Robert F. Klie

High‐Quality Black Phosphorus Atomic Layers by Liquid‐Phase Exfoliation

P. Yasaei, Dr. B. Kumar, M. Asadi, Prof. A. Salehi-Khojin Department of Mechanical and Industrial Engineering University of Illinois at Chicago Chicago , IL 60607 , USA E-mail: salehikh@uic.edu T. Foroozan, Prof. J. E. Indacochea Department of Civil and Materials Engineering University of Illinois at Chicago Chicago , IL 60607 , USA C. Wang, Prof. R. F. Klie Department of Physics University of Illinois at Chicago Chicago , IL 60607 , USA D. Tuschel HORIBA Scientifi c HORIBA Scientifi c Inc. Edison , NJ 08820 , USA

Robust carbon dioxide reduction on molybdenum disulphide edges

Electrochemical reduction of carbon dioxide has been recognized as an efficient way to convert carbon dioxide to energy-rich products. Noble metals (for example, gold and silver) have been demonstrated to reduce carbon dioxide at moderate rates and low overpotentials. Nevertheless, the development of inexpensive systems with an efficient carbon dioxide reduction capability remains a challenge. Here we identify molybdenum disulphide as a promising cost-effective substitute for noble metal catalysts. We uncover that molybdenum disulphide shows superior carbon dioxide reduction performance compared with the noble metals with a high current density and low overpotential (54 mV) in an ionic liquid. Scanning transmission electron microscopy analysis and first principle modelling reveal that the molybdenum-terminated edges of molybdenum disulphide are mainly responsible for its catalytic performance due to their metallic character and a high d-electron density. This is further experimentally supported by the carbon dioxide reduction performance of vertically aligned molybdenum disulphide.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

Small and salty CO2 reduction scheme Most artificial photosynthesis approaches focus on making hydrogen. Modifying CO2, as plants and microbes do, is more chemically complex. Asadi et al. report that fashioning WSe2 and related electrochemical catalysts into nanometer-scale flakes greatly improves their activity for the reduction of CO2 to CO. An ionic liquid reaction medium further enhances efficiency. An artificial leaf with WSe2 reduced CO2 on one side while a cobalt catalyst oxidized water on the other side. Science, this issue p. 467 Nanostructuring tungsten diselenide enhances catalytic activity for carbon dioxide conversion to carbon monoxide in an ionic liquid medium. Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform that concurrently oxidized water in the absence of any external potential.

Atomic-scale observation of lithiation reaction front in nanoscale SnO2 materials.

In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1[overline]1[overline]1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors. At the later stages of lithiation, the Li-induced amorphization of rutile SnO2 and the formation of crystalline Sn and LixSn particles in the Li2O matrix were observed.

Electrical characterization of single GaN nanowires

In this paper a statistically significant study of 1096 individual GaN nanowire (NW) devices is presented. We have correlated the effects of changing growth parameters for hot-wall chemically-vapour-deposited (HW-CVD) NW sf abricated via the vapour–liquid–solid mechanism. We first describe an optical lithographic method for creating Ohmic contacts to NW field effect transistors with both top and bottom electrostatic gates to characterize carrier density and mobility. Multiprobe measurements show that carrier modulation occurs in the channel and is not a contact effect. We then show that NW fabrication runs with nominally identical growth parameters yield similar electrical results across sample populations of >50 devices. By systematically altering th eg rowth parameters we were able to decrease the average carrier concentration for these as-grown GaN NWs ∼10-fold, from 2.29 × 10 20 to 2.45 × 10 19 cm −3 ,a nd successfully elucidate the parameters that exert the strongest influence on wire quality. Furthermore, this study shows that nitrogen vacancies, and not oxygen impurities, are the dominant intrinsic dopant in HW-CVD GaN NWs.

Nanoscale-SiC doping for enhancing Jc and Hc2 in superconducting MgB2

The effect of nanoscale-SiC doping of MgB2 was investigated in comparison with undoped, clean-limit, and Mg-vapor-exposed samples using transport and magnetic measurements. It was found that there are two distinguishable but related mechanisms that control the critical current-density-field Jc(H) behavior: increase of upper critical field Hc2 and improvement of flux pinning. There is a clear correlation between the critical temperature Tc, the resistivity ρ, the residual resistivity ratio RRR=R(300K)∕R(40K), the irreversibility field H*, and the alloying state in the samples. The Hc2 is about the same within the measured field range for both the Mg-vapor-treated and the SiC-doped samples. However, the Jc(H) for the latter is higher than the former in a high-field regime by an order of magnitude. Mg vapor treatment induced intrinsic scattering and contributed to an increase in Hc2. SiC doping, on the other hand, introduced many nanoscale precipitates and disorder at B and Mg sites, provoking an increase of...

Polaron melting and ordering as key mechanisms for colossal resistance effects in manganites.

Polarons, the combined motion of electrons in a cloth of their lattice distortions, are a key transport feature in doped manganites. To develop a profound understanding of the colossal resistance effects induced by external fields, the study of polaron correlations and the resulting collective polaron behavior, i.e., polaron ordering and transition from polaronic transport to metallic transport is essential. We show that static long-range ordering of Jahn–Teller polarons forms a polaron solid which represents a new type of charge and orbital ordered state. The related noncentrosymmetric lattice distortions establish a connection between colossal resistance effects and multiferroic properties, i.e., the coexistence of ferroelectric and antiferromagnetic ordering. Colossal resistance effects due to an electrically induced polaron solid–liquid transition are directly observed in a transmission electron microscope with local electric stimulus applied in situ using a piezo-controlled tip. Our results shed light onto the colossal resistance effects in magnetic field and have a strong impact on the development of correlated electron-device applications such as resistive random access memory (RRAM).

Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures.

To be able to control the functions of engineered multicomponent nanomaterials, a detailed understanding of heterogeneous nucleation at the nanoscale is essential. Here, by using in situ synchrotron X-ray scattering, we show that in the heterogeneous nucleation and growth of Au on Pt or Pt-alloy seeds the heteroepitaxial growth of the Au shell exerts high stress (∼2 GPa) on the seed by forming a core/shell structure in the early stage of the reaction. The development of lattice strain and subsequent strain relaxation, which we show using atomic-resolution transmission electron microscopy to occur through the slip of {111} layers, induces morphological changes from a core/shell to a dumbbell structure, and governs the nucleation and growth kinetics. We also propose a thermodynamic model for the nucleation and growth of dumbbell metallic heteronanostructures.

Atomic scale characterization of oxygen vacancy segregation at SrTiO3 grain boundaries

We have examined the atomic structure, composition, and bonding at a nominally undoped 58° [001] tilt grain boundary in SrTiO3 in order to develop an understanding of the control that the grain boundary plane exerts over the bulk properties. Room temperature and in situ heating experiments show that there is a segregation of oxygen vacancies to the grain boundary that is increased at elevated temperatures and is independent of the cation arrangement. These measurements provide direct support for recent experimental and theoretical predictions that nonstoichiometry, and in particular oxygen vacancies, are responsible for the widely observed grain boundary properties.

Metalorganic chemical vapor deposition of aluminum oxide on Si: Evidence of interface SiO2 formation

Thin films of aluminum oxide were deposited on H-passivated Si(100) substrate using trimethylaluminum and oxygen at 0.5 Torr and 300 °C. Fourier transform infrared (FTIR) and x-ray photoelectron spectroscopic analyses of these films showed no aluminum silicate phase at the film–substrate interface. The O/Al ratio in the deposited film was found to be higher than that in stoichiometric Al2O3. On annealing the as-deposited samples in Ar at 900 °C, an absorption peak due to the transverse optical phonon for the Si–O–Si stretching mode appeared in the FTIR spectra. A combination of Z-contrast imaging and electron energy-loss spectroscopy in the scanning transmission electron microscope confirmed that the annealed samples developed a layer of silicon dioxide at the aluminum oxide–Si interface. Our results suggest that excess oxygen present in the deposited film reacts with the underlying Si substrate and forms silicon oxide.