Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

Tailoring the chemical heterogeneity of Mn-modified 0.75BiFeO3-0.25BaTiO3 ceramics for piezoelectric sensor applications

The Mn-modified 0.75BiFeO₃-0.25BaTiO₃ (75BFBTMn) piezoelectric ceramic possesses a high depolarization temperature of 500 °C and a large piezoelectric coefficient of 110 pC/N, showing the potential for high temperature piezoelectric sensors. However, 75BFBTMn ceramic usually suffers dielectric degradation and abrupt drop of piezoelectric coefficient in the range of 300 °C to 500 °C. Combined the high-energy synchrotron X-ray diffraction analysis with Backscatter-SEM results, it is demonstrated that the electrical thermal instability is owing to the existence of chemical inhomogeneity. The Air-annealing treatment is able to decrease the volume fraction of pseudo-cubic phase and the lattice distortion, removes the chemical inhomogeneity in the grain and free Bi₂O₃ at grain boundary, and then eliminates dielectric anomalies and piezoelectric degradation with temperature. These results indicate that air-annealing is a simple but effective method to eliminate the chemical inhomogeneity in 75BFBTMn ceramics, thereby improving the property thermal stability for high temperature piezoelectric sensor applications.     

Modes of making smart cities: Or,practices of variegated smart urbanism

The ‘actually existing’ smart city is not a monolith. It is not directed by a universal logic, nor does it develop in a standardised way. As recent research has argued, the spatial, material, and political contexts of cities have major influence over what smart urbanism looks like in practice. This paper adds analytical depth to, and broadens the geographical scope of, research on the variegated modes of making smart cities. Based on empirical research in multiple Australian cities we use three case studies to explore three different modes of smart urbanism, each one centred on the interests of a different key actor: corporate-centric, citizen-centric, and planner-centric. These different modes can, and do, co-exist in the same city. At times, they are competing logics that fight to pull the city in different directions. Yet, they can also work together to shape smart city initiatives. In describing these different modes, we pay particular attention to the ways that these projects and strategies must contend with the already existing spatial, cultural, and political contexts of each place.     

Two low-permittivity melilite ceramics in the SrO-MO-GeO2 (M = Mg,Zn) system and their temperature stability through compositional modifications

Two melilite ceramics Sr₂AGe₂O₇ (A = Mg, Zn) with low permittivity were prepared by a solid-state reaction method. The crystal structure and microstructure of the ceramics were characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and scanning electron microscopy. Both ceramics crystallized in a single melilite structure with a tetragonal space group P-42m (113) and exhibited homogeneous microstructures. Optimum microwave dielectric properties with relative permittivity (ε_r) of 8.56, quality factor (Q × f) of 28,800 GHz, and temperature coefficient of resonance frequency (τ_f) of −70.5 ppm/°C were obtained in Sr₂MgGe₂O₇ sintered at 1330 °C. Sr₂ZnGe₂O₇ possessed ε_r of 8.81, Q × f of 35,700 GHz, and τ_f of −84.4 ppm/°C when sintered at 1290 °C. Thermal stability of resonance frequency was accessible when the negative τ_f values of Sr₂AGe₂O₇ were adjusted after the formation of composite ceramics with CaTiO₃.     

Achieving both large piezoelectric constant and high Curie temperature in BiFeO3-PbTiO3-BaTiO3 solid solution

The high-temperature and high-performance piezoelectric ceramics are required urgently in the petrochemical, automotive, and aerospace industries. In this work, the (0.85-x)BiFeO₃-xPbTiO₃-0.15BaTiO₃ (BF-PT-BT, x = 0.21, 0.22, 0.23, 0.24 and 0.25) piezoelectric ceramics with both high Curie temperature and large piezoelectric constant d₃₃ were presented. X-ray diffraction analysis shows that BF-PT-BT ceramics exhibit dominant perovskite structure with the coexistence of tetragonal (T) and rhombohedral (R) phases. The c/a ratio, Curie temperature, piezoelectric constant, dielectric constant and loss of the BF-PT-BT ceramics for x = 0.23 are 1.06, 546 °C, 222 pC/N, 545 and 0.013, respectively. Room temperature piezoelectric constant of BF-PT-BT ceramics is much higher than those of PbTiO₃, PbNb₂O₆ and other ABO₃ perovskite compounds (BaZrO₃, Bi(Zn, Ti)O₃, PbZrO₃ and Pb(Mg, Nb)O₃) modified ternary BiFeO₃-PbTiO₃ ceramics with similar Curie temperatures. The piezoelectric constant is almost unchanged after BF-PT-BT ceramics was annealed at 450 °C for 30 min, which is due to the stable switched non-180° domain and transformed R phase by annealing treatment.     

Structure,dielectric properties of novel Ba(Zr,Ti)O3 based ceramics for energy storage application

(1-x) Ba(Zr_0.2Ti_0.8)O₃-x Na_0.5Bi_0.5TiO₃ (x = 0, 10, 20 30, 40, 50 mol%) (BZTN) ceramics are prepared by the traditional solid phase method. All BZTN ceramics exhibit a pseudo-cubic BZT based perovskite structure. Both the average grain size and the relaxor ferroelectricity of BZTN ceramics gradually increase with increasing NBT content. The W_rec of 3.22 J/cm³ and η of 91.2% is obtained for the BZTN40 ceramic at 241 kV/cm. BZTN40 ceramic also exhibits good temperature stability from room temperature to 150 °C and frequency stability from 1 Hz to 100 Hz. A P_D of 0.621 J/cm³ and a t_0.9 of 82 ns is obtained for the BZTN40 ceramic at 120 kV/cm. BZTN ceramics show application potential in energy storage and pulse power capacitors.     

Highly textured and strongly anisotropic TiB2 ceramics prepared using magnetic field alignment (9T)

Highly textured TiB₂ ceramics were prepared by slip casting an aqueous suspension in a magnetic field of 9 T, followed by sintering using Field Assisted Sintering Technology (FAST). Particle size refinement by ball milling improved both the degree of texturing and densification of the material (RD > 98 %). The sintered material exhibited a Lotgering orientation factor of 0.90, with the c-axis of TiB₂ oriented parallel to the magnetic field and FAST pressing direction. The texturing effect induced by the uniaxial pressing was negligible. The textured TiB₂ material exhibited a significant anisotropy in mechanical properties; the values of hardness and indentation elastic modulus measured along directions transverse to the c-axis of TiB₂ were 37 % and 13 % higher than the ones measured along the c-axis direction. Moreover, the specific wear rate of a surface of textured TiB₂ parallel to the field was one order of magnitude lower than a surface perpendicular to the field.     

Smart “Sticky Note” for strain and temperature sensing using few-layer graphene from exfoliation in red spinach solution

The synthesis of few-layer graphene from graphite typically uses N, N methyl pyrrolidone (NMP) or dimethylformamide (DMF) due to the strong affinity of both solvents for graphite. However, NMP and DMF are known as carcinogens and a long-time exposure to these substances may subject users to potential risk of major health issue later. Therefore, a replacement with dispersing solvent that is not only harmless but also able to exfoliate graphite at an excellent concentration yield must be outlined for a sustainable mass-production of graphene. In this work, we have successfully exfoliated graphite to few-layer graphene with a recorded yield concentration of up to 0.75°mg/ml (2.5°h) just by using extracted red spinach/water mixture as an exfoliating medium. The prepared graphene was found to possess less structural defect (I_D/I_G: 0.5) and high C/O ratio (6.8) and can be used further as an electrical conductive ink for smart “Sticky Note” sensor. The fabricated device was able to detect strain and temperature with gauge factor and temperature coefficient resistance of 23.5 and −32.14 $\times$ 10^-4°Ω/°;C, respectively. We believe that this study would be useful for the preparation of environmental-friendly graphene that is not only strain and thermally sensitive but also producible at low -cost.     

An approach to measure infill matric suction of irregular infilled rock joints under constant normal stiffness shearing

Rock joints infilled with sediments can strongly influence the strength of rock mass. As infilled joints often exist under unsaturated condition, this study investigated the influence of matric suction of infill on the overall joint shear strength. A novel technique that allows direct measurement of matric suction of infill using high capacity tensiometers (HCTs) during direct shear of infilled joints under constant normal stiffness (CNS) is described. The CNS apparatus was modified to accommodate the HCT and the procedure is explained in detail. Joint specimens were simulated by gypsum plaster using three-dimensional (3D) printed surface moulds, and filled with kaolin and sand mixture prepared at different water contents. Shear behaviours of both planar infilled joints and rough joints having joint roughness coefficients (JRCs) of 8–10 and 18–20 with the ratios of infill thickness to asperity height (t/a) equal to 0.5 were investigated. Matric suction shows predominantly unimodal behaviour during shearing of both planar and rough joints, which is closely associated with the variation of unloading rate and volumetric changes of the infill material. As expected, two-peak behaviour was observed for the rough joints and both peaks increased with the increase of infill matric suction. The results suggest that the contribution of matric suction of infill on the joint peak normalised shear stress is relatively independent of the joint roughness.     

Tribological behavior of graphene reinforced chemically bonded ceramic coatings

To investigate tribological behavior of graphene reinforced chemically bonded ceramic coatings at different temperatures, tribological tests at room temperature, 200 °C and 500 °C were carried out. Results show that the fracture toughness and the hardness of the coating are improved with the introduction of graphene. Besides, the friction coefficient of the coating decreases with the addition of graphene at the room temperature and 200 °C. The coating without graphene achieves the similar friction coefficient at all temperatures. However, the coating with graphene achieves the lowest friction coefficient at 200 °C, and achieves the highest at 500 °C. In addition, the wear rate of the coating decreases with the increase of graphene. Besides, the wear rate at 200 °C is almost similar with that at room temperature. In contrast, the wear rate at 500 °C is much larger than those at room temperature and 200 °C. The mechanisms for graphene to decrease the friction coefficient and improve the wear resistance of chemically bonded ceramic coatings at evaluated temperatures are clarified.