25162, 2019 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-31268661

RESUMO

Transition-metal dichalcogenides (TMDs) are being widely pursued as inexpensive, earth-abundant substitutes for precious-metal catalysts in technologically important reactions such as electrochemical hydrogen evolution reaction (HER). However, the relatively high onset potentials of TMDs relative to Pt remain a persistent challenge in widespread adoption of these materials. Here, we demonstrate a one-pot synthesis approach for substitutional Mn-doping of MoSe2 nanoflowers to achieve appreciable reduction in the overpotential for HER along with a substantial improvement in the charge-transfer kinetics. Electron microscopy and elemental characterization of our samples show that the MoSe2 nanoflowers retain their structural integrity without any evidence for dopant clustering, thus confirming true substitutional doping of the catalyst. Complementary density functional theory calculations reveal that the substitutional Mn-dopants act as promoters, rather than enhanced active sites, for the formation of Se-vacancies in MoSe2 that are known to be catalytically active for HER. Our work advances possible strategies for activating MoSe2 and similar TMDs by the use of substitutional dopants, not for their inherent activity, but as promoters of active chalcogen vacancies.

2.
Phys Chem Chem Phys ; 20(36): 23262-23271, 2018 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-30191205

RESUMO

Platinum (Pt) is among the best electrocatalysts for the hydrogen evolution reaction (HER), a potentially fossil-free route for hydrogen production. Reduction in Pt loading and overall catalyst cost, without sacrificing catalytic activity, can be achieved by the synthesis of stable core-shell nanoparticles of transition-metal carbides and Pt. We employ density-functional theory (DFT) calculations to study and contrast the suitability of the α and ß phases of tungsten carbide (WC) as support (core) materials for Pt shells. We examine the thermodynamic stability of 1-2 layers of Pt on α- and ß-WC surfaces, carefully accounting for the delicate balance between epitaxial mismatch strains and chemical bonding between cores and shells. We also study the effects of alloying ß-WC with Ti to modulate the stability and electronic structure of the core-shell structures. We compare the electronic structures of Pt overlayers supported on α-WC and ß-TixW1-xC surfaces and compare their activities for HER using the hydrogen binding energy as a descriptor of catalytic activity. Our studies reveal that moderate Ti doping of the metastable ß-WC phase significantly improves its stability and, with merely two layers of Pt loading, HER activity comparable or superior to Pt(111) can be attained. Overall, our results provide detailed insight into experimental observations of the excellent stability and high catalytic activity of ß-TixW1-xC@Pt core-shell nanoparticles.

4.
ACS Nano ; 12(2): 1928-1933, 2018 02 27.
Artigo em Inglês | MEDLINE | ID: mdl-29378391

RESUMO

Two-dimensional (2D) materials are believed to hold significant promise in nanoscale optoelectronics. While significant progress has been made in this field over the past decade, the ability to control charge carrier density with high spatial precision remains an outstanding challenge in 2D devices. We present an approach that simultaneously addresses the dual issues of charge-carrier doping and spatial precision based on a functional lithographic resist that employs methacrylate polymers containing zwitterionic sulfobetaine pendent groups for noncovalent surface doping of 2D materials. We demonstrate scalable approaches for patterning these polymer films via electron-beam lithography, achieving precise spatial control over carrier doping for fabrication of high-quality, all-2D, lateral p-n junctions in graphene. Our approach preserves all of the desirable structural and electronic properties of graphene while exclusively modifying its surface potential. The functional polymer resist platform and concept offers a facile route toward lithographic doping of graphene- and other 2D material-based optoelectronic devices.

5.
ACS Appl Mater Interfaces ; 9(27): 23092-23098, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28621129

RESUMO

Graphene and other two-dimensional (2D) materials are of emerging interest as functional fillers in polymer-matrix composites. In this study, we present a multiscale atomistic-to-continuum approach for modeling interfacial stress transfer in graphene-high-density polyethylene (HDPE) nanocomposites. Via detailed characterization of atomic-level stress profiles in submicron graphene fillers, we develop a modified shear-lag model for short fillers. A key feature of our approach lies in the correct accounting of stress concentration at the ends of fillers that exhibits a power-law dependence on filler ("flaw") size, determined explicitly from atomistic simulations, without any ad hoc modeling assumptions. In addition to two parameters that quantify the end stress concentration, only one additional shear-lag parameter is required to quantify the atomic-level stress profiles in graphene fillers. This three-parameter model is found to be reliable for fillers with dimensions as small as ∼10 nm. Our model predicts accurately the elastic response of aligned graphene-HDPE composites and provides appropriate upper bounds for the elastic moduli of nanocomposites with more realistic randomly distributed and oriented fillers. This study provides a systematic approach for developing hierarchical multiscale models of 2D material-based nanocomposites and is of particular relevance for short fillers, which are, currently, typical of solution-processed 2D materials.

6.
J Phys Chem A ; 121(12): 2497-2502, 2017 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-28267337

RESUMO

We present a self-consistent charge density-functional tight-binding (SCC-DFTB) parametrization for PtRu alloys, which is developed by employing a training set of alloy cluster energies and forces obtained from Kohn-Sham density-functional theory (DFT) calculations. Extensive simulations of a testing set of PtRu alloy nanoclusters show that this SCC-DFTB scheme is capable of capturing cluster formation energies with high accuracy relative to DFT calculations. The new SCC-DFTB parametrization is employed within a genetic algorithm to search for global minima of PtRu clusters in the range of 13-81 atoms and the emergence of Ru-core/Pt-shell structures at intermediate alloy compositions, consistent with known results, is systematically demonstrated. Our new SCC-DFTB parametrization enables computationally inexpensive and accurate modeling of Pt-Ru clusters that are among the best-performing catalysts in numerous energy applications.

7.
Nano Lett ; 16(9): 5852-60, 2016 09 14.
Artigo em Inglês | MEDLINE | ID: mdl-27517466

RESUMO

We synthesized distorted octahedral (T') molybdenum ditelluride (MoTe2) and investigated its vibrational properties with Raman spectroscopy, density functional theory, and symmetry analysis. Compared to results from the high-temperature centrosymmetric monoclinic (T'mo) phase, four new Raman bands emerge in the low-temperature orthorhombic (T'or) phase, which was recently predicted to be a type II Weyl semimetal. Crystal-angle-dependent, light-polarization-resolved measurements indicate that all the observed Raman peaks belong to two categories: those vibrating along the zigzag Mo atomic chain (z-modes) and those vibrating in the mirror plane (m-modes) perpendicular to the zigzag chain. Interestingly, the low-energy shear z-mode and shear m-mode, absent from the T'mo spectra, become activated when sample cooling induces a phase transition to the T'or crystal structure. We interpret this observation as a consequence of inversion-symmetry breaking, which is crucial for the existence of Weyl fermions in the layered crystal. Our temperature-dependent Raman measurements further show that both the high-energy m-mode at ∼130 cm(-1) and the low-energy shear m-mode at ∼12 cm(-1) provide useful gauges for monitoring the broken inversion symmetry in the crystal.

8.
Sci Rep ; 6: 31735, 2016 08 22.
Artigo em Inglês | MEDLINE | ID: mdl-27546738

RESUMO

Nanoscale carbon-based fillers are known to significantly alter the mechanical and electrical properties of polymers even at relatively low loadings. We report results from extensive molecular-dynamics simulations of mechanical testing of model polymer (high-density polyethylene) nanocomposites reinforced by nanocarbon fillers consisting of graphene flakes and fullerenes. By systematically varying filler concentration, morphology, and size, we identify clear trends in composite stiffness with reinforcement. To within statistical error, spherical fullerenes provide a nearly size-independent level of reinforcement. In contrast, two-dimensional graphene flakes induce a strongly size-dependent response: we find that flakes with radii in the 2-4 nm range provide appreciable enhancement in stiffness, which scales linearly with flake radius. Thus, with flakes approaching typical experimental sizes (~0.1-1 µm), we expect graphene fillers to provide substantial reinforcement, which also is much greater than what could be achieved with fullerene fillers. We identify the atomic-scale features responsible for this size- and morphology-dependent response, notably, ordering and densification of polymer chains at the filler-matrix interface, thereby providing insights into avenues for further control and enhancement of the mechanical properties of polymer nanocomposites.

9.
Sci Rep ; 6: 28024, 2016 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-27324297

RESUMO

Stokes and anti-Stokes Raman scattering are performed on atomic layers of hexagonal molybdenum ditelluride (MoTe2), a prototypical transition metal dichalcogenide (TMDC) semiconductor. The data reveal all six types of zone center optical phonons, along with their corresponding Davydov splittings, which have been challenging to see in other TMDCs. We discover that the anti-Stokes Raman intensity of the low energy layer-breathing mode becomes more intense than the Stokes peak under certain experimental conditions, and find the effect to be tunable by excitation frequency and number of atomic layers. These observations are interpreted as a result of resonance effects arising from the C excitons in the vicinity of the Brillouin zone center in the photon-electron-phonon interaction process.

10.
ACS Nano ; 10(6): 6248-56, 2016 06 28.
Artigo em Inglês | MEDLINE | ID: mdl-27215812

RESUMO

Misfit layered compounds (MLCs) have generated significant interest in recent years as potential thermoelectric materials. MLC nanotubes could reveal behavior that is entirely different from the bulk material. Recently, new chemical strategies were exploited for the synthesis of nanotubular forms of chalcogenide-based MLCs, which are promising candidates for thermoelectric materials. However, analogous synthesis of oxide-based MLC nanotubes has not been demonstrated until now. Here, we report a chemical strategy for synthesis of cobalt-oxide-based misfit nanotubes. A combination of high-resolution (scanning) transmission electron microscopy (including image simulations), spatially resolved electron energy-loss spectroscopy, electron diffraction, and density functional theory (DFT) calculations is used to discover the formation of a phase within these nanotubes that differs significantly from bulk calcium cobaltite MLCs. Furthermore, DFT calculations show that this phase is semiconducting with a band gap in excess of 1 eV, unlike bulk calcium cobaltite MLCs, which are known to be metallic. Through systematic experiments, we propose a formation mechanism for these nanotubes that could also apply more generally to realizing other oxide-based MLC nanotubes.

11.
Chem Sci ; 7(7): 4698-4705, 2016 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-30155118

RESUMO

Transition metal dichalcogenides (TMDCs) such as MoS2 comprise an important class of 2D semiconductors with numerous interesting electronic and mechanical features. Full utilization of TMDCs in materials and devices, however, necessitates robust functionalization methods. We report well-defined tetrathiafulvalene (TTF)-based polymers, exploiting synthetic routes that overcome challenges previously associated with these systems. These platforms enable basal plane coordinative interactions with MoS2, conceptually in parallel with pyrene-containing platforms for graphene and carbon nanotube modification. Not yet reported for TMDCs, these non-covalent interactions are universal and effective for MoS2 irrespective of the lattice structure, affording significantly enhanced solution stabilization of the nanosheets. Additionally, the TTF-functionalized polymers offer electronic structure modulation of MoS2 by ground state charge transfer and work function reduction, demonstrated using Kelvin probe force microscopy (KPFM). Notably, coordination and electronic effects are amplified for the TTF-polymers over TTF itself. Experiments are supported by first-principles density functional theory (DFT) calculations that probe polymer-TTF surface interactions with MoS2 and the resultant impact on electronic properties.

12.
Phys Rev Lett ; 112(18): 186802, 2014 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-24856713

RESUMO

Monolayer transition-metal dichalcogenides (TMDCs) display valley-selective circular dichroism due to the presence of time-reversal symmetry and the absence of inversion symmetry, making them promising candidates for valleytronics. In contrast, in bilayer TMDCs both symmetries are present and these desirable valley-selective properties are lost. Here, by using density-functional tight-binding electronic structure simulations and revised periodic boundary conditions, we show that bending of bilayer MoS2 sheets breaks band degeneracies and localizes states on separate layers due to bending-induced strain gradients across the sheets. We propose a strategy for employing bending deformations in bilayer TMDCs as a simple yet effective means of dynamically and reversibly tuning their band gaps while simultaneously tuning valley-selective physics.

13.
J Comput Chem ; 34(1): 60-6, 2013 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-22941861

RESUMO

Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p(z) orbitals and the metal d(z(2)) and d(yz) orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25%. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well.


Assuntos
Oxigênio/química , Paládio/química , Floroglucinol/química , Platina/química , Água/química , Adsorção , Teoria Quântica , Propriedades de Superfície
15.
Nano Lett ; 11(3): 1070-5, 2011 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-21275424

RESUMO

We investigate band gap tuning of bilayer graphene between hexagonal boron nitride sheets, by external electric fields. Using density functional theory, we show that the gap is continuously tunable from 0 to 0.2 eV and is robust to stacking disorder. Moreover, boron nitride sheets do not alter the fundamental response from that of free-standing bilayer graphene, apart from additional screening. The calculations suggest that graphene-boron nitride heterostructures could provide a viable route to graphene-based electronic devices.

16.
ACS Nano ; 4(4): 2300-6, 2010 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-20380417

RESUMO

A multilayered composite structure formed by a random stacking of graphene oxide (GO) platelets is an attractive candidate for novel applications in nanoelectromechanical systems and paper-like composites. We employ molecular dynamics simulations with reactive force fields to elucidate the structural and mechanical properties of GO paper-like materials. We find that the large-scale properties of these composites are controlled by hydrogen bond networks that involve functional groups on individual GO platelets and water molecules within the interlayer cavities. Water content controls both the extent and collective strength of these interlayer hydrogen bond networks, thereby affecting the interlayer spacing and elastic moduli of the composite. Additionally, the chemical composition of the individual GO platelets also plays a critical role in establishing the mechanical properties of the composite--a higher density of functional groups leads to increased hydrogen bonding and a corresponding increase in stiffness. Our studies suggest the possibility of tuning the properties of GO composites by altering the density of functional groups on individual platelets, the water content, and possibly the functional groups participating in hydrogen bonding with interlayer water molecules.

17.
Phys Rev E Stat Nonlin Soft Matter Phys ; 77(2 Pt 1): 021601, 2008 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-18352033

RESUMO

As an alloy surface evolves under capillary forces, differing mobilities of the individual components can lead to kinetic alloy decomposition at the surface. In this paper, we address the relaxation of nanoscale sinusoidal ripples on alloy surfaces by considering the effects of both surface and bulk diffusion. In the absence of bulk diffusion, we derive exact analytical expressions for relaxation rates and identify two natural time scales that govern the relaxation dynamics. Bulk diffusion is shown to reduce kinetic surface segregation and enhance relaxation rates, owing to intermixing near the surface. Our results provide a quantitative framework for the interpretation of relaxation experiments on alloy surfaces.

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