Comparative study of catalytic activities among transition metal-doped IrO2 nanoparticles.

Catalytic activities of transition metal-doped IrO2 nanoparticles (TM-IrO2 NPs; TM = Cr, Mn, Fe, Co, or Ni) are compared for various oxidation reactions such as electrochemical oxygen evolution reaction (OER), gas-phase photo-oxidation of thiol function group, and CO oxidative conversion. Here, we discovered a series of TM-IrO2 catalysts have a common activity trend for these oxidation reactions, and their activities are closely related with modified electronic states of IrO2, strongly affected by the types of the transition metal across the periodic table. For all oxidation reactions, Cr- and Mn-IrO2 achieved the highest oxidation catalytic activity, and sequentially decreased activities were obtained with Fe, Co, and Ni doped IrO2. For instance, the highest OER activity was achieved by Cr or Mn doping exhibiting the smallest overpotential η = 275~230 mV at 10 mA/cm2, while Ni-IrO2 showed rather larger overpotential (η = 347 mV) even compared with non-doped IrO2 (η = 314 mV). Scanning transmission X-ray microscopy and high-resolution photoemission spectra of TM-IrO2 indicated dopant metals modified the Ir-O interaction and thus increasing oxygen vacancy defects in IrO2. Strongly positive correlation was observed between the catalytic activities and vacancy states. The amount of defect related signals was observed the most for Cr- or Mn-IrO2, less so for Fe- or Co-IrO2, and unnoted for Ni-IrO2 compared with bare IrO2. Based on these catalytic activities and surface spectroscopic analysis results, vacancy defects induced by doping in TM-IrO2 NPs are proposed to contribute to enhance the oxidation activities.

A scanning transmission X-ray microscope at the Pohang Light Source.

A scanning transmission X-ray microscope is operational at the 10A beamline at the Pohang Light Source. The 10A beamline provides soft X-rays in the photon energy range 100-2000 eV using an elliptically polarized undulator. The practically usable photon energy range of the scanning transmission X-ray microscopy (STXM) setup is from ∼150 to ∼1600 eV. With a zone plate of 25 nm outermost zone width, the diffraction-limited space resolution, ∼30 nm, is achieved in the photon energy range up to ∼850 eV. In transmission mode for thin samples, STXM provides the element, chemical state and magnetic moment specific distributions, based on absorption spectroscopy. A soft X-ray fluorescence measurement setup has been implemented in order to provide the elemental distribution of thicker samples as well as chemical state information with a space resolution of ∼50 nm. A ptychography setup has been implemented in order to improve the space resolution down to 10 nm. Hardware setups and application activities of the STXM are presented.

Spectromicroscopic observation of a live single cell in a biocompatible liquid-enclosing graphene system.

On-the-spot visualization of biochemical responses of intact live cells is vital for a clear understanding of cell biology. The main obstacles for instant visualization of biochemical responses of living cells arise from the lack of a sophisticated detecting technique which can simultaneously provide chemical analysis tools and the biocompatible wet conditions. Here we introduce scanning transmission X-ray microscopy (STXM) combined with a liquid-enclosing graphene system (LGS), offering biocompatible conditions and improved X-ray absorption spectra to probe the chemical responses of live cells under wet conditions. This set-up enables us to probe a subtle change in absorption spectra depending on the oxidation state of a miniscule amount of oxygen in the functional groups present in each cell and its surroundings containing a minimal amount of liquid water. As an example of in situ biochemical responses of wet cells, chemical responses of a single Colo 205 cell are visualized and analyzed using X-ray absorption near the oxygen K-edge. This spectromicroscopic method using LGS can be applied to diverse biological samples under wet conditions for the analysis of their biochemical responses.

Topological modification of the electronic structure by Bi-bilayers lying deep inside bulk Bi2Se3.

We observe the modified surface states of an epitaxial thin film of a homologous series of (Bi2)m(Bi2Se3)n, as a topological insulator (TI), by angle-resolved photoemission spectroscopy measurements. A thin film with m : n = 1 : 3 (Bi8Se9) has been grown with Bi2 bilayers embedded every other three quintuple layers (QLs) of Bi2Se3. Despite the reduced dimension of continuous QLs due to the Bi2 heterolayers, we find that the topological surface states stem from the inverted Bi and Se states and the topologically nontrivial structures are mainly based on the prototype of 3D TI Bi2Se3 without affecting the overall topological order.

Enhancement of Photo-Oxidation Activities Depending on Structural Distortion of Fe-Doped TiO2 Nanoparticles.

To design a high-performance photocatalytic system with TiO2, it is necessary to reduce the bandgap and enhance the absorption efficiency. The reduction of the bandgap to the visible range was investigated with reference to the surface distortion of anatase TiO2 nanoparticles induced by varying Fe doping concentrations. Fe-doped TiO2 nanoparticles (Fe@TiO2) were synthesized by a hydrothermal method and analyzed by various surface analysis techniques such as transmission electron microscopy, Raman spectroscopy, X-ray diffraction, scanning transmission X-ray microscopy, and high-resolution photoemission spectroscopy. We observed that Fe doping over 5 wt.% gave rise to a distorted structure, i.e., Fe2Ti3O9, indicating numerous Ti(3+) and oxygen-vacancy sites. The Ti(3+) sites act as electron trap sites to deliver the electron to O2 as well as introduce the dopant level inside the bandgap, resulting in a significant increase in the photocatalytic oxidation reaction of thiol (-SH) of 2-aminothiophenol to sulfonic acid (-SO3H) under ultraviolet and visible light illumination.

Friction and conductance imaging of sp(2)- and sp(3)-hybridized subdomains on single-layer graphene oxide.

We investigated the subdomain structures of single-layer graphene oxide (GO) by characterizing local friction and conductance using conductive atomic force microscopy. Friction and conductance mapping showed that a single-layer GO flake has subdomains several tens to a few hundreds of nanometers in lateral size. The GO subdomains exhibited low friction (high conductance) in the sp(2)-rich phase and high friction (low conductance) in the sp(3)-rich phase. Current-voltage spectroscopy revealed that the local current flow in single-layer GO depends on the quantity of hydroxyl and carboxyl groups, and epoxy bridges within the 2-dimensional carbon layer. The presence of subdomains with different sp(2)/sp(3) carbon ratios on a GO flake was also confirmed by chemical mapping using scanning transmission X-ray microscopy. These results suggest that spatial mapping of the friction and conductance can be used to rapidly identify the composition of heterogeneous single-layer GO at nanometer scale, which is essential for understanding charge transport in nanoelectronic devices.

Proximity Effect Induced Electronic Properties of Graphene on Bi2Te2Se.

We report that the π-electrons of graphene can be spin-polarized to create a phase with a significant spin-orbit gap at the Dirac point (DP) using a graphene-interfaced topological insulator hybrid material. We have grown epitaxial Bi2Te2Se (BTS) films on a chemical vapor deposition (CVD) graphene. We observe two linear surface bands from both the CVD graphene notably flattened and BTS coexisting with their DPs separated by 0.53 eV in the photoemission data measured with synchrotron photons. We further demonstrate that the separation between the two DPs, Δ(D-D), can be artificially fine-tuned by adjusting the amount of Cs atoms adsorbed on the graphene to a value as small as Δ(D-D) = 0.12 eV to find any proximity effect induced by the DPs. Our density functional theory calculation shows the opening of a spin-orbit gap of ∼20 meV in the π-band, enhanced by 3 orders of magnitude from that of a pristine graphene, and a concomitant phase transition from a semimetallic to a quantum spin Hall phase when Δ(D-D) ≤ 0.20 eV. We thus present a practical means of spin-polarizing the π-band of graphene, which can be pivotal to advance graphene-based spintronics.

Comparative study of photocatalytic activities of hydrothermally grown ZnO nanorod on Si(001) wafer and FTO glass substrates.

ZnO nanorods have been grown on Si(001) wafer and fluorine-doped tin oxide (FTO) glass substrates for 1 and 4 h with the hydrothermal methods. The morphologies and photocatalytic activities of the ZnO nanorods were found to depend on the substrates. We investigated their properties by using spectroscopic analysis and demonstrated that the shape of nanorod and the ratios of external defects can be controlled by varying the substrates. Our experiments revealed that the nanorods grown on Si(001) have a single-crystalline wurtzite structure with (002) facets and that the number of surface oxygen defects increases with their length as the growth time increases. The nanorods grown on Si(001) have different facets, in particular wider (002) facets, and a higher ratio of the oxygen defect than the nanorods on FTO glass substrate. Moreover, the photocatalytic activities with respect to 2-aminothiophenol (2-ATP) of these nanorods were investigated with high-resolution photoemission spectroscopy (HRPES). We demonstrated that their photocatalytic activity is influenced by the ratios of surface oxygen defects, which varies with the substrate surface.

Persistent topological surface state at the interface of Bi2Se3 film grown on patterned graphene.

We employed graphene as a patternable template to protect the intrinsic surface states of thin films of topological insulators (TIs) from environment. Here we find that the graphene provides high-quality interface so that the Shubnikov de Haas (SdH) oscillation associated with a topological surface state could be observed at the interface of a metallic Bi2Se3 film with a carrier density higher than ∼ 10(19) cm(-3). Our in situ X-ray diffraction study shows that the Bi2Se3 film grows epitaxially in a quintuple layer-by-layer fashion from the bottom layer without any structural distortion by interfacial strain. The magnetotransport measurements including SdH oscillations stemming from multiple conductance channels reveal that the topological surface state, with the mobility as high as ∼ 0.5 m(2)/(V s), remains intact from the graphene underneath without degradation. Given that the graphene was prepatterned on arbitrary insulating substrates, the TI-based microelectronic design could be exploited. Our study thus provides a step forward to observe the topological surface states at the interface without degradation by tuning the interface between TI and graphene into a measurable current for device application.

Fast benchtop visualization of graphene grain boundaries using adhesive properties of defects.

Highly adhesive properties of graphene grain boundaries to permanganate lead to a very quick, easy and convenient method to visualize the grain boundaries simply using an optical microscope, which would be vital to improve specific properties of graphene.

Optical reflectivity and Raman scattering in few-layer-thick graphene highly doped by K and Rb.

We report the optical reflectivity and Raman scattering of few layer (L) graphene exposed to K and Rb vapors. Samples many tens of layers thick show the reflectivity and Raman spectra of the stage 1 bulk alkali intercalation compounds (GICs) KC(8) and RbC(8). However, these bulk optical and Raman properties only begin to appear in samples more than about 15 graphene layers thick. The 1 L to 4 L alkali exposed graphene Raman spectra are profoundly different than the Breit-Wigner-Fano (BWF) spectra of the bulk stage 1 compounds. Samples less than 10 layers thick show Drude-like plasma edge reflectivity dip in the visible; alkali exposed few layer graphenes are significantly more transparent than intrinsic graphene. Simulations show the in-plane free electron density is lower than in the bulk stage 1 GICs. In few layer graphenes, alkalis both intercalate between layers and adsorb on the graphene surfaces. Charge transfer electrically dopes the graphene sheets to densities near and above 10(+14) electrons/cm(2). New intrinsic Raman modes at 1128 and 1264 cm(-1) are activated by in-plane graphene zone folding caused by strongly interacting, locally crystalline alkali adlayers. The K Raman spectra are independent of thickness for L = 1-4, indicating that charge transfer from adsorbed and intercalated K layers are similar. The Raman G mode is downshifted and significantly broadened from intrinsic graphene. In contrast, the Rb spectra vary strongly with L and show increased doping by intercalated alkali as L increases. Rb adlayers appear to be disordered liquids, while intercalated layers are locally crystalline solids. A significant intramolecular G mode electronic resonance Raman enhancement is observed in K exposed graphene, as compared with intrinsic graphene.

Synthesis and electrical characterization of magnetic bilayer graphene intercalate.

We report synthesis and transport properties of the minimal graphite intercalation compound, a ferric chloride (FeCl(3))(n) island monolayer inside bilayer graphene. Chemical doping by the intercalant is simultaneously probed by micro-Raman spectroscopy and Hall measurements. Quantum oscillations of conductivity originate from microscopic domains of intercalated and unintercalated regions. A slight upturn in resistance related to magnetic transition is observed. Two-dimensional intercalation in bilayer graphene opens new possibilities to engineer two-dimensional properties of intercalates.

Raman enhancement on graphene: adsorbed and intercalated molecular species.

Strong Raman scattering is observed from iodine anions adsorbed at ca. 3% coverage on single layer graphene. In addition, the Raman signal from just one bromine intercalation layer inside three and four layer thick graphenes is observed. We analyze and model the intramolecular electronic, charge-transfer, and multiple reflection electromagnetic mechanisms responsible for this unusual sensitivity. Graphene is an excellent Raman substrate for adsorbed species showing intramolecular electronic resonance, because graphene efficiently quenches interfering excited-state luminescence. The Raman sensitivity for adsorbed and intercalated molecular species is highest for single layer graphene and decreases with increasing thickness. These phenomena are compared with surface enhanced Raman spectroscopy field enhancement and "chemical" Raman processes in aggregated Ag particles and on flat, highly reflective metal surfaces. The Raman spectra of adsorbed bromine layers are not observed, despite significant charge transfer to graphene. Charge transfer from adsorbed bromine is about one-half of charge transfer from intercalated bromine. We attribute the large Raman signal for both adsorbed iodine and intercalated bromine species to intramolecular electronic resonance enhancement. The signal evolution with varying graphene thickness is explained by multiple reflection electromagnetic calculations.

Charge transfer chemical doping of few layer graphenes: charge distribution and band gap formation.

The properties of few layer (one layer (1 L) to four layer (4 L)) graphenes doped by adsorption and intercalation of Br(2) and I(2) vapors are investigated. The Raman spectra of the graphene G vibrations are observed as a function of the number of layers. There is no evidence for chemical reaction disrupting the basal plane pi electron conjugation. Adsorption of bromine on 1 L graphene creates a high doped hole density, well beyond that achieved by electrical gating with an ionic polymer electrolyte. In addition, the 2D Raman band is completely quenched. The 2 L bilayer spectra indicate that the doping by adsorbed I(2) and Br(2) is symmetrical on the top and bottom layers. Br(2) intercalates into 3 L and 4 L graphenes. The combination of both surface and interior doping with Br(2) in 3 L and 4 L creates a relatively constant doping level per layer. In contrast, the G spectra of 3 L and 4 L with surface adsorbed I(2) indicate that the hole doping density is larger on the surface layers than on the interior layers and that I(2) does not intercalate into 3 L and 4 L. This adsorption-induced potential difference between surface and interior layers implies that a band gap opens in the bilayer type bands of 3 L and 4 L.