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At least 163 records · Page 9

Stable Carbon-Selenium Bonds for Enhanced Performance in Tremella -Like 2D Chalcogenide Battery Anode [Stable Carbon-Selenium Bonds for Enhanced Performance in Tremella -Like Two-Dimensional Chalcogenide Battery Anode]

Two-dimensional cobalt selenide based on conversion reaction has attracted much attention due to its open layered structure and high specific capacity. However, effectively suppressing the fast capacity fade caused by the irreversible Se dissolution and serious volume change during the cycling process is still a challenges. Herein, we tune the concentration of dispersion liquid under supercritical condition to induce the CoSe crystal to grow along the graphene oxide (GO), and finally obtain the Tremella -like CoSe-rGO hybrid. The nature of epitaxial growth leads to the formation of stable C–Se bonds, which maintains favorable conductive connection between CoSe and reduced GO (rGO) as well as enhances the mechanical strength of active material to suppress Se dissolution and volume expansion during Na/Li intercalation and deintercalation. The unique microstructural merits of the hybrid result in superior sodium/lithium storage performance (400.8 mAh g -1 at 1 A g -1 after 100 cycles for NIBs and 769.6 mAh g -1 at 2 A g -1 after 500 cycles for LIBs). Moreover, the transmission X-ray microscopy technique is firstly used to directly observe the Se segregation in cobalt selenide and it being suppressed by the C–Se bonds.

25 ENERGY STORAGE↗

Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

M(TpyNO 2 )(NO 3 ) 3 (H 2 O)·THF (M = La, Ce, Nd, Sm, Eu, Am; TpyNO 2 = 4’-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO 3 ) 3 ·nH 2 O with TpyNO 2 in THF. Structural analysis shows that the metal centers are ten-coordinate, providing the first example of Am III with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the Am III complex. Comparison of Nd‒L, Eu‒L, and Am‒L bond distances demonstrates that some caution should be taken in comparing Eu III versus Am III in extraction experiments.

anions↗

Relativistic effects for the reaction Sg + 6 CO → Sg(CO){sub 6}: Prediction of the mean bond energy, atomization energy, and existence of the first organometallic transactinide superheavy hexacarbonyl Sg(CO){sub 6}

Our ab initio all-electron fully relativistic Dirac–Fock (DF) and nonrelativistic (NR) Hartree-Fock calculations predict the DF relativistic and NR energies for the reaction: Sg + 6 CO → Sg(CO){sub 6} as −7.39 and −6.96 eV, respectively, i.e., our calculated ground state total DF relativistic and NR energies for the reaction product Sg(CO){sub 6} are lower by 7.39 and 6.96 eV than the total DF and NR ground state energies of the reactants, viz., one Sg atom plus six CO molecules, respectively. Our calculated DF relativistic and NR atomization energies (Ae) are 65.23 and 64.82 eV, respectively, and so the contribution of relativistic effects to the Ae of ∼0.40 eV is marginal. The Sg–C and C–O optimized bond distances for the octahedral geometry as calculated in our DF (NR) calculations are 2.151 (2.318 Å) and 1.119 (1.114 Å), respectively. The BSSE correction calculated using the DIRAC code ∼14 kcal/mol. The relativistic DF and NR mean energies predicted by us are 118.8 and 111.9 kJ/mol, respectively, and the contribution of ∼7 kJ/mol due to relativistic effects to the mean energy of Sg(CO){sub 6} is negligible. Ours are the first calculations of the relativistic effects for the atomization energy, mean bond energy, and energy of the reaction for possible formation of Sg(CO){sub 6}, and both our relativistic DF and the NR treatments clearly predict for the first time the existence of hexacarbonyl of the transactinide superheavy element seaborgium Sg. In conclusion, relativistic effects are not significant for Sg(CO){sub 6}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Abnormal variation of band gap in Zn doped Bi{sub 0.9}La{sub 0.1}FeO{sub 3} nanoparticles: Role of Fe-O-Fe bond angle and Fe-O bond anisotropy

Bi{sub 0.9}La{sub 0.1}FeO{sub 3} (BLFO) and Bi{sub 0.9}La{sub 0.1}Fe{sub 0.99}Zn{sub 0.01}O{sub 3} (BLFZO) nanoparticles were prepared via a sol-gel method. The oxygen vacancies and holes increase with Zn doping analyzed through X-ray photoelectron spectroscopy, which could contribute to the increase of leakage current density. However, with the increase of the defects (oxygen vacancies and holes), the band gap of BLFZO also is increased. To explain the abnormal phenomenon, the bandwidth of occupied and unoccupied bands was analyzed based on the structural symmetry driven by the Fe-O-Fe bond angle and Fe-O bond anisotropy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds Using Isotopic Labeling

Abstract: Surface functionalization of two-dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced here is a mild, surface-specific protocol for the surface functionalization of few-layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational (infrared, Raman), Xray (emission, photoelectron), CPMAS NMR, and UV-vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15N-labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

Walz, Kendall↗

Fabrication of highly dense isotropic Nd-Fe-B nylon bonded magnets via extrusion-based additive manufacturing [Fabrication of highly dense isotropic Nd-Fe-B bonded magnets via extrusion-based additive manufacturing]

Magnetically isotropic bonded magnets with a high loading fraction of 70 vol.% Nd-Fe-B are fabricated via an extrusion-based additive manufacturing, or 3D printing system that enables rapid production of large parts. The density of the printed magnet is ~5.2 g/cm 3 . The room temperature magnetic properties are: intrinsic coercivity H ci = 8.9 kOe (708.2 kA/m), remanence B r = 5.8 kG (0.58 T), and energy product (BH)max = 7.3 MGOe (58.1 kJ/m 3 ). The as-printed magnets are then coated with two types of polymers, both of which improve the thermal stability as revealed by flux aging loss measurements. Tensile tests performed at 25 °C and 100 °C show that the ultimate tensile stress (UTS) increases with increasing loading fraction of the magnet powder, and decreases with increasing temperature. AC magnetic susceptibility and resistivity measurements show that the 3D printed Nd-Fe-B bonded magnets exhibit extremely low eddy current loss and high resistivity. Lastly, we demonstrate the performance of the 3D printed magnets in a DC motor configuration via back electromotive force measurements.

36 MATERIALS SCIENCE↗

Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides

In this paper, we describe the solid-state structural evolution in four hybrid hexaiodoplatinate(IV) compounds, demonstrating the increasingly important role that extended hydrogen bonding plays in directing the structure across the series. The compounds are A 2 PtI 6 , where A is one of the following amines: ammonium, NH 4 + ; methylammonium, CH 3 NH 3 + ; formamidinium, CH(NH 2 ) 2 + ; guanidinium, C(NH 2 ) 3 + . These are closely related in structure and properties to the hybrid halide perovskites of lead(II) that have recently established their prowess in optoelectronics. The first three of these compounds crystallize in the vacancy-ordered double perovskite A 2 Pt$\square$I 6 ($\square$ indicates a vacant site) structure in the K 2 PtCl 6 archetype, despite the relatively large perovskite tolerance factors involved. The last compound, (GUA) 2 PtI 6 , crystallizes in a vacancy-ordered variant of the hexagonal CsNiCl 3 structure: the K 2 MnF 6 structure. A combination of solid-state 195 Pt and 1 H NMR spectroscopy and detailed density functional theory calculations helps to reveal structural trends and establish the hydrogen-bonding tendencies. Finally, the calculations and measured optical properties support the surprising observation in these iodosalt compounds that, for smaller A cations, the conduction bands are considerably disperse, despite lacking extended I–Pt–I connectivity.

36 MATERIALS SCIENCE↗

Quasi-Atomic Bond Analyses in the Sixth Period: II. Bond Analyses of Cerium Oxides

The role of the 4f orbitals in bonding is examined for the molecules cerium monoxide and cerium dioxide that have cerium formally in the +2 and +4 oxidation states, respectively. It is demonstrated that the 4f orbitals are used primarily for polarization of the 5d orbitals when cerium is in the lower oxidation state, while the 4f orbitals play a critical role in chemical bonding via 5d/4f hybridization when cerium is in the +4 oxidation state.

74 ATOMIC AND MOLECULAR PHYSICS↗

Resolving the Impact of Hydrogen Bonding on the Phylloquinone Cofactor through Two-Dimensional Infrared Spectroscopy

Phylloquinone (PhQ) is a molecule involved in photosynthetic electron transfer, where the local protein environment is known to tune the properties of PhQ through various noncovalent interactions. In this work, we determine how hydrogen bonding, one of these noncovalent interactions, alters the vibrational potential energy surface of PhQ. In addition, this work demonstrates how hydrogen bonding to PhQ manifests in ultrafast multidimensional vibrational spectra, which is an important step towards using ultrafast vibrational based spectroscopies to probe PhQ embedded in the binding pocket of photosynthetic reaction centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing Hydrogen-Bonding Interactions of Water Molecules Adsorbed on Silica, Sodium Calcium Silicate, and Calcium Aluminosilicate Glasses

Vibrational sum frequency generation (SFG) spectroscopy was used to study how hydrogen bonding interactions of physisorbed water layers vary with the glass composition and surface condition. Three different glass materials were used: amorphous silica (fused quartz), sodium calcium silicate (also called soda lime silica), and calcium aluminosilicate (boron-/fluorine-free E-glass). Two different surface conditions were compared: (i) a mechanically polished, fire-polished, and then annealed surface and (ii) an acid-leached surface (pH 1, 90 °C, 24 h). Compositional and structural information obtained by X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and attenuated total reflection infrared spectroscopy were correlated with SFG spectral features. The temperature dependence of SFG spectral features revealed that regardless of the glass composition, the glass surface is free of physisorbed water at 250 °C, and during cooling in ambient air, it starts absorbing water at a temperature corresponding to a relative humidity of 1–2%. Humidity-controlled SFG measurements at room temperature showed that the hydrogen bonding interactions of water physisorbed on the glass surface cleaned with UV/O 3 are quite different depending on the glass composition and surface preparation history. This finding will be useful in understanding how surface properties of different glasses are altered by humidity in ambient air.

36 MATERIALS SCIENCE↗