Efficient Hydrogen Isotope Separation by Tunneling Effect Using Graphene-Based Heterogeneous Electrocatalysts in Electrochemical Hydrogen Isotope Pumping.

The fabrication of a hydrogen isotope enrichment system is essential for the development of industrial, medical, life science, and nuclear fusion fields, and therefore, efficient enrichment techniques with a high separation factor and economic feasibility are still being explored. Herein, we report a hydrogen/deuterium (H/D) separation ability with polymer electrolyte membrane electrochemical hydrogen pumping (PEM-ECHP) using a heterogeneous electrode consisting of palladium and graphene layers (PdGr). By mass spectroscopic analysis, we demonstrate significant bias voltage dependence of the H/D separation factor with a maximum of ∼25 at 0.15 V and room temperature, which is superior to those of conventional separation methods. Theoretical analysis demonstrated that the observed high H/D factor stems from tunneling of hydrogen isotopes through atomically thick graphene during the electrochemical reaction and that the bias dependence of H/D results from a transition from the quantum tunneling regime to the classical overbarrier regime for hydrogen isotopes transfer through the graphene. These findings will help us understand the origin of the isotope separation ability of graphene discussed so far and contribute to developing an economical hydrogen isotope enrichment system using two-dimensional materials.

Probing Copper and Copper-Gold Alloy Surfaces with Space-Quantized Oxygen Molecular Beam.

The orientation and motion of reactants play important roles in reactions. The small rotational excitations involved render the reactants susceptible to dynamical steering, making direct comparison between experiments and theory rather challenging. Using space-quantized molecular beams, we directly probed the (polar and azimuthal) orientation dependence of O2 chemisorption on Cu(110) and Cu3Au(110). We observed polar and azimuthal anisotropies on both surfaces. Chemisorption proceeded rather favorably with the O-O bond axis oriented parallel (vs perpendicular) to the surface and rather favorably with the O-O bond axis oriented along [001] (vs along [1̅10]). The presence of Au hindered the surface from further oxidation, introducing a higher activation barrier to chemisorption and rendering an almost negligible azimuthal anisotropy. The presence of Au also prevented the cartwheel-like rotations of O2.

Defluorination and adsorption of tetrafluoroethylene (TFE) on TiO2(110) and Cr2O3(0001).

Here, we show that metal oxide surfaces catalyze the formation of intermediate defluorinated tetrafluoroethylene (TFE) radicals, resulting in enhanced binding on the corresponding metal oxide surfaces. We attribute the preferential adsorption and radical formation of TFE on Cr2O3(0001) relative to TiO2(110) to the low oxygen coordination of Cr surface atoms. This hints at a possible dependence of the TFE binding strength to the surface stoichiometry of metal-oxide surfaces.

Interface atom mobility and charge transfer effects on CuO and Cu2O formation on Cu3Pd(111) and Cu3Pt(111).

We bombarded [Formula: see text] and [Formula: see text] with a 2.3 eV hyperthermal oxygen molecular beam (HOMB) source, and characterized the corresponding (oxide) surfaces with synchrotron-radiation X-ray photoemission spectroscopy (SR-XPS). At [Formula: see text], CuO forms on both [Formula: see text] and [Formula: see text]. When we increase the surface temperature to [Formula: see text], [Formula: see text] also forms on [Formula: see text], but not on [Formula: see text]. For comparison, [Formula: see text] forms even at [Formula: see text] on Cu(111). On [Formula: see text], [Formula: see text] forms only after [Formula: see text], and no oxides can be found at [Formula: see text]. We ascribe this difference in Cu oxide formation to the mobility of the interfacial species (Cu/Pd/Pt) and charge transfer between the surface Cu oxides and subsurface species (Cu/Pd/Pt).

Dynamical Quantum Filtering via Enhanced Scattering of para-H2 on the Orientationally Anisotropic Potential of SrTiO3(001).

Quantum dynamics calculation, performed on top of density functional theory (DFT)-based total energy calculations, show dynamical quantum filtering via enhanced scattering of para-H2 on SrTiO3(001). We attribute this to the strongly orientation-dependent (electrostatic) interaction potential between the H2 (induced) quadrupole moment and the surface electric field gradient of ionic SrTiO3(001). These results suggest that ionic surfaces could function as a scattering/filtering media to realize rotationally state-resolved H2. This could find significant applications not only in H2 storage and transport, but also in realizing materials with pre-determined characteristic properties.

Positive and negative hydrogen ion reflections of low-energy atomic and molecular hydrogen ion beam from HOPG and Mo surfaces.

Positive and negative hydrogen ion reflections from surfaces by injecting singly charged hydrogen ion beams show a clear difference between atomic and molecular ion injections at low energy and grazing incidence. The intensity ratio of reflected negative to positive ions H-/H+ increased as the incident beam energy per nucleon decreased only when molecular ion beams are injected. It implies that negative ions are more produced upon beam-surface interaction when molecules are injected. A possible reason was discussed in terms of difference in the negative ion production processes between atomic and molecular ions.

Quantitative Multilayer Cu(410) Structure and Relaxation Determined by QLEED.

Industrially relevant catalytically active surfaces exhibit defects. These defects serve as active sites; expose incoming adsorbates to both high and low coordinated surface atoms; determine morphology, reactivity, energetics, and surface relaxation. These, in turn, affect crystal growth, oxidation, catalysis, and corrosion. Systematic experimental analyses of such surface defects pose challenges, esp., when they do not exhibit order. High Miller index surfaces can provide access to these features and information, albeit indirectly. Here, we show that with quantitative low-energy electron diffraction (QLEED) intensity analyses and density functional theory (DFT) calculations, we can visualize the local atomic configuration, the corresponding electron distribution, and local reactivity. The QLEED-determined Cu(410) structure (Pendry reliability factor RP ≃ 0.0797) exhibits alternating sequences of expansion (+) and contraction (-) (of the first 16 atomic interlayers) relative to the bulk-truncated interlayer spacing of ca. 0.437 Å. The corresponding electron distribution shows smoothening relative to the bulk-determined structure. These results should aid us to further gain an atomic-scale understanding of the nature of defects in materials.

Density functional study of methyl butanoate adsorption and its C-O bonds cleavage on MoS2-based catalyst with various loads of Ni promoters.

Due to the increasing demands of new and renewable energy sources by utilising plant oils, uncovering the underlying physico-chemical phenomena at the atomic level responsible for the effective deoxygenation plays a vital role in improving the performance of well-known as well as in looking for the possible new catalysts. This study aims at investigating the adsorption and C-O bonds cleavage of methyl butanoate (MB) over MoS2-based catalyst with various loads of Ni promoters by using first-principles density functional theory (DFT). This study employs surface model that never been used by previous researchers for their investigations of adsorption and bonds cleavage on Ni promoted MoS2-based catalysts. The introduction of nickel into MoS2-based catalyst allows the surface charges when interacts with MB to redistribute in such a way that induces stronger Coulombic attractive forces. This in turn could result in a more stable adsorption configuration. However only in certain Ni-loads will results in the most stable adsorption. Nevertheless the most stable adsorption of MB occurs on M-edge configuration which consists of two Ni atoms, i.e. M-2-Ni-A with adsorption energy at about -2.96 eV. As a comparison, the adsorption energy of MoS2 with the absent of Ni, i.e. M-0-Ni is just -2.79 eV. Since there are three C-O bonds in MB, this study proposes three possible reactions for these bonds to cleave. By using CI-NEB method, the activation energies of those three reaction are calculated. It shows that the presence of Ni with appropriate load could promote C-O bond cleavage, especially in one reaction C-O bond is weaken considerably. Further evaluation on bond dissociation energies of the closest C-C bond to the catalyst surface, M-2-Ni-A shows better reactivity on C-C bond cleavage than M-0-Ni, disregarding of those three reaction routes.

Spin-Dependent O2 Binding to Hemoglobin.

We report results of our study on the mechanism of spin-dependent O2 binding to hemoglobin, which we represent as FePIm (Fe = iron, P = porphyrin, Im = imidazole). This involves the transition between two states, viz., the oxyhemoglobin state and the deoxyhemoglobin state. The deoxyhemoglobin state pertains to FePIm and a free O2 molecule, while the oxyhemoglobin state pertains to an O2 bound to FePIm. The deoxyhemoglobin and oxyhemoglobin systems have triplet and singlet total magnetizations, respectively. We found that a spin transition from triplet to quintet to singlet mediates the O2 binding process, and this accelerates the reaction. We also found that the position of the Fe atom out of the porphyrin plane is an important indicator of O2 affinity.

Experimental and Theoretical Studies on Oxidation of Cu-Au Alloy Surfaces: Effect of Bulk Au Concentration.

We report results of our experimental and theoretical studies on the oxidation of Cu-Au alloy surfaces, viz., Cu3Au(111), CuAu(111), and Au3Cu(111), using hyperthermal O2 molecular beam (HOMB). We observed strong Au segregation to the top layer of the corresponding clean (111) surfaces. This forms a protective layer that hinders further oxidation into the bulk. The higher the concentration of Au in the protective layer formed, the higher the protective efficacy. As a result, of the three Cu-Au surfaces studied, Au3Cu(111) is the most stable against dissociative adsorption of O2, even with HOMB. We also found that this protective property breaks down for oxidations occurring at temperatures above 300 K.

Initial stages of Cu3Au(111) oxidation: oxygen induced Cu segregation and the protective Au layer profile.

We report results of our experimental and theoretical studies on the Au concentration profile of Cu3Au(111) during oxidation by a hyperthermal O2 molecular beam at room temperature, using X-ray photoemission spectroscopy (XPS), in conjunction with synchrotron radiation (SR), and density functional theory (DFT). Before O2 exposure, we observe strong Au segregation to the top layer, i.e., Au surface enrichment of the clean surface. We also observe a gradual Cu surface enrichment, and Au enrichment of the second and third (subsurface) layers, with increasing O coverage. Complete Cu segregation to the surface occurs at 0.5 ML O surface coverage. The Au-rich second and third layers of the oxidized surface demonstrate the protective layer formation against oxidation deeper into the bulk.

Magnetic domain patterns on strong perpendicular magnetization of Co/Ni multilayers as spintronics materials: I. Dynamic observations.

Materials with perpendicular magnetic anisotropy can reduce the threshold current density of the current-induced domain wall motion. Co/Ni multilayers show strong perpendicular magnetic anisotropy and therefore it has become a highly potential candidate of current-induced domain wall motion memories. However, the details of the mechanism which stabilizes the strong perpendicular magnetization in Co/Ni multilayers have not yet been understood. In the present work, the evolution of the magnetic domain structure of multilayers consisting of pairs of 2 or 3 monolayers (ML) of Ni and 1 ML of Co on W(110) was investigated during growth with spin-polarized low-energy electron microscopy. An interesting phenomenon, that the magnetic domain structure changed drastically during growth, was revealed. In the early stages of the growth the magnetization alternated between in-plane upon Co deposition and out-of-plane upon Ni deposition. The change of the magnetization direction occurred within a range of less than 0.2 ML during Ni or Co deposition, with break-up of the existing domains followed by growth of new domains. The Ni and Co thickness at which the magnetization direction switched shifted gradually with the number of Co/Ni pairs. Above 3-4 Co/Ni pairs it stayed out-of-plane. The results indicate clearly that the Co-Ni interfaces play the important role of enhancing the perpendicular magnetic anisotropy.

Magnetic domain patterns on strong perpendicular magnetization of Co/Ni multilayers as spintronics materials: II. Numerical simulations.

Magnetic domains in ultrathin films form domain patterns, which strongly depend on the magnetic anisotropy. The magnetic anisotropy in Co/Ni multilayers changes with the number of layers. We provide a model to simulate the experimentally observed domain patterns. The model assumes a layer-dependent magnetic anisotropy. With the anisotropy parameter estimated from experimental data, we reproduce the magnetic domain patterns.