Kane Michael O'Donnell

Sulfur and nitrogen co-doped graphene for metal-free catalytic oxidation reactions

Sulfur and nitrogen co-doped reduced graphene oxide (rGO) is synthesized by a facile method and demonstrated remarkably enhanced activities in metal-free activation of peroxymonosulfate (PMS) for catalytic oxidation of phenol. Based on first-order kinetic model, S-N co-doped rGO (SNG) presents an apparent reaction rate constant of 0.043 ± 0.002 min(-1) , which is 86.6, 22.8, 19.7, and 4.5-fold as high as that over graphene oxide (GO), rGO, S-doped rGO (S-rGO), and N-doped rGO (N-rGO), respectively. A variety of characterization techniques and density functional theory calculations are employed to investigate the synergistic effect of sulfur and nitrogen co-doping. Co-doping of rGO at an optimal sulfur loading can effectively break the inertness of carbon systems, activate the sp(2) -hybridized carbon lattice and facilitate the electron transfer from covalent graphene sheets for PMS activation. Moreover, both electron paramagnetic resonance (EPR) spectroscopy and classical quenching tests are employed to investigate the generation and evolution of reactive radicals on the SNG sample for phenol catalytic oxidation. This study presents a novel metal-free catalyst for green remediation of organic pollutants in water.

Creating a Stable Oxide at the Surface of Black Phosphorus.

The stability of the surface of in situ cleaved black phosphorus crystals upon exposure to atmosphere is investigated with synchrotron-based photoelectron spectroscopy. After 2 days atmosphere exposure a stable subnanometer layer of primarily P2O5 forms at the surface. The work function increases by 0.1 eV from 3.9 eV for as-cleaved black phosphorus to 4.0 eV after formation of the 0.4 nm thick oxide, with phosphorus core levels shifting by <0.1 eV. The results indicate minimal charge transfer, suggesting that the oxide layer is suitable for passivation or as an interface layer for further dielectric deposition.

Performance, morphology and photophysics of high open-circuit voltage, low band gap all-polymer solar cells

The microstructure and photophysics of low-band gap, all-polymer photovoltaic blends are presented. Blends are based on the donor polymer BFS4 (a dithienyl-benzo[1,2-b:4,5-b]dithiophene/5-fluoro-2,1,3-benzothiadiazole co-polymer) paired with the naphthalene diimide-based acceptor polymer P(NDI2OD-T2). Efficiencies of over 4% are demonstrated, with an open circuit voltage of greater than 0.9 V achieved. Transmission electron microscopy reveals a relatively coarse phase-separated morphology, with elongated domains up to 200 nm in width. Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy and atomic force microscopy (AFM) measurements reveal that the top surface of BFS4:P(NDI2OD-T2) blends is covered with a pure BFS4 capping layer. Depth profiling measurements confirm this vertical phase separation with a surface-directed spinodal decomposition wave observed. Grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements confirm that BFS4 and P(NDI2OD-T2) are semicrystalline with both polymers retaining their semicrystalline nature when blended. Photoluminescence spectroscopy reveals incomplete photoluminescence quenching with as much as 30% of excitons failing to reach a donor/acceptor interface. Transient absorption spectroscopy measurements also find evidence for rapid geminate recombination.

Triconstituent co-assembly synthesis of N,S-doped carbon–silica nanospheres with smooth and rough surfaces

Multifunctional porous nanospheres are desirable for many applications, but their synthesis involves multi-step procedures and their simplification still remains a challenge. Herein, we demonstrate a facile synthesis of polymer–silica nanospheres by using an extended Stober method via triconstituent co-assembly of 3-aminophenol, formaldehyde, and bis[3-(triethoxysilyl)propyl]tetrasulfide followed by copolymerization. N,S-doped carbon–silica nanospheres with either smooth or rough surface can be obtained by direct carbonization of the polymer–silica nanospheres. The carbon–silica spheres feature multifunctional properties and exhibit very good performance as adsorbents for CO2 capture (67 cm3 g−1 at 0 ± 1 °C and 1.0 bar) and as supercapacitor electrodes with high specific capacitance (221 F g−1). This strategy could pave the way for design of carbon nanostructures at molecular level for multi-purpose applications.

Work function and electron affinity of the fluorine-terminated (100) diamond surface

The work function and electron affinity of fluorine-terminated (100) diamond surfaces prepared by exposure to dissociated XeF2 have been determined using synchrotron-based photoemission. After vacuum annealing to 350 °C a clean, monofluoride terminated C(100):F surface was obtained for which an electron affinity of 2.56 eV was measured. This is the highest electron affinity reported for any diamond surface termination so far, and it exceeds the value predicted by recent density functional theory calculations by 0.43 eV. The work function of 7.24 eV measured for the same surface places the Fermi energy of 0.79 eV above the valence band maximum.

Air-Stable Electron Depletion of Bi2Se3 Using Molybdenum Trioxide into the Topological Regime

We perform high-resolution photoelectron spectroscopy on in situ cleaved topological insulator Bi2Se3 single crystals and in situ transport measurements on Bi2Se3 films grown by molecular beam epitaxy. We demonstrate efficient electron depletion of Bi2Se3 via vacuum deposition of molecular MoO3, lowering the surface Fermi energy to within ∼100 meV of the Dirac point, well into the topological regime. A 100 nm MoO3 film provides an air-stable doping and passivation layer.

Electronic Properties of High-Quality Epitaxial Topological Dirac Semimetal Thin Films

Topological Dirac semimetals (TDS) are three-dimensional analogues of graphene, with linear electronic dispersions in three dimensions. Nanoscale confinement of TDSs in thin films is a necessary step toward observing the conventional-to-topological quantum phase transition (QPT) with increasing film thickness, gated devices for electric-field control of topological states, and devices with surface-state-dominated transport phenomena. Thin films can also be interfaced with superconductors (realizing a host for Majorana Fermions) or ferromagnets (realizing Weyl Fermions or T-broken topological states). Here we report structural and electrical characterization of large-area epitaxial thin films of TDS Na3Bi on single crystal Al2O3[0001] substrates. Charge carrier mobilities exceeding 6,000 cm(2)/(V s) and carrier densities below 1 × 10(18) cm(-3) are comparable to the best single crystal values. Perpendicular magnetoresistance at low field shows the perfect weak antilocalization behavior expected for Dirac Fermions in the absence of intervalley scattering. At higher fields up to 0.5 T anomalously large quadratic magnetoresistance is observed, indicating that some aspects of the low field magnetotransport (μB < 1) in this TDS are yet to be explained.

Manipulating the orientation of an organic adsorbate on silicon: a NEXAFS study of acetophenone on Si(0 0 1)

We investigate the chemical and structural configuration of acetophenone on Si(0 0 1) using synchrotron radiation core-level spectroscopy techniques and density functional theory calculations. Samples were prepared by vapour phase dosing of clean Si(0 0 1) surfaces with acetophenone in ultrahigh vacuum. Near edge x-ray absorption fine structure spectroscopy and photoelectron spectroscopy measurements were made at room temperature as a function of coverage density and post-deposition anneal temperature. We show that the dominant room temperature adsorption structure lies flat on the substrate, while moderate thermal annealing induces the breaking of Si-C bonds between the phenyl ring and the surface resulting in the reorientation of the adsorbate into an upright configuration.

Formation of a silicon terminated (100) diamond surface

We report the preparation of an ordered silicon terminated diamond (100) surface with a two domain 3 × 1 reconstruction as determined by low energy electron diffraction. Based on the dimensions of the surface unit cell and on chemical information provided by core level photoemission spectra, a model for the structure is proposed. The termination should provide a homogeneous, nuclear, and electron spin-free surface for the development of future near-surface diamond quantum device architectures.

A desktop supersonic free-jet beam source for a scanning helium microscope (SHeM)

A simple design for an inexpensive, compact, desktop-sized helium free-jet beam source is described. The apparatus, which is Campargue-like in design and utilizes mostly off-the-shelf parts, is capable of producing a centreline intensity of 1.2???1019?atoms per second per steradian. The beam performance was investigated using a conventional ion gauge and a stagnation detector, with the latter being used to produce beam flux profiles. The profile of the macroskimmed beam has been experimentally demonstrated to be strongly Gaussian.