Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

Effect of sintering temperature on lightweight aggregates manufacturing from copper contaminated soil

Manufacturing lightweight aggregate (LWA) at high temperature is an effective way to immobilize heavy metals in solid waste. This work investigated the performance and solidification mechanism of LWA prepared from copper contaminated soil. The volume expansion of LWA could reach a maximum of 28%, and its lowest density accounted of 1.5 g/cm³, which met the standard requirements. Optical microscope and micro-CT test illustrated that the addition of Cu leaded to obvious phase separation in LWA. The Cu leaching result of LWA first increased and then dropped with the temperature. The XRD test found that the main formation phase of Cu in LWA were t-CuFe₂O₄ and amorphous phase that they had different acid resistance ability. XPS revealed that the main cause of the agglomeration of liquid phase in LWA was the chain broken reaction between Cu and Si–O tetrahedron. SEM-EDS results showed that the distribution of Cu and Si had a strong correlation, which meant that Cu mostly formed amorphous phase. This work showed the uniqueness of Cu in the high temperature immobilization and pointed out the best immobilization target phase.     

Phosphorylated chitosan/poly(vinyl alcohol) based proton exchange membranes modified with propylammonium nitrate ionic liquid and silica filler for fuel cell applications

In our previous work, phosphorylated chitosan was modified through polymer blending with poly(vinyl alcohol) (PVA) polymer to produce N-methylene phosphonic chitosan/poly(vinyl alcohol) (NMPC/PVA) composite membranes. The aim of this work is to further investigate the effects of a propylammonium nitrate (PAN) ionic liquid and/or silicon dioxide (SiO₂) filler on the morphology and physical properties of NMPC/PVA composite membranes. The temperature-dependent ionic conductivity of the composite membranes with various ionic liquid and filler compositions was studied by varying the loading of PAN ionic liquid and SiO₂-PAN filler in the range of 5–20 wt%. As the loading of PAN ionic liquid increased in the NMPC/PVA membrane matrix, the ionic conductivity value also increased with the highest value of 0.53 × 10^?3 S cm^?1 at 25 °C and increased to 1.54 × 10^?3 S cm^?1 at 100 °C with 20 wt% PAN. The NMPC/PVA-PAN (20 wt%) composite membrane also exhibited the highest water uptake and ion exchange capacity, with values of 60.5% and 0.60 mequiv g^?1, respectively. In addition, in the single-cell performance test, the NMPC/PVA-PAN (20 wt%) composite membrane displayed a maximum power density, which was increased by approximately 14% compared to the NMPC/PVA composite membrane with 5 wt% SiO₂-PAN. This work demonstrated that modified NMPC/PVA composite membranes with ionic liquid PAN and/or SiO₂ filler showed enhanced performance compared with unmodified NMPC/PVA composite membranes for proton exchange membrane fuel cells.     

Reactive Oxygen and Nitrogen Species in Defense/Stress Responses Activated by Chitosan in Sycamore Cultured Cells

Chitosan (CHT) is a non-toxic and inexpensive compound obtained by deacetylation of chitin, the main component of the exoskeleton of arthropods as well as of the cell walls of many fungi. In agriculture CHT is used to control numerous diseases on various horticultural commodities but, although different mechanisms have been proposed, the exact mode of action of CHT is still unknown. In sycamore (Acer pseudoplatanus L.) cultured cells, CHT induces a set of defense/stress responses that includes production of H₂O₂ and nitric oxide (NO). We investigated the possible signaling role of these reactive molecules in some CHT-induced responses by means of inhibitors of production and/or scavengers. The results show that both reactive nitrogen and oxygen species are not only a mere symptom of stress conditions but are involved in the responses induced by CHT in sycamore cells. In particular, NO appears to be involved in a cell death form induced by CHT that shows apoptotic features like DNA fragmentation, increase in caspase-3-like activity and release of cytochrome c from the mitochondrion. On the contrary, reactive oxygen species (ROS) appear involved in a cell death form induced by CHT that does not show these apoptotic features but presents increase in lipid peroxidation.     

A unified critical state model for geomaterials with an application to tunnelling

This paper is prepared in honour of Professor E.T. Brown for his outstanding contributions to rock mechanics and geotechnical engineering and also for his personal influence on the first author's research career in geomechanics and geotechnical engineering. As a result, we have picked a topic that reflects two key research areas in which Professor E.T. Brown has made seminal contributions over a long and distinguished career. These two areas are concerned with the application of the critical state concept to modelling geomaterials and the analysis of underground excavation or tunnelling in geomaterials.Partially due to Professor Brown's influence, the first author has also been conducting research in these two areas over many years. In particular, this paper aims to describe briefly the development of a unified critical state model for geomaterials together with an application to cavity contraction problems and tunnelling in soils.     

Seismic behavior of geosynthetic-reinforced retaining walls backfilled with cohesive soil

This study investigates the seismic performance of geosynthetic-reinforced modular block retaining walls backfilled with cohesive, fine grained clay-sand soil mixture. Shaking table tests were performed for three ½ scaled (wall height 190 cm) and ¼ scaled model walls to investigate the effects of backfill type, the influence of reinforcement length and reinforcement stiffness effects. The El Centro and Kobe earthquake records of varying amplitudes were used as base acceleration. Displacement of the front wall, accelerations at different locations, strains on the reinforcements, and the visual observations of the facing and the backfill surface were used to evaluate the seismic performance of model walls. The model walls were subjected to rigorous shaking and the walls did not exhibit any stability problems or signs of impending failure. The maximum deformations observed on the models with cohesive backfill was less than half of the deformation of the sand model. The load transfers between the geogrid and cohesive soil was comparable to that of sand and hence the needed reinforcement length was similar as well. As a result; the model walls with cohesive backfills performed within acceptable limits under seismic loading conditions when compared with granular backfilled counterparts.     

Critical state model for structured soil

Structure is an evident determinant for macroscopic behaviors of soils. However, this is not taken into account in most constitutive models, as structure is a rather complex issue in models. For this, it is important to develop and implement simple models that can reflect this important aspect of soil behavior. This paper tried to model structured soils based on well-established concepts, such as critical state and sub-loading. Critical state is the core of the classic Cam Clay model. The sub-loading concept implies adoption of an inner (sub-loading) yield surface, according to specific hardening rules for some internal strain-like state variables. Nakai and co-workers proposed such internal variables for controlling density (ρ) and structure (ω), using a modified stress space, called t_ij. Herein, similar variables are used in the context of the better-known invariants (p and q) of the Cam Clay model. This change requires explicit adoption of a non-associated flow rule for the sub-loading surface. This is accomplished by modifying the dilatancy ratio of the Cam Clay model, as a function of the new internal variables. These modifications are described and implemented under three-dimensional (3D) conditions. The model is then applied to simulating laboratory tests under different stress paths and the results are compared to experiments reported for different types of structured soils. The good agreements show the capacity and potential of the proposed model.