Novel energy-saving window coating based on F doped TiO2 nanocrystals with enhanced NIR shielding performance

To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR shielding materials for buildings is of great value. In this report, monodispersed F doped TiO₂ nanocrystals with an average size of 8.6 nm were synthesized as novel solar shielding materials for energy-saving windows. All the products adopted an anatase TiO₂ structure. After doping of F ions, the morphology of TiO₂ was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F⁻ ions into the lattice oxygen sites in the TiO₂ structure. The introduction of F⁻ ions generated free electrons and bulk Ti³⁺ in TiO₂ crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO₂ films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO₂ films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO₂ films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO₂ nanocrystals show a great potential to be used for energy-saving windows.     

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g^?1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li⁺ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.     

Enhanced electrochemical performance of LiNi0.8Co0.1Mn0.1O2 via titanium and boron co-doping

Titanium and boron are simultaneously introduced into LiNi_0.8Co_0.1Mn_0.1O₂ to improve the structural stability and electrochemical performance of the material. X-ray diffraction studies reveal that Ti⁴⁺ ion replaces Li⁺ ion and reduces the cation mixing; B³⁺ ion enters the tetrahedron of the transition metal layers and enlarges the distance of the [LiO₆] layers. The co-doped sample has spherical secondary particles with elongated and enlarged primary particles, in which Ti and B elements distribute uniformly. Electrochemical studies reveal the co-doped sample has improved rate performance (183.1 mAh·g^-1 at 1 C and 155.5 mAh·g^-1 at 10 C) and cycle stability (capacity retention of 94.7% after 100 cycles at 1 C). EIS and CV disclose that Ti and B co-doping reduces charge transfer impedance and suppresses phase change of LiNi_0.8Co_0.1Mn_0.1O_2.     

Investigation of corrosion properties with Ni–P/TiNO coating on aluminum alloy bipolar plates in proton exchange membrane fuel cell

Aluminum alloy bipolar plates have unique application potential in proton exchange membrane fuel cell (PEMFC) due to the characteristics of lightweight and low cost. However, extreme susceptibility to corrosion in PEMFC operation condition limits the application. To promote the corrosion resistance of aluminum alloy bipolar plates, a Ni–P/TiNO coating was prepared by electroless plating and closed field unbalanced magnetron sputter ion plating (CFUMSIP) technology on the 6061 Al substrate. The research results show that Ni–P interlayer improves the deposition effect of TiNO outer layer and increase the content of TiN and TiO_xN_y phases. Compared to Ni–P and TiNO single-layer coatings, the Ni–P/TiNO coating samples exhibited the lowest current density value of (1.10 ± 0.02) × 10^?6 A·cm^?2 in simulated PEMFC cathode environment. Additionally, potential cyclic polarization measurements were carried out aiming to evaluate the durability of the aluminum alloy bipolar plate during the PEMFC start-up/shut-up process. The results illustrate that the Ni–P/TiNO coating samples exhibit excellent stability and corrosion resistance.     

Stabilization and superconductivity of AlB2-type nonstoichiometric molybdenum diboride by Sc doping

Molybdenum diboride is unique among transition metal diborides because it exists in both hexagonal (AlB₂-type) and rhombohedral structures. However, it is difficult to stabilize the superconducting AlB₂-type phase, which requires either extreme synthesis condition or suitable chemical doping. Here we report the structural and physical properties of Sc-doped nonstoichiometric molybdenum diborides (Mo_0.95Sc_0.05)_1-xB₂ and (Mo_1-ySc_y)_0.71B₂ prepared by the common arc melting method. The AlB₂-type phase is found to form over wide ranges of 0 ≤ x ≤ 0.29 and 0.025 ≤ y ≤ 0.30 for the first time, and bulk superconductivity with T_c up to 7.9 K is observed. T_c increases with increasing x in the (Mo_0.95Sc_0.05)_1-xB₂ series, but evolves nonmonotonically with varying y in the (Mo_1-ySc_y)_0.71B₂ series. Despite this contrast, T_c of both borides follows nearly the same linear dependence on the electron-phonon coupling constant, suggesting that it is mainly controlled by the electron-phonon interaction. In addition, the stabilization of AlB₂-type structure is attributed to the decrease in the number of d electrons as a consequence of Sc doping, which suggests that a similar effect may be achieved by substituting Mo with other d electron-poorer metal elements.     

Mechanism for the hydrolysis resistance of aluminum nitride powder modified by boric acid

Aluminum nitride (AlN) ceramics are becoming cutting-edge materials for electronic information and communication. However, raw AlN hydrolyzed rapidly, and the high storage costs of this material prevent widespread application. In this study, raw AlN was modified by boric acid (H₃BO₃) at 30 °C to enhance hydrolysis resistance. Transmission electron microscope (TEM), X-ray diffraction (XRD), the magic angle spinning nuclear magnetic resonance (²⁷Al-MAS-NMR and ¹¹B-MAS-NMR), and the fourier transform infrared spectrometer (FTIR) were used to characterize the powder before and after treatment, and the mechanism of hydrolysis resistance was determined. Modification with 0.1 M boric acid did not change the crystal phase of the AlN particles. The modified powder did not hydrolyse at 90% humidity and 70° Celsius. In the presence of boric acid, a network structure of B–O–B linkages ([BO_n], n = 3 or 4) formed that was connected to the AlN core via chemical bonds of B–N–Al and B–O–Al. The protective 6 – 10 nm-thick layer that formed on the surface of the AlN crystal, prevented attack by water molecules and hindered the hydrolysis of aluminium nitride. This study provides an alternative means of preparing anti-hydrolysis AlN powders.     

Stability,reactivity and decomposition kinetics of surface passivated α-AlH3 crystals

As a novel high energy fuel, aluminum hydride (AlH₃) has great potential in the field of solid propellants because of its high hydrogen capacity, which can significantly improve the specific impulse of solid propellants. In order to improve the stability of α-AlH₃, hydrochloric acid has been used to stabilize AlH₃ and the stabilization mechanism has been investigated. Various characterization techniques including scanning electron microscopy, X-ray electron spectrometer, X-ray diffraction, thermal analysis, and vacuum stability test have been employed to investigate the morphology, crystal structure, thermal stability, and decomposition kinetics of raw and passivated α-AlH₃. The results showed that the honeycomb-like structures could be formed on the surface of α-AlH₃ after passivation. First of all, the initial decomposition temperatures of the passivated samples were slightly increased. In particular, for the optimized sample with 105 min passivation time (AlH₃-105min), the initial decomposition temperature (173.4 °C) is increased by 5.6 °C. Moreover, the total decomposition time (1652 min) is improved by about 50% than that of the raw sample (1098 min). Besides, the decomposition activation energies (E_a) of passivated samples are much higher than that of the raw sample (84.8 kJ mol^?1), in which the optimized sample (AlH₃-105min) reaches 107.1 kJ. mol^?1. The decomposition kinetics model may change from 3-D nucleation and nucleus growth model to 2-D nucleation and nucleus growth model. It demonstrates the passivated samples have a lower decomposition rate and higher thermal stability. The stabilization mechanism is as follows: removing the impurities on the surface and accelerating the hydrolysis reaction of AlH₃ to generate complete and dense oxide layers.     

Nitrogen-doped hierarchically porous carbon obtained via single step method for high performance supercapacitors

In the present work, nitrogen doped hierarchically activated porous carbon (APC) samples have been synthesized via single step scalable method using ethylene di-amine tetra acetic acid (EDTA) as precursor and KOH as activating agent. Activated porous carbons with different pore sizes have been developed by varying the activation temperature. SEM, TEM and SAXS analysis suggest that with variation of activation temperature, a hierarchical porous structure with interconnected meso-pore and micro pores has been achieved. The sufficiently high surface area of the synthesized materials provides active sites to enhance the diffusion of ions between the electrolyte and the carbon electrodes. The electrode prepared at 800 °C activated sample exhibited highest specific capacitance of 274 Fg^-1 in two electrode setup, at a current density of 0.1 Ag^-1 in 1 M aqueous H₂SO₄. Along with this, it showed maximum energy density of 9.5 Whkg^?1 at a power density of 64.5 Wkg^-1. The remarkable electrochemical performance reveals that the synthesized nitrogen doped activated carbon electrodes derived from EDTA can be tuned to have optimum pore structure and pore size distribution for better electrochemical performance, so it can be considered as a potential electrode material for applications in electrochemical energy storage.     

High performance H2 sensor based on rGO-wrapped SnO2–Pd porous hollow spheres

Hydrogen (H₂) sensors based on metal oxide semiconductors (MOS) are promising for many applications such as a rocket propellant, industrial gas and the safety of storage. However, poor selectivity at low analyte concentrations, and independent response on high humidity limit the practical applications. Herein, we designed rGO-wrapped SnO₂–Pd porous hollow spheres composite (SnO₂–Pd@rGO) for high performance H₂ sensor. The porous hollow structure was from the carbon sphere template. The rGO wrapping was via self-assembly of GO on SnO₂-based spheres with subsequent thermal reduction in H₂ ambient. This sensor exhibited excellently selective H₂ sensing performances at 390 °C, linear response over a broad concentration range (0.1–1000 ppm) with recovery time of only 3 s, a high response of ～8 to 0.1 ppm H₂ in a minute, and acceptable stability under high humidity conditions (e. g. 80%). The calculated detection limit of 16.5 ppb opened up the possibility of trace H₂ monitoring. Furthermore, this sensor demonstrated certain response to H₂ at the minimum concentration of 50 ppm at 130 °C. These performances mainly benefited from the special hollow porous structure with abundant heterojunctions, the catalysis of the doped-PdO_x, the relative hydrophobic surface from rGO, and the deoxygenation after H₂ reduction.