Exceptionally high saturation magnetisation in Eu-doped magnetite stabilised by spin-orbit interaction.

The significance of the spin-orbit interaction is very well known in compounds containing heavier elements such as the rare-earth Eu ion. Here, through density functional calculations, we investigated the effect of the spin-orbit interaction on the magnetic ground state of Eu doped magnetite (Fe3O4:EuFe). By examining all possible spin alignments between Eu and magnetite's Fe, we demonstrate that Eu, which is most stable when doped at the tetrahedral site, adapts a spin almost opposite the substituted Fe. Consequently, because of smaller spin cancellation between the cations on the tetrahedral site (FeTet and EuTet) and the cations on the octahedral sites (FeOct), Fe3O4:EuFe exhibits a maximum saturation magnetisation of 9.451 µB per f.u. which is significantly larger than that of undoped magnetite (calculated to be 3.929 µB per f.u.). We further show that this large magnetisation persists through additional electron doping. However, additional hole doping, which may unintentionally occur in Fe deficient magnetite, can reduce the magnetisation to values smaller than that of the undoped magnetite. The results presented here can aid in designing highly efficient magnetically recoverable catalysts for which both magnetite and rare earth dopants are common materials.

Enhancement of Ce/Cr Codopant Solubility and Chemical Homogeneity in TiO2 Nanoparticles through Sol-Gel versus Pechini Syntheses.

Ce/Cr codoped TiO2 nanoparticles were synthesized using sol-gel and Pechini methods with heat treatment at 400 °C for 4 h. A conventional sol-gel process produced well-crystallized anatase, while Pechini synthesis yielded less-ordered mixed-phase anatase + rutile; this suggests that the latter method enhances Ce solubility and increases chemical homogeneity but destabilizes the TiO2 lattice. Greater structural disruption from the decomposition of the Pechini precursor formed more open agglomerated morphologies, while the lower levels of structural disruption from pyrolysis of the dried sol-gel precursor resulted in denser agglomerates of lower surface areas. Codoping and associated destabilization of the lattice reduced the binding energies in both powders. Cr4+ formation in sol-gel powders and Cr6+ formation in Pechini powders suggest that these valence changes derive from synergistic electron exchange from intervalence and/or multivalence charge transfer. Since Ce is too large to allow either substitutional or interstitial solid solubility, the concept of integrated solubility is introduced, in which the Ti site and an adjacent interstice are occupied by the large Ce ion. The photocatalytic performance data show that codoping was detrimental owing to the effects of reduced crystallinity from lattice destabilization and surface area. Two regimes of mechanistic behavior are seen, which are attributed to the unsaturated solid solutions at lower codopant levels and supersaturated solid solutions at higher levels. The present work demonstrates that the Pechini method offers a processing technique that is superior to sol-gel because the former facilitates solid solubility and consequent chemical homogeneity.

Evaporation Limited Radial Capillary Penetration in Porous Media.

The capillary penetration of fluids in thin porous layers is of fundamental interest in nature and various industrial applications. When capillary flows occur in porous media, the extent of penetration is known to increase with the square root of time following the Lucas-Washburn law. In practice, volatile liquid evaporates at the surface of porous media, which restricts penetration to a limited region. In this work, on the basis of Darcy's law and mass conservation, a general theoretical model is developed for the evaporation-limited radial capillary penetration in porous media. The presented model predicts that evaporation decreases the rate of fluid penetration and limits it to a critical radius. Furthermore, we construct a unified phase diagram that describes the limited penetration in an annular porous medium, in which the boundaries of outward and inward liquid are predicted quantitatively. It is expected that the proposed theoretical model will advance the understanding of penetration dynamics in porous media and facilitate the design of engineered porous architectures.

Scalable surface area characterization by electrokinetic analysis of complex anion adsorption.

By means of the in situ electrokinetic assessment of aqueous particles in conjunction with the addition of anionic adsorbates, we develop and examine a new approach to the scalable characterization of the specific accessible surface area of particles in water. For alumina powders of differing morphology in mildly acidic aqueous suspensions, the effective surface charge was modified by carboxylate anion adsorption through the incremental addition of oxalic and citric acids. The observed zeta potential variation as a function of the proportional reagent additive was found to exhibit inverse hyperbolic sine-type behavior predicted to arise from monolayer adsorption following the Grahame-Langmuir model. Through parameter optimization by inverse problem solving, the zeta potential shift with relative adsorbate addition revealed a nearly linear correlation of a defined surface-area-dependent parameter with the conventionally measured surface area values of the powders, demonstrating that the proposed analytical framework is applicable for the in situ surface area characterization of aqueous particulate matter. The investigated methods have advantages over some conventional surface analysis techniques owing to their direct applicability in aqueous environments at ambient temperature and the ability to modify analysis scales by variation of the adsorption cross section.

Additive manufacturing and performance of bioceramic scaffolds with different hollow strut geometries.

Additively manufactured hollow-strut bioceramic scaffolds present a promising strategy towards enhanced performance in patient-tailored bone tissue engineering. The channels in such scaffolds offer pathways for nutrient and cell transport and facilitate effective osseointegration and vascularization. In this study, we report an approach for the slurry based additive manufacturing of modified diopside bioceramics that enables the production of hollow-strut scaffolds with diverse cross-sectional forms, distinguished by different configurations of channel and strut geometries. The prepared scaffolds exhibit levels of porosity and mechanical strength that are well suited for osteoporotic bone repair. Mechanical characterization in orthogonal orientations revealed that a square outer cross-section for hollow struts in woodpile scaffolds gives rise to levels of compressive strength that are higher than those of conventional solid cylindrical strut scaffolds despite a significantly lower density. Finite element analysis confirms that this improved strength arises from lower stress concentration in such geometries. It was shown that hollow struts in bioceramic scaffolds dramatically increase cell attachment and proliferation, potentially promoting new bone tissue formation within the scaffold channel. This work provides an easily controlled method for the extrusion-based 3D printing of hollow strut scaffolds. We show here how the production of hollow struts with controllable geometry can serve to enhance both the functional and mechanical performance of porous structures, with particular relevance for bone tissue engineering scaffolds.

Templated Synthesis of Exfoliated Porous Carbon with Dominant Graphitic Nitrogen.

We present here a new approach for the synthesis of nitrogen-doped porous graphitic carbon (g-NC) with a stoichiometry of C6.3H3.6N1.0O1.2, using layered silicate as a hard sacrificial template. Autogenous exfoliation is achieved due to the heterostacking of 2D silicate and nitrogen-doped carbon layers. Micro- and meso-porosity is induced by melamine and cetyltrimethylammonium (C16TMA). Our density functional calculations and X-ray photoelectron spectroscopy (XPS) observations confirm that the most dominant nitrogen configuration in g-CN is graphitic, while pyridinic and pyrrolic nitrogens are thermodynamically less favored. Our large-scale lattice dynamics calculations show that surface termination with H and OH groups at pores accounts for the observed H and O in the composition of the synthesized g-NC. We further evaluate the electrocatalytic and the supercapacitance activities of g-NC. Interestingly, this material exhibits a specific capacitance of ca. 202 F g-1 at 1 A g-1, retaining 90% of its initial capacitance after 10,000 cycles.

MOF-derived nanocrystalline ZnO with controlled orientation and photocatalytic activity.

We show here that MOF-5, a sample Zn-based MOF, can uniquely transform into distinct zinc oxide nanostructures. Inspired by the interconversion synthesis of zeolites, we converted MOF-5 into nanocrystalline ZnO. We found the conversion of MOF-5 into ZnO to be tunable and straightforward simply by controlling the treatment temperature and choosing an appropriate structure-directing agent (SDA). Refined X-ray diffraction (XRD) patterns showed that a synthesis temperature of 180 °C (sample ZnO-180) was optimal for achieving high crystallinity. We examined ZnO-180 with high-resolution transmission electron microscopy (HRTEM), which confirmed that the samples were made of individual crystallites grown along the c-axis, or the (001) direction, thus exposing lower energy surfaces and corroborating the XRD pattern and the molecular dynamics calculations. Further investigations revealed that the obtained ZnO at 180 °C has a superior photocatalytic activity in degrading methylene blue to other ZnO nanostructures obtained at lower temperatures.

Bispropylurea bridged polysilsesquioxane: A microporous MOF-like material for molecular recognition.

Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of ∼1 nm, with POSS cages possessing an approximate edge length of ∼3.16 Å.

Freeze Casting: From Low-Dimensional Building Blocks to Aligned Porous Structures-A Review of Novel Materials, Methods, and Applications.

Freeze casting, also known as ice templating, is a particularly versatile technique that has been applied extensively for the fabrication of well-controlled biomimetic porous materials based on ceramics, metals, polymers, biomacromolecules, and carbon nanomaterials, endowing them with novel properties and broadening their applicability. The principles of different directional freeze-casting processes are described and the relationships between processing and structure are examined. Recent progress in freeze-casting assisted assembly of low dimensional building blocks, including graphene and carbon nanotubes, into tailored micro- and macrostructures is then summarized. Emerging trends relating to novel materials as building blocks and novel freeze-cast geometries-beads, fibers, films, complex macrostructures, and nacre-mimetic composites-are presented. Thereafter, the means by which aligned porous structures and nacre mimetic materials obtainable through recently developed freeze-casting techniques and low-dimensional building blocks can facilitate material functionality across multiple fields of application, including energy storage and conversion, environmental remediation, thermal management, and smart materials, are discussed.

Polymer-Derived SiOC Integrated with a Graphene Aerogel As a Highly Stable Li-Ion Battery Anode.

Amorphous polymer-derived silicon oxycarbide (SiOC) is an attractive candidate for Li-ion battery anodes, as an alternative to graphite, which is limited to a theoretical capacity of 372 mAh/g. However, SiOC tends to exhibit poor transport properties and cycling performance as a result of sparsely distributed carbon clusters and inefficient active sites. To overcome these limitations, we designed and fabricated a layered graphene/SiOC heterostructure by solvent-assisted infiltration of a polymeric precursor into a modified three-dimensional (3D) graphene aerogel skeleton. The use of a high-melting-point solvent facilitated the precursor's freeze drying, which following pyrolysis yielded SiOC as a layer supported on the surface of nitrogen-doped reduced graphene oxide aerogels. The fabrication method employed here modifies the composition and microstructure of the SiOC phase. Among the studied materials, the highest levels of performance were obtained for a sample of moderate SiOC content, in which the graphene network constituted 19.8 wt % of the system. In these materials, a stable reversible charge capacity of 751 mAh/g was achieved at low charge rates. At high charge rates of 1480 mA/g, the capacity retention was ∼95% (352 mAh/g) after 1000 consecutive cycles. At all rates, Coulombic efficiencies >99% were maintained following the first cycle. Performance across all indicators was majorly improved in the graphene aerogel/SiOC nanocomposites, compared with unsupported SiOC. The performance was attributed to mechanisms across multiple length scales. The presence of oxygen-rich SiO4-xCx tetrahedral units and a continuous free-carbon network within the SiOC provides sites for reversible lithiation, while high ionic and electronic transport is provided by the layered graphene/SiOC heterostructure.

Materials and Applications for Low-Cost Ceramic Membranes.

In water treatment applications, the use of ceramic membranes is associated with numerous advantages relative to polymer-based filtration systems. High-temperature stability, fouling resistance, and low maintenance requirements contribute to lower lifecycle costs in such systems. However, the high production costs of most commercially available ceramic membranes, stemming from raw materials and processing, are uneconomical for such systems in most water treatment applications. For this reason, there is a growing demand for new ceramic membranes based on low-cost raw materials and processes. The use of unrefined mineral feedstocks, clays, cement, sands, and ash as the basis for the fabrication of ceramic membranes offers a promising pathway towards the obtainment of effective filtration systems that can be economically implemented in large volumes. The design of effective ceramic filtration membranes based on low-cost raw materials and energy-efficient processes requires a balance of pore structure, mass flow, and robustness, all of which are highly dependent on the composition of materials used, the inclusion of various pore-forming and binding additives, and the thermal treatments to which membranes are subjected. In this review, we present recent developments in materials and processes for the fabrication of low-cost membranes from unrefined raw materials, including clays, zeolites, apatite, waste products, including fly ash and rice husk ash, and cement. We examine multiple aspects of materials design and address the challenges relating to their further development.

Tailoring porous media for controllable capillary flow.

HYPOTHESIS: Control of capillary flow through porous media has broad practical implications. However, achieving accurate and reliable control of such processes by tuning the pore size or by modification of interface wettability remains challenging. Here we propose that the liquid flow by capillary penetration can be accurately adjusted by tuning the geometry of porous media. METHODOLOGIES: On the basis of Darcy's law, a general framework is proposed to facilitate the control of capillary flow in porous systems by tailoring the geometric shape of porous structures. A numerical simulation approach based on finite element method is also employed to validate the theoretical prediction. FINDINGS: A basic capillary component with a tunable velocity gradient is designed according to the proposed framework. By using the basic component, two functional capillary elements, namely, (i) flow accelerator and (ii) flow resistor, are demonstrated. Then, multi-functional fluidic devices with controllable capillary flow are realized by assembling the designed capillary elements. All the theoretical designs are validated by numerical simulations. Finally, it is shown that the proposed concept can be extended to three-dimensional design of porous media.

Universality of the emergent scaling in finite random binary percolation networks.

In this paper we apply lattice models of finite binary percolation networks to examine the effects of network configuration on macroscopic network responses. We consider both square and rectangular lattice structures in which bonds between nodes are randomly assigned to be either resistors or capacitors. Results show that for given network geometries, the overall normalised frequency-dependent electrical conductivities for different capacitor proportions are found to converge at a characteristic frequency. Networks with sufficiently large size tend to share the same convergence point uninfluenced by the boundary and electrode conditions, can be then regarded as homogeneous media. For these networks, the span of the emergent scaling region is found to be primarily determined by the smaller network dimension (width or length). This study identifies the applicability of power-law scaling in random two phase systems of different topological configurations. This understanding has implications in the design and testing of disordered systems in diverse applications.

Static friction between rigid fractal surfaces.

Using spheropolygon-based simulations and contact slope analysis, we investigate the effects of surface topography and atomic scale friction on the macroscopically observed friction between rigid blocks with fractal surface structures. From our mathematical derivation, the angle of macroscopic friction is the result of the sum of the angle of atomic friction and the slope angle between the contact surfaces. The latter is obtained from the determination of all possible contact slopes between the two surface profiles through an alternative signature function. Our theory is validated through numerical simulations of spheropolygons with fractal Koch surfaces and is applied to the description of frictional properties of Weierstrass-Mandelbrot surfaces. The agreement between simulations and theory suggests that for interpreting macroscopic frictional behavior, the descriptors of surface morphology should be defined from the signature function rather than from the slopes of the contacting surfaces.