251 research outputs found
The catalytic potential of high-k dielectrics for graphene formation
The growth of single and multilayer graphene nano-flakes on MgO and ZrO2 at
low temperatures is shown through transmission electron microscopy. The
graphene nano-flakes are ubiquitously anchored at step edges on MgO (100)
surfaces. Density functional theory investigations on MgO (100) indicate C2H2
decomposition and carbon adsorption at step-edges. Hence, both the experimental
and theoretical data highlight the importance of step sites for graphene growth
on MgO
Room-temperature exciton-polaritons with two-dimensional WS2
Two-dimensional transition metal dichalcogenides exhibit strong optical
transitions with significant potential for optoelectronic devices. In
particular they are suited for cavity quantum electrodynamics in which strong
coupling leads to polariton formation as a root to realisation of inversionless
lasing, polariton condensationand superfluidity. Demonstrations of such
strongly correlated phenomena to date have often relied on cryogenic
temperatures, high excitation densities and were frequently impaired by strong
material disorder. At room-temperature, experiments approaching the strong
coupling regime with transition metal dichalcogenides have been reported, but
well resolved exciton-polaritons have yet to be achieved. Here we report a
study of monolayer WS coupled to an open Fabry-Perot cavity at
room-temperature, in which polariton eigenstates are unambiguously displayed.
In-situ tunability of the cavity length results in a maximal Rabi splitting of
meV, exceeding the exciton linewidth. Our data
are well described by a transfer matrix model appropriate for the large
linewidth regime. This work provides a platform towards observing strongly
correlated polariton phenomena in compact photonic devices for ambient
temperature applications.Comment: 12 pages, 6 figure
Resilient High Catalytic Performance of Platinum Nanocatalysts with Porous Graphene Envelope.
Despite the innumerable developments of nanosized and well dispersed noble metal catalysts, the degradation of metal nanoparticle catalysts has proven to be a significant obstacle for the commercialization of the hydrogen fuel cell. Here, the formation of Pt nanoparticle catalysts with a porous graphene envelope has been achieved using a single step low temperature vaporization process. While these Pt-Gr core-shell nanoparticles possess superior resilience to degradation, it comes at the cost of degraded overall catalyst efficacy. However, it is possible to combat this lower overall performance through inclusion of low concentrations of nitrogen precursor in the initial stage of single-step synthesis, inhibiting the formation of complete graphene shells, as verified by atomic resolution aberration-corrected transmission electron microscopy (AC-TEM) imaging. The resultant porous graphene encapsulated Pt catalysts are found to have both the high peak performance of the bare Pt nanoparticle catalysts and the increased resilience of the fully shielded Pt-Gr core-shells, with the optimal N-doped Pt-Gr yielding a peak efficiency of 87% compared to bare Pt, and maintaining 90% of its catalytic activity after extended potential cycling. The nitrogen treated Pt-Gr core-shells thus act as an effective substitute catalyst for conventional bare Pt nanoparticles, maintaining their catalytic performance over prolonged use
Electron spin coherence in metallofullerenes: Y, Sc and La@C82
Endohedral fullerenes encapsulating a spin-active atom or ion within a carbon
cage offer a route to self-assembled arrays such as spin chains. In the case of
metallofullerenes the charge transfer between the atom and the fullerene cage
has been thought to limit the electron spin phase coherence time (T2) to the
order of a few microseconds. We study electron spin relaxation in several
species of metallofullerene as a function of temperature and solvent
environment, yielding a maximum T2 in deuterated o-terphenyl greater than 200
microseconds for Y, Sc and La@C82. The mechanisms governing relaxation (T1, T2)
arise from metal-cage vibrational modes, spin-orbit coupling and the nuclear
spin environment. The T2 times are over 2 orders of magnitude longer than
previously reported and consequently make metallofullerenes of interest in
areas such as spin-labelling, spintronics and quantum computing.Comment: 5 pages, 4 figure
Atomic Structure and Dynamics of Single Platinum Atom Interactions with Monolayer MoS
We have studied atomic level interactions between single Pt atoms and the surface of monolayer MoSâ‚‚ using aberration-corrected annular dark field scanning transmission electron microscopy at an accelerating voltage of 60 kV. Strong contrast from single Pt atoms on the atomically resolved monolayer MoSâ‚‚ lattice enables their exact position to be determined with respect to the MoSâ‚‚ lattice, revealing stable binding sites. In regions of MoSâ‚‚ free from surface contamination, the Pt atoms are localized in S vacancy sites and exhibit dynamic hopping to nearby vacancy sites driven by the energy supplied by the electron beam. However, in areas of MoSâ‚‚ contaminated with carbon surface layers, the Pt atoms appear at various positions with respect to the underlying MoSâ‚‚ lattice, including on top of Mo and in off-axis positions. These variations are due to the Pt bonding with the surrounding amorphous carbon layer, which disrupts the intrinsic Pt-MoSâ‚‚ interactions, leading to more varied positions. Density functional theory (DFT) calculations reveal that Pt atoms on the surface of MoSâ‚‚ have a small barrier for migration and are stabilized when bound to either a single or double sulfur vacancies. DFT calculations have been used to understand how the catalytic activity of the MoSâ‚‚ basal plane for hydrogen evolution reaction is influenced by Pt dopants by variation of the hydrogen adsorption free energy. This strong dependence of catalytic effect on interfacial configurations is shown to be common for a series of dopants, which may provide a means to create and optimize reaction centers
Structure–property relationship of defect-trapped Pt single-site electrocatalysts for the hydrogen evolution reaction
Single-site catalysts (SSCs) have attracted significant research interest due to their high metal atom utilization. Platinum single sites trapped in the defects of carbon substrates (trapped Pt-SSCs) have been proposed as efficient and stable electrocatalysts for the hydrogen evolution reaction (HER). However, the correlation between Pt bonding environment, its evolution during operation, and catalytic activity is still unclear. Here, a trapped Pt-SSC is synthesized by pyrolysis of H2PtCl6 chemisorbed on a polyaniline substrate. In situ heated scanning transmission electron microscopy and temperature-dependent X-ray photoelectron spectroscopy clarify the thermally induced structural evolution of Pt during pyrolysis. The results show that the nitrogen in polyaniline coordinates with Pt ions and atomically disperses them before pyrolysis and traps Pt sites at pyridinic N defects generated during the substrate graphitization. Operando X-ray absorption spectroscopy confirms that the trapped Pt-SSC is stable at the HER working potentials but with inferior electrocatalytic activity compared with metallic Pt nanoparticles. First principle calculations suggest that the inferior activity of trapped Pt-SSCs is due to their unfavorable hydrogen chemisorption energy relative to metallic Pt(111) surfaces. These results further the understanding of the structure–property relationship in trapped Pt-SSCs and motivate a detailed techno-economic analysis to evaluate their commercial applicability
Mapping nanoscale electrostatic field fluctuations around graphene dislocation cores using four-dimensional scanning transmission electron microscopy (4D-STEM)
Defects in crystalline lattices cause modulation of the atomic density, and this leads to variations in the associated electrostatics at the nanoscale. Mapping these spatially varying charge fluctuations using transmission electron microscopy has typically been challenging due to complicated contrast transfer inherent to conventional phase contrast imaging. To overcome this, we used four-dimensional scanning transmission electron microscopy (4D-STEM) to measure electrostatic fields near point dislocations in a monolayer. The asymmetry of the atomic density in a (1,0) edge dislocation core in graphene yields a local enhancement of the electric field in part of the dislocation core. Through experiment and simulation, the increased electric field magnitude is shown to arise from "long-range" interactions from beyond the nearest atomic neighbor. These results provide insights into the use of 4D-STEM to quantify electrostatics in thin materials and map out the lateral potential variations that are important for molecular and atomic bonding through Coulombic interactions
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