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.     

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.     

A stiffness parameter and truncation error criterion for adaptive path following in structural mechanics

We explore a truncation error criterion to steer adaptive step length refinement and coarsening in incremental-iterative path following procedures, applied to problems in large-deformation structural mechanics. Elaborating on ideas proposed by Bergan and collaborators in the 1970s, we first describe an easily computable scalar stiffness parameter whose sign and rate of change provide reliable information on the local behavior and complexity of the equilibrium path. We then derive a simple scaling law that adaptively adjusts the length of the next step based on the rate of change of the stiffness parameter at previous points on the path. We show that this scaling is equivalent to keeping a local truncation error constant in each step. We demonstrate with numerical examples that our adaptive method follows a path with a significantly reduced number of points compared to an analysis with uniform step length of the same fidelity level. A comparison with Abaqus illustrates that the truncation error criterion effectively concentrates points around the smallest-scale features of the path, which is generally not possible with automatic incrementation solely based on local convergence properties.     

Static and free vibration analysis of functionally graded plates based on a new quasi-3D and 2D shear deformation theories

In this study, two dimensional (2D) and quasi three-dimensional (quasi-3D) shear deformation theories are presented for static and free vibration analysis of single-layer functionally graded (FG) plates using a new hyperbolic shape function. The material of the plate is inhomogeneous and the material properties assumed to vary continuously in the thickness direction by three different distributions; power-law, exponential and Mori–Tanaka model, in terms of the volume fractions of the constituents. The fundamental governing equations which take into account the effects of both transverse shear and normal stresses are derived through the Hamilton's principle. The closed form solutions are obtained by using Navier technique and then fundamental frequencies are found by solving the results of eigenvalue problems. In-plane stress components have been obtained by the constitutive equations of composite plates. The transverse stress components have been obtained by integrating the three-dimensional stress equilibrium equations in the thickness direction of the plate. The accuracy of the present method is demonstrated by comparisons with the different 2D, 3D and quasi-3D solutions available in the literature.     

Fabrication of 3D structures via direct ink writing of kaolin/graphene oxide composite suspensions at ambient temperature

Kaolin/graphene oxide composite has been widely utilized in aero-space and architectural engineering applications due to its excellent mechanical property. Direct ink writing (DIW) is a freeform rapid prototyping technology that could be used to accurately fabricate the resulting size with complex shapes. In this study, we reported the DIW of kaolin/graphene oxide (GO) composite suspensions (KGCS) to assemble 3D structures at ambient temperature for the first time. The effects of GO on the chemical constitution and microstructure of kaolin suspensions were investigated. Rheology was characterized to ensure printability of KGCS. The addition of GO in kaolin suspensions quickened a flocculation structure, which dramatically changed their rheology properties. The DIW of 3D structures from the optimal KGCS sample maintained their initial shape without spreading. The flexural and compressive strengths of the dried optimal KGCS samples were obviously enhanced due to the improvement and reduction of the micro-defects compared from cured kaolin matrix.     

Mechanical properties of graphene films enhanced by homo-telechelic functionalized polymer fillers via π–π stacking interactions

Most researches on graphene/polymer composites are focusing on improving the mechanical and electrical properties of polymers at low graphene content instead of paying attention to constructing graphene’s macroscopic structures. In current study the homo-telechelic functionalized polyethylene glycols (FPEGs) were tailored with π-orbital-rich groups (namely phenyl, pyrene and di-pyrene) via esterification reactions, which enhanced the interaction between polyethylene glycol (PEG) molecules and chemical reduced graphene oxide (RGO) sheets. The π–π stacking interactions between graphene sheets and π-orbital-rich groups endowed the composite films with enhanced tensile strength and tunable electrical conductivity. The formation of graphene network structure mediated by the FPEGs fillers via π–π stacking non-covalent interactions should account for the experimental results. The experimental investigations were also complemented with theoretical calculation using a density functional theory. Atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), UV–vis and fluorescence spectroscopy were used to monitor the step-wise preparation of graphene composite films.