Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.     

High lithium storage of Co3O4 enabled by integrating hollow and porous carbon scaffolds

The Co₃O₄, as a potential anode of lithium-ion batteries, has gained considerable attention because of high theoretical capacity. However, the Co₃O₄ is suffering from serious structure deterioration and rapid capacity fading due to its bulky volume change during cyclic charge/discharge process. Herein, to stabilize the lithium storage performance of the Co₃O₄ nanoparticles, a characteristic carbon scaffold (HPC) integrating hollow and porous structures has been fabricated by a well-designed method for the first time. The ultrafine Co₃O₄ nanoparticles are cleverly anchored on the HPC (HPC@Co₃O₄) and hence achieve significantly improved electrochemical properties including high capacity, improved reaction kinetics and outstanding cycle stability, showing high capacity of 1084.7 mAh g^-1 after 200 cycles at 200 mA g^-1 as well as 681.4 mAh g^-1 after 300 cycles at 1000 mA g^-1. The HPC@Co₃O₄ therefore shows good promising for application in advanced lithium-ion battery anodes. The results of the systematically material and electrochemical characterizations indicate that the synergistic effects of ultrafine Co₃O₄ nanoparticles and well-designed HPC scaffolds are responsible for the outstand performance of the HPC@Co₃O₄ anode. Moreover, this work can enrich the understanding and development of stable and high-performance metal oxide-based lithium-ion battery anodes for advanced lithium storage.     

Cubic B-splines method for Hall and ion slip impacts on unsteady MHD rotating flow past a vertical moving porous plate

The heat and mass transfer of unsteady magnetohydrodynamic (MHD) flow of Newtonian fluid with Hall current and ion-slip currents due to vast possible engineering applications is very important in areas like power generators, MHD accelerators, refrigeration coils, electric transformers, and heating elements. A quality-based research on Hall and ion-slip consequences on the rotating unsteady MHD flow past an infinite perpendicular moving absorbent plate have not been performed. Therefore, the Hall and ion-slip consequences on rotating unsteady MHD flow past an infinite perpendicular moving absorbent plate have not been performed. The similarity transformations are engaged to transfer the governing partial differential equations within favor of the scheme of nonlinear ordinary differential equations and elucidated numerically making use of cubic B-splines collocation mechanism. The influences of felicitous parameters on basic equations are remarked on through graphical profiles. Even though the computational estimations of frictional forces, Nusselt number, and Sherwood number for various parameters are distributed in tabular format and exchanged of views comparatively.     

Cu-template-dependent synthesis of PtCu nanotubes for oxygen reduction reactions

The development of electrocatalysts with high activity and durability for oxygen reduction reaction (ORR) in acidic electrolyte environments remains a serious challenge for clean and efficient energy conversion. Synergistic effects between Pt and inexpensive metals, the d band center of Pt and catalyst morphology could adjust the adsorption and desorption of oxygen intermediates by the Pt. All the factors affect the catalytic performance of Pt-based nanocrystals. Here, we prepared Cu@PtCu₃ NWs with an average diameter of 74.9 nm for Cu and about 10 nm PtCu₃ layer. After etching, the Cu@PtCu₃ nanowires is transformed into PtCu nanotube structure, due to the removal of copper from the surface and interior. PtCu NTs for ORR shows excellent activities and durability due to the integration of structural advantages and synergistic effects. Notably, the mass activity and specific activity of PtCu NTs (0.105 A mg^?1_Pt and 0.230 mA cm^?2_Pt) are 2.0 and 3.8 times higher than that of commercial Pt/C (0.053 A mg^?1_Pt and 0.06 mA cm^?2_Pt). The etching process to change the morphology of the catalyst and alter the electronic structure of the catalyst is expected to be useful for the design of future structured Pt-based alloy nanocatalysts.     

Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Dual pH‐ and thermal‐responsive nanocomposite hydrogels for controllable delivery of hydrophobic drug baicalein

Hydrogels have been widely used as mild biomaterials due to their bio‐affinity, high drug loading capability and controllable release profiles. However, hydrogel‐based carriers are greatly limited for the delivery of hydrophobic payloads due to the lack of hydrophobic binding sites. Herein, nano‐liposome micelles were embedded in semi‐interpenetrating poly[(N‐isopropylacrylamide)‐co‐chitosan] (PNIPAAm‐co‐CS) and poly[(N‐isopropylacrylamide)‐co‐(sodium alginate)] (PNIPAAm‐co‐SA) hydrogels which were responsive to both temperature and pH, thereby establishing tunable nanocomposite hydrogel delivery systems. Nano‐micelles formed via the self‐assembly of phospholipid could serve as the link between hydrophobic drug and hydrophilic hydrogel due to their special amphiphilic structure. The results of transmission and scanning electron microscopies and infrared spectroscopy showed that the porous hydrogels were successfully fabricated and the liposomes encapsulated with baicalein could be well contained in the network. In addition, the experimental results of response release in vitro revealed that the smart hydrogels showed different degree of sensitiveness under different pH and temperature stimuli. The results of the study demonstrate that combining PNIPAAm‐co‐SA and PNIPAAm‐co‐CS hydrogels with liposomes encapsulated with hydrophobic drugs is a feasible method for hydrophobic drug delivery and have potential application prospects in the medical field. © 2018 Society of Chemical Industry     

Surface structure and quenching effects in BiFeO3-BaTiO3 ceramics

The structure and properties of Mn-doped 0.67BiFeO₃-0.33BaTiO₃ ceramics are systematically investigated with respect to the effects of annealing prior to rapid cooling by quenching in air. Air-quenching induces a change in crystal structure from pseudo-cubic to rhombohedral, with higher quenching temperatures leading to an increased rhombohedral distortion. These structural changes are correlated with the appearance of more well-defined ferroelectric domain configurations. It is shown that the surface preparation procedures for XRD measurements can induce significant changes in the peak profiles, indicating differences in crystal structure between the surface and bulk regions. Frequency dispersion in the temperature-dependent relative permittivity for the as-sintered sample is significantly reduced after quenching, accompanied by enhancement of the Curie point and improved temperature-stability of piezoelectric properties. It is proposed that the formation of defect clusters by A-site cation diffusion during cooling is circumvented by quenching, leading to the observed modification of structural distortion and ferroelectric properties.     

Surface modification mechanism of SiC particles using KH5X0 (X=5,6,7,8,9) silane coupling agents: First principle study

Silicon carbide surface modification is still a challenging task. Its modification mechanism is also still unclear. This paper provides a study of the surface modification mechanism of KH5X0 (X = 5, 6, 7, 8, 9) on the silicon carbide (111) using density functional theory. The electronic structures and densities of states of KH5X0 (X = 5, 6, 7, 8, 9) on SiC surfaces indicates that the surface modification mechanism is attributed to the electronic effects of the functional groups of KH5X0 (X = 5, 6, 7, 8, 9). From the results the easier it is for a functional group to obtain electrons, the better the modifying performance of silane coupling agent will be. Furthermore, the interface energy results showed that silicon carbide (111) modification performance by KH580 silane and KH590 silane is better than KH550, KH560, and KH570. The present work provides theoretical guidance for the fabrication of SiC heat sink products.