Electrodeposition of the manganese-doped nickel-phosphorus catalyst with enhanced hydrogen evolution reaction activity and durability

Hydrogen technology is widely considered a novel clean energy source, and electrolysis is an effective method for hydrogen evolution. Therefore, efficient hydrogen evolution reaction (HER) catalysts are urgently needed to replace precious metal catalysts and meet ecological and environmental protection standards. Herein, Ni–Mn–P electrocatalysts are synthesized using facile electrodeposition technology. The influence of the Mn addition on the catalytic behavior is studied by the comprehensive analysis of catalytic performance and morphology of the catalysts. Among them, the Ni–Mn–P0.01 catalyst exhibits small coral-like structures, greatly improving the adsorption and desorption of hydrogen ions and reducing the overpotential hydrogen evolution. Consequently, overpotential at 10 mA cm^?2 electric current density is 113 mV, and the value of the Tafel slope achieves 74 mV/dec. Furthermore, the Ni–Mn–P catalyst shows long-time (20 h) stability at current densities of 10 and 60 mA/cm². The results confirm that the synergistic effect of Ni, Mn, and P accelerates the electrochemical reaction. Meanwhile, the addition of manganese element can change the micromorphology of the catalyst, thereby exposing more active sites to participate in the reaction, enhancing water ionization, improving the catalytic performance. This study opens a new way toward improving the activity of the catalyst by adjusting Mn concentration during the electrodeposition process.     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Adding new floors to old timber-framed buildings: An assessment of demolished and preserved courtyard houses in the historic centre of Madrid

The constructive analysis of Madrid's old timber-framed collective courtyard buildings, whether demolished, preserved intact, or enlarged, has achieved the dating of relevant case studies. New parameters established in this study set a chronology based on front sector original projects: old (1737–1788), pre-modern (1788–1847) and modern (1847–1892). The on-site inspection and archival research point to ongoing misleading construction in the historic Southern area. Some modern corralas erected on top of pre-existing buildings confirm the initial hypothesis. First dimensioning rules for new façades and the stability required in old ones before adding new storeys, maintaining the original masonry or double-layered system, are discovered. Undated buildings suggest their possible origin a la malicia and a later transformation into transitional corralas. Finally, an analysis of the demolished courtyards narrows down the dating and points to new conjectures in some preserved by showing their uneven layout, old features, and structural discordances in each sector.     

Synthesis and characterization of superoleophobic fumed alumina nanocomposite coated via the sol-gel process onto ceramic-based hollow fibre membrane for oil-water separation

Oily wastewater treatment is a global challenge due to the substantial amount of effluent resulted from many industrial and domestic activities. To overcome the challenge of using existing treatment approach and fouling, superoleophobic coatings were fabricated. In this study, a superoleophobic membrane surface was obtained using the sol-gel technique with perfluorooctanoate (PFO), poly (diallyl dimethylammonium chloride) (PDADMAC), and nanoparticles as complex-polymer nanocomposites. The effects of coating cycles on the surface structure, chemical properties, surface chemistry, and oleophobicity of the surface were examined using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and oil contact angle measurement. The results showed that the coated layer successfully adhered to the substrate surface. However, the chemical stability with respect to oil contact angle (OCA) revealed a decline at pH 7 and pH 9 and maintained stability at pH 3. Besides, oil flux at 63.0 L/m². h was achieved for PDADMAC-Al₂O₃/44 wt% PFO and the highest separation efficiency of 98% was obtained. Furthermore, the oil rejection decreases as the oil concentration increases from 1 to 3 g/L. OCA of 155° was obtained after 5 coating cycles. Apart from mitigating substrate fouling, the superoleophobic and superhydrophilic coating can be applied to a ceramic-based hollow fibre membrane and efficiently used for the separation of oil from oily wastewater.     

Preparation and antifouling performance of thin inorganic ultrafiltration membrane via assisted sol-gel method with different composition of dual additives

A novel TiO₂ thin film was prepared on the ceramic hollow fiber by the sol-gel method using poly(vinylpyrrolidone) (PVP) and polyvinyl alcohol (PVA) as additives. SEM images verified the formation of TiO₂ layer with various thickness using different composition of titania sols. The effect of the PVP and PVA contents on the TiO₂ sol properties, the separation and the antifouling performance of the ultrafiltration membranes were investigated thoroughly. When the contents of PVP and PVA were 1.0 wt% and 0.8 wt%, respectively, the resultant membrane showed a thickness of 0.55 μm with a pure water flux of 255 L m^?2 h^?1. In addition, the adherent foulant bovine serum albumin was applied to evaluate the antifouling performance. During the three fouling-recovery cycles, the flux recovery ratio and the flux decay ratio maintained about 99% and 30%. The BSA flux and rejection were still 169 L m^?2 h^?1 and 96.9% after the cycles, indicating a superior antifouling property.     

Progressive NO2 Sensors with Rapid Alarm and Persistent Memory-Type Responses for Wide-Range Sensing Using Antimony Triselenide Nanoflakes

Antimony triselenide (Sb₂Se₃) nanoflake-based nitrogen dioxide (NO₂) sensors exhibit a progressive bifunctional gas-sensing performance, with a rapid alarm for hazardous highly concentrated gases, and an advanced memory-type function for low-concentration (<1 ppm) monitoring repeated under potentially fatal exposure. Rectangular and cuboid shaped Sb₂Se₃ nanoflakes, comprising van der Waals planes with large surface areas and covalent bond planes with small areas, can rapidly detect a wide range of NO₂ gas concentrations from 0.1 to 100 ppm. These Sb₂Se₃ nanoflakes are found to be suitable for physisorption-based gas sensing owing to their anisotropic quasi-2D crystal structure with extremely enlarged van der Waals planes, where they are humidity-insensitive and consequently exhibit an extremely stable baseline current. The Sb₂Se₃ nanoflake sensor exhibits a room-temperature/low-voltage operation, which is noticeable owing to its low energy consumption and rapid response even under a NO₂ gas flow of only 1 ppm. As a result, the Sb₂Se₃ nanoflake sensor is suitable for the development of a rapid alarm system. Furthermore, the persistent gas-sensing conductivity of the sensor with a slow decaying current can enable the development of a progressive memory-type sensor that retains the previous signal under irregular gas injection at low concentrations.     

Influence of pores arrangement on stability of photonic structures during sintering

Discrete Element Method (DEM) has been used for numerical investigation of sintering-induced structural deformations occurring in inverse opal photonic structures. The influence of the initial arrangement of template particles on the stability of highly porous inverse opal α-Al₂O₃ structures has been analyzed. The material transport, densification, as well as formation of defects and cracks have been compared for various case studies. Three different stages of defects formation have been distinguished starting with local defects ending with intrapore cracks. The results show that the packing of the template particles defined during the template self-assembly process play a crucial role in the later structural deformation upon thermal exposure. The simulation results are in very good agreement with experimental data obtained from SEM images and previous studies by ptychographic X-ray tomography.     

Core–shell NTC materials with low thermal constant and high resistivity for wide-temperature thermistor ceramics

Core–shell structures have been proposed to improve the electrical properties of negative-temperature coefficient (NTC) thermistor ceramics. In this work, Al₂O₃-modified Co_1.5Mn_1.2Ni_0.3O₄ NTC thermistor ceramics with adjustable electrical properties were prepared through citrate-chelation followed by conventional sintering. Co_1.5Mn_1.2Ni_0.3O₄ powder was coated with a thin Al₂O₃ shell layer to form a core–shell structure. Resistivity (ρ) increased rapidly with increasing thickness of the Al₂O₃ layer, and the thermal constant (B) varied moderately between 3706 and 3846 K. In particular, Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ ceramic with 0.08 wt% Al₂O₃ showed the increase of ρ double, and the change in its B was less than 140 K. The Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics showed high stability, and their grain size was relatively uniform due to the protection offered by the shell. The aging coefficient of the ceramic was less than 0.2% after aging for 500 hours at 125°C. Taken together, the results indicate that as-prepared Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics with a core–shell structure may be promising candidates for application as wide-temperature NTC thermistor ceramics.