Enhanced photoreactivity of MOFs by intercalating interlayer bands via simultaneous ?NCO and ?SCu modification

Herein, we propose a novel method to enhance the photoreactivity of an MOF catalyst by grafting isocyanate bonds ( NCO) and sulfhydryl-complexed copper ( SCu) onto ZIF-8 (NIF-SCu). The grafting process intercalated interlayer bands between the conduction and valence bands of ZIF-8, thereby providing a “ladder” for facile electron transition. The extreme improvement in the photoreactivity of NIF-SCu could be attributed to the enhancement in light responses in the range of 350–450 nm by  NCO groups and the widening of the visible light range of the MOF by  SCu groups. The formation of staggered energy levels in NIF-SCu could also narrow the band gap, lower the resistance, and facilitate the transfer of photogenerated carriers, thereby generating electrons with strong reduction potential in the  SCu conduction band. This study provides a new strategy for improving or even endowing the photoactivity of environmental functional materials with wide bandgaps.     

The impacts of cattle access points on deposited sediment levels in headwater streams in Ireland

Cattle access to streams has been linked globally with degradation of stream water quality, driven largely by bank erosion and resultant instream, fine sediment deposition. The majority of evidence on such effects is however based in arid and semiarid regions of the United States and Australia, with few studies relating to cool temperate climates such as Northwest Europe. In this study, “Quorer” resuspendable sediment samples were taken from riffle geomorphic units upstream (control) and at two points downstream (pressure and recovery) of cattle access points in headwater streams in agricultural catchments in Ireland to assess levels of deposited stream sediment. Samples were taken in April/May (2016) prior to the grazing season and in October (2016) at the end of the grazing season. Sites in good‐high ecological status catchments and less than good ecological status catchments were included in the study. Higher levels of sediment were found downstream of cattle access points in both good‐high status and less than good status catchments; however, the impacts of access points were spatially confined to, in most cases, the area immediately downstream of the point of access. There was a strong correlation between deposited sediment mass and organic matter (OM) mass, with levels of OM increasing linearly with deposited sediment mass. Levels of measured sediment were negatively correlated with riparian habitat health (measured using a qualitative habitat assessment). The results of this study highlight the need for measures to prevent cattle access to headwater streams where access points can be many in order to manage local habitat quality and downstream water quality issues.     

Influence of geosynthetic reinforcement on the stability of an embankment with rigid columns embedded in an inclined underlying stratum

Incompressible dipping substrata are commonly encountered in engineering practice. Compared to horizontal underlying strata, the inclined underlying stratum increase the risk of collapse of embankments reinforced with columns because it weakens the restraint of the column base. The objective of this study is to investigate the effectiveness of geosynthetics on improving the embankment stability when the underlying stratum is inclined. The influence of geosynthetic tensile stiffness on the ultimate surcharge and failure mechanism is studied. A deep-seated failure with column tilting occurs when the geosynthetic tensile stiffness is low, whereas a lateral sliding occurs when the geosynthetic tensile stiffness is high. To illustrate the contribution of geosynthetics, the distribution of the lateral pressures acting on the columns is analyzed.     

In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

Cyclic thermal shock resistance of h-BN composite ceramics with La2O3–Al2O3–SiO2 addition

The effects of La₂O₃–Al₂O₃–SiO₂ addition on the thermal conductivity, coefficient of thermal expansion (CTE), Young's modulus and cyclic thermal shock resistance of hot-pressed h-BN composite ceramics were investigated. The samples were heated to 1000 °C and then quenched to room temperature with 1–50 cycles, and the residual flexural strength was used to evaluate cyclic thermal shock resistance. h-BN composite ceramics containing 10 vol% La₂O₃–Al₂O₃ and 20 vol% SiO₂ addition exhibited the highest flexural strength, thermal conductivity and relatively low CTE, which were beneficial to the excellent thermal shock resistance. In addition, the viscous amorphous phase of ternary La₂O₃–Al₂O₃–SiO₂ system could accommodate and relax thermal stress contributing to the high thermal shock resistance. Therefore, the residual flexural strength still maintained the value of 234.3 MPa (86.9% of initial strength) after 50 cycles of thermal shock.     

Synthesis of Diamond@SiO2@Ag composite materials for high SERS effect

Among various carbon materials, diamond stands out due to excellent physical and chemical properties. In this work, we designed Dia@SiO₂@Ag composites combining diamond micropowder and Ag nanoparticles by a simple chemical method and obtained stable substrate for surface enhanced Raman scattering (SERS) owing to its high surface-to-volume ratio, low density, as well as close bond between diamond and Ag. As-prepared Dia@SiO₂@Ag presented high activity to detect crystal violet and rhodamine 6G molecules, which was demonstrated by significantly enhanced SERS spectra and high enhancement factor values (10⁸-10⁹). Moreover, Dia@SiO₂@Ag also showed desired sensitivity, which was investigated by detection limit. Therefore, our study provided more theoretical support and broadened the functional applications of diamond, particularly in Raman detection.     

Fabrication of direct Z-scheme FeIn2S4/Bi2WO6 hierarchical heterostructures with enhanced photocatalytic activity for tetracycline hydrochloride photodagradation

A series of direct Z-scheme FeIn₂S₄/Bi₂WO₆ hierarchical heterostructures with intimate interface contacts were synthesized by in-situ growth route and characterized by systematical analyses. All as-prepared FeIn₂S₄/Bi₂WO₆ nanocomposites showed significantly enhanced photocatalytic activity towards photodegradation for the removal of tetracycline hydrochloride (TCH) in comparison with individual FeIn₂S₄ and Bi₂WO₆. Meanwhile, the highest photocatalytic degradation activity can be achieved by modulating adding amount of FeIn₂S₄ in FeIn₂S₄/Bi₂WO₆ nanocomposites and the optimized component ratio of FeIn₂S₄ to Bi₂WO₆ is determined to be 10 wt%. The enhanced photocatalytic activity could be ascribed to efficient separation between photogenerated holes and electrons based on the construction of direct Z-scheme system. The high photocatalytic stability of resultant 10 wt% FeIn₂S₄/Bi₂WO₆ nanocomposites was revealed through six successive recycling reactions. The main intermediate generated during TCH photodegradation was explored by HPLC-MS. Besides, the direct Z-scheme photocatalytic mechanism was confirmed by band position analysis, electron spin resonance (ESR) and active species capture experiment.     

On the capacity of the state‐dependent interference relay channel

This paper considers the state‐dependent interference relay channel (SIRC) in which one of the two users may operate as a secondary user and the relay has a noncausal access to the signals from both users. For discrete memoryless SIRC, we first establish the achievable rate region by carefully merging Han‐Kobayashi rate splitting encoding technique, superposition encoding, and Gelfand‐Pinsker encoding technique. Then, based on the achievable rate region that we derive, the capacity of the SIRC is established in many different scenarios including (a) the weak interference regime, (b) the strong interference regime, and (c) the very strong interference regime. This means that our capacity results contain all available known results in the literature. Next, the achievable rate region and the associated capacity results are also evaluated in the case of additive Gaussian noise. Additionally, many numerical examples are investigated to show the value of our theoretical derivations.