Methylboronic acid MIDA ester (ADM) as an effective additive in electrolyte to improve cathode electrolyte interlayer performance of LiNi0.8Co0.15Al0.05O2 electrode.

We investigated the effectiveness of using methylboronic acid MIDA ester (ADM) as an additive in an electrolyte to enhance the overall electrochemical and material properties of an LNCAO (LiNi0.8Co0.15Al0.05O2) cathode. The cyclic stability of the cathode material measured at 40 °C (@ 0.2 C) showed an enhanced capacity of 144.28 mAh g-1 (@ 100 cycles), a capacity retention of 80%, and a high coulombic efficiency (99.5%), in contrast to these same properties without the electrolyte additive (37.5 mAh g-1, ~ 20%, and 90.4%), thus confirming the effectiveness of the additive. A Fourier transform infrared spectroscopy (FTIR) analysis distinctly showed that the ADM additive suppressed the EC-Li+ ion coordination (1197 cm-1 and 728 cm-1) in the electrolyte, thereby improving the cyclic performance of the LNCAO cathode. The cathode after 100 charge/discharge cycles revealed that the ADM-containing system exhibited better surface stability of the grains in the LNCAO cathode, whereas distinct cracks were observed in the system without the ADM in the electrolyte. A transmission electron microscopy (TEM) analysis revealed the presence of a thin, uniform and dense cathode electrolyte interface (CEI) film on the surface of LNCAO cathode. An operando synchrotron X-ray diffraction (XRD) test identified the high structural reversibility of the LNCAO cathode with a CEI layer formed by the ADM, which effectively maintained the structural stability of the layered material. The additive effectively inhibited the decomposition of electrolyte compositions, as confirmed by X-ray photoelectron spectroscopy (XPS).

Bis(acetyl-acetonato-κO,O')(pyridine-κN)zinc(II).

In the title compound, [Zn(C(5)H(7)O(2))(2)(C(5)H(5)N)], the metal atom has square-pyramidal coordination geometry with the basal plane defined by the four O atoms of the chelating acetyl-acetonate ligands and with the axial position occupied by the pyridine N atom. The crystal packing is characterized by a C-H⋯O hydrogen-bonded ribbon structure approximately parallel to [10[Formula: see text]].

Synergistic effects of Ga doping and Mg alloying over the enhancement of the stress sensitivity of a Ga-doped MgZnO pressure sensor.

We demonstrate the synergistic effects of Ga doping and Mg alloying into ZnO on the large enhancement of the piezopotential and stress sensing performance of piezotronic pressure sensors made of Ga-doped MgZnO films. Piezopotential-induced pressure sensitivity was enhanced through the modulation of the Schottky barrier height. Doping with Ga (0.62 Å) of larger ionic radius and alloying with Mg (0.57 Å) of smaller ionic radius than Zn ions can synergistically affect the overall structural, optical and piezoelectric properties of the resulting thin films. The crystal quality of Ga-doped MgZnO films either improved (X Ga ≦ 0.041) or deteriorated (X Ga ≧ 0.041) depending on the Ga doping concentration. The band gap increased from 3.90 eV for pristine MgZnO to 3.93 eV at X Ga = 0.076, and the piezoelectric coefficient (d 33) improved from ∼23.25 pm V-1 to ∼33.17 pm V-1 at an optimum Ga concentration (X Ga = 0.027) by ∼2.65 times. The change in the Schottky barrier height ΔΦ b increased from -4.41 meV (MgZnO) to -4.81 meV (X Ga = 0.027) and decreased to -3.99 meV at a high Ga doping concentration (X Ga = 0.041). The stress sensitivity (0.2 kgf) enhanced from 28.50 MPa-1 for the pristine MgZnO to 31.36 MPa-1 (X Ga = 0.027) and decreased to 25.56 MPa-1 at higher Ga doping concentrations, indicating the synergistic effects of Ga doping and Mg alloying over the pressure sensing performance of Ga-doped MgZnO films.

MoS2-Carbon Inter-overlapped Structures as Effective Electrocatalysts for the Hydrogen Evolution Reaction.

The ability to generate hydrogen in an economic and sustainable manner is critical to the realization of a future hydrogen economy. Electrocatalytic water splitting into molecular hydrogen using the hydrogen evolution reaction (HER) provides a viable option for hydrogen generation. Consequently, advanced non-precious metal based electrocatalysts that promote HER and reduce the overpotential are being widely researched. Here, we report on the development of MoS2-carbon inter-overlapped structures and their applicability for enhancing electrocatalytic HER. These structures were synthesized by a facile hot-injection method using ammonium tetrathiomolybdate ((NH4)2MoS4) as the precursor and oleylamine (OLA) as the solvent, followed by a carbonization step. During the synthesis protocol, OLA not only plays the role of a reacting solvent but also acts as an intercalating agent which enlarges the interlayer spacing of MoS2 to form OLA-protected monolayer MoS2. After the carbonization step, the crystallinity improves substantially, and OLA can be completely converted into carbon, thus forming an inter-overlapped superstructure, as characterized in detail using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). A Tafel slope of 118 mV/dec is obtained for the monolayer MoS2-carbon superstructure, which shows a significant improvement, as compared to the 202 mV/dec observed for OLA-protected monolayer MoS2. The enhanced HER performance is attributed to the improved conductivity along the c-axis due to the presence of carbon and the abundance of active sites due to the interlayer expansion of the monolayer MoS2 by OLA.

Strong correlation between optical properties and mechanism in deficiency of normalized self-assembly ZnO nanorods.

Although, post annealing is an efficient way to annihilate/restructure deficiencies in self-assembly (SA) ZnO nanorods (ZNRs), the detailed investigation about the surface properties of annealed SA-ZNRs is a long standing issue and the major discrepancy is mainly due to single step annealing. We demonstrate the strategic two step annealing process to create reliable structural configuration in SA-ZNRs during the first round of annealing at 800 °C in vacuum (VA process), and create intrinsic defects in the second step of annealing in oxygen rich atmosphere (OA process) to correlate the formation of the defects related to green/orange-red emission. SA-ZNRs annealed in VA-OA processes reveal positive correlations between the oxygen flow rate and formation of oxygen interstitials (Oi) and zinc vacancies (VZn). The OA-VA processes exhibit the relation of residual Oi and additional Vo. According to VA-OA and OA-VA processes, we propose that the green emission in ZnO annealed in oxygen poor/rich condition is mainly due to the formation of Vo/VZn and annealing at oxygen rich condition creates Oi that lead to strong orange-red emission. Rather than O1s, we propose a reliable method by considering the peak shift of Zn2p in XPS to inspect the ZnO matrix, which has good interdependence with the characteristics of PL.

Adducts of bis(acetylacetonato)zinc(II) with 1,10-phenanthroline and 2,2'-bipyridine.

In each of the zinc(II) complexes bis(acetylacetonato-kappa(2)O,O')(1,10-phenanthroline-kappa(2)N,N')zinc(II), [Zn(C(5)H(7)O(2))(2)(C(12)H(8)N(2))], (I), and bis(acetylacetonato-kappa(2)O,O')(2,2'-bipyridine-kappa(2)N,N')zinc(II), [Zn(C(5)H(7)O(2))(2)(C(10)H(8)N(2))], (II), the metal center has a distorted octahedral coordination geometry. Compound (I) has crystallographically imposed twofold symmetry, with Z' = 0.5. The presence of a rigid phenanthroline group precludes intramolecular hydrogen bonding, whereas the rather flexible bipyridyl ligand is twisted to form an intramolecular C-H...O interaction [the chelated bipyridyl ligand is nonplanar, with the pyridyl rings inclined at an angle of 13.4 (1) degrees]. The two metal complexes are linked by dissimilar C-H...O interactions into one-dimensional chains. The present study demonstrates the distinct effects of two commonly used ligands, viz. 1,10-phenanthroline and 2,2'-bipyridine, on the structures of metal complexes and their assembly.

Migration Energy Barriers for the Surface and Bulk of Self-Assembly ZnO Nanorods.

Post-annealing treatment is a necessary process to create/eliminate/repair defects in self⁻assembly (SA) metal oxide by providing enough thermal energy to the O atoms to overcome the migration energy barrier in ZnO. The height of migration energy barrier is dependent on the depth from the surface, which is hard to be estimated by theoretical calculations, as well as the optical analyses. SA ZnO nanorods (ZNRs) have high surface-to-volume ratio to provide complete picture between the optical and surface properties obtained by photoluminescence (PL) and ultraviolet/X-ray photoemission spectroscopy (UPS/XPS), which is used to investigate the evolution of structure and chemical states of the surface layers to reveal mutual agreement on all observations in PL, XPS, and UPS. We demonstrate variation of the surface structure of SA-ZNRs by scanning over a range of annealing temperatures and time to regulate the structure variation of SA-ZNRs, and their optical analyses agrees well with PL, XPS and UPS, which indicates the dependence of migration energy barriers on the depth from the surface of ZNR. The results reveal the well ZNRs formed at 570 °C and the further oxidation process and the formation of hydroperoxide on the Zn-rich surface of ZNRs at 640 °C.

Synthesis and characterization of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)] hybrid organic-inorganic complexes as solid metal organic precursors.

We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)]. Taking C10H14O4Zn0.7Cu0.3 (Z0.7C0.3AA) as an example, the crystals are composed of Z0.7C0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z0.7C0.3AA crystallizes in the monoclinic system, space group P21/n. The unit cell dimensions are a = 10.329(4) Å, b = 4.6947(18) Å, and c = 11.369(4) Å; the angles are α = 90°, ß = 91.881(6)°, and γ = 90°, the volume is 551.0(4) Å(3), and Z = 2. In this process, the M(ii) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O-M-O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z0.7C0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.

Crystal Orientation Dynamics of Collective Zn dots before Preferential Nucleation.

The island nucleation in the context of heterogeneous thin film growth is often complicated by the growth kinetics involved in the subsequent thermodynamics. We show how the evolution of sputtered Zn island nucleation on Si(111) by magnetron sputtering in a large area can be completely understood as a model system by combining reflective second harmonic generation (RSHG), a 2D pole figure with synchrotron X-ray diffraction. Zn dots are then oxidized on the surfaces when exposed to the atmosphere as Zn/ZnO dots. Derived from the RSHG patterns of Zn dots at different growth times, the Zn dots grow following a unique transition from kinetic to thermodynamic control. Under kinetic-favoring growth, tiny Zn dots prefer arranging themselves with a tilted c-axis to the Si(111) substrate toward any of the sixfold in-plane Si<110> directions. Upon growth, the Zn dots subsequently evolve themselves to a metastable state with a smaller tilting angle toward selective <110> directions. As the Zn dots grow over a critical size, they become most thermodynamically stable with the c-axis vertical to the Si(111) substrate. For a system with large lattice mismatch, small volume dots take kinetic pathways with insignificant deviations in energy barriers.