Inorganic Structures Research Articles

2D organic-inorganic supercrystalline structures with 3D layered ion channels for efficient aqueous zinc ion storage

Aqueous zinc ion batteries (AZIBs) have become powerful substitutes for large-scale energy storage because of their high safety and low cost, so the design of high-performance cathode materials has always been a requirement. Layered VxOy is one key type of cathode materials for rechargeable AZBs. Usually, it shows two-dimensional (2D) ion diffusion mechanism through the intercalation/deintercalation of Zn2+ at edge sites, but is plagued by the inert basal planes. Here, polymelamine (PME) was successfully inserted into the layered structure of VO2 nH2O and an organic–inorganic supercrystalline structure (PMVO-sls) with layered structure along the c-axis and ab plane was formed, thus providing additional ion diffusion channels and abundant active sites. The highly efficient and ultrafast 3D Zn2+ intercalation/deintercalation behaviors along both the c-axis and ab plane of VO2 nH2O are realized for the first time in AZIBs. Moreover, PMVO-sls has rich oxygen vacancy (Od) which is beneficial to electrolyte transport and ion diffusion, and it is a very competitive electrode material. Experimental data and density functional theory calculation (DFT) have confirmed that the intercalation of PEM can improve the electronic conductivity of materials and explained the possibility of Zn2+ diffusion through 3D interlayer structural channels. As cathode materials for AZIBs in 3 M Zn (CF3SO3)2, PMVO-sls exhibited an ideal reversible capacity of 344 mA h g−1 at 0.2 A g−1, and excellent cyclic stability (121 mA h g−1 retained after 4,500 cycles at 10 A g−1, a retention rate of 93%). Furthermore, in PMVO-sls/2.8 M Zn (CF3SO3)2 + 0.2 M ZnSO4/Zn AZIBs, PMVO-sls has a higher reversible capacity with an reversible capacity of 392.1 mA h g−1 at 0.2 A g−1 and better cyclic stability (180 mA h g−1 retained after 6,000 cycles at 10 A g−1, a retention rate of 90%). This method can provide a new way for the synthesis of high quality cathode materials for AZIBs and other metal ion batteries.

Ligand-induced incompatible curvatures control ultrathin nanoplatelet polymorphism and chirality

The ability of thin materials to shape-shift is a common occurrence that leads to dynamic pattern formation and function in natural and man-made structures. However, harnessing this concept to rationally design inorganic structures at the nanoscale has remained far from reach due to a lack of fundamental understanding of the essential physical components. Here, we show that the interaction between organic ligands and the nanocrystal surface is responsible for the full range of chiral shapes seen in colloidal nanoplatelets. The adsorption of ligands results in incompatible curvatures on the top and bottom surfaces of the NPL, causing them to deform into helicoïds, helical ribbons, or tubes depending on the lateral dimensions and crystallographic orientation of the NPL. We demonstrate that nanoplatelets belong to the broad class of geometrically frustrated assemblies and exhibit one of their hallmark features: a transition between helicoïds and helical ribbons at a critical width. The effective curvature [Formula: see text] is the single aggregate parameter that encodes the details of the ligand/surface interaction, determining the nanoplatelets' geometry for a given width and crystallographic orientation. The conceptual framework described here will aid the rational design of dynamic, chiral nanostructures with high fundamental and practical relevance.

A self-assembled 3D nanoflowers based nano-ELISA platform for the sensitive detection of pyridaben

Biomimetic methods are invariably employed to synthesize hybrid organic–inorganic multilevel structure nanoflowers with self-assembly processes in aqueous solutions, which is an ideal way to meet the challenges of immobilizing antibodies or enzymes in nanomaterial based enzyme-linked immunosorbent assay (nano-ELISA). In this study, we developed protein-inorganic hybrid 3D nanoflowers composed of bovine serum albumin (BSA), horseradish peroxidase (HRP)-conjugated goat anti-mouse IgG (IgG-HRP) and copper(Ⅱ) phosphate (BSA-(IgG-HRP)-Cu3(PO4)2) using a self-assembly biomimetic method. The preparation process avoided the use of any organic solvent and protein immobilization did not require covalent modifications. Additionally, the unique hierarchical structure enhances the thermal and storage stability of HRP. The BSA-(IgG-HRP)-Cu3(PO4)2 hybrid 3D nanoflower was then applied to a nano-ELISA platform for pyridaben detection, achieving a 50% inhibition concentration of 3.90 ng mL−1. The nano-ELISA achieved excellent accuracy for pyridaben detection. Such a novel BSA-(IgG-HRP)-Cu3(PO4)2 hybrid 3D nanoflower provide an excellent reagent for small molecule immunoassay.

Inspection of antimicrobial particles in milk using RGB-laser scattering imaging combined with chemometric procedures

The immobilisation of phytochemicals on inert particles has demonstrated high potential to develop new formulations of natural antimicrobials for preserving liquid foods such as milk. This work aimed to test the capability of the laser scattering imaging technique combined with chemometric procedures to inspect antimicrobial particles in milk matrices non-destructively. The RGB laser's interactions with the milk matrix were captured as diffraction patterns in digital images, from which data were extracted after imaging processing and modelled by chemometric procedures. The antimicrobials were based on solid inorganic particles (silica) functionalised with a plant essential oil (eugenol). The effect of the natural variability from five types of milk was studied (cow 0, 1.5 and 3.5% lipids, goat and sheep). The inspection functions focused on predicting the type of milk, presence of antimicrobial particles, functionalisation of particles and type of inorganic structure. PLS-DA was applied to perform classification models for each property prediction, combined with pre-processing and variable selection procedures to isolate the variability of the property of interest. The results revealed a high classification capacity for milk types. The properties of antimicrobials were also successfully predicted. In this case, data pre-processing and variable selection procedures had to be applied to reduce structural noise and improve the models from raw data. Combining imaging and chemometrics techniques could capture and model the variability generated by antimicrobial particles independently of the nature of milk. It established the basis for developing a possible non-destructive inspection system to control liquid food containing these new antimicrobials.

Understanding extended homometry based on complementary crystallographic orbit sets.

Extended homometry is a phenomenon in which distinct structures have the same X-ray diffraction (XRD) intensities, which may lead to incorrect results of structural analysis based on XRD methods. It is proposed and proved herein that half of a crystallographic orbit has the same powder X-ray diffraction intensity as its complementary set; three more theorems are deduced. These results are conducive to understanding the formation of extended homometric structures. Also analyzed are some reported or potential homometric or weakly homometric structures in the Inorganic Crystal Structure Database to confirm the theorems. This work presents a quick approach to analyze and construct extended homometric structures based on crystallographic orbits.

Chemical Rules for Stacked Kagome and Honeycomb Topological Semimetals.

The chemical rules for predicting and understanding topological states in stacked kagome and honeycomb lattices are studied in both analytical and numerical ways. Starting with a minimal five-band tight-binding model, all the topological states are sorted into five groups, which are determined by the interlayer and intralayer hopping parameters. Combined with the model, an algorithm is designed to obtain a series of experimentally synthesized topological semimetals with kagome and honeycomb layers, i.e., IAMX family (IA = Alkali metal element, M = Rare earth metal element, X = Carbon group element), in the inorganic crystal structure database. A follow-up high-throughput calculation shows that IAMX family materials are all nodal-line semimetals and they will be Weyl semimetals after taking spin-orbit coupling into consideration. To have further insights into the topology of the IAMX family, a detailed chemical rule analysis is carried out on the high-throughput calculations, including the lattice constants of the structure, intralayer and interlayer couplings, bond strengths, electronegativity, and so on, which are consistent with the tight-binding model. This study provides a way to discover and modulate topological properties in stacked kagome and honeycomb crystals and offers candidates for studying topology-related properties like topological superconductors and axioninsulators.

A Self-Healing Gel with an Organic-Inorganic Network Structure for Mitigating Circulation Loss.

Lost circulation control remains a challenge in drilling operations. Self-healing gels, capable of self-healing in fractures and forming entire gel block, exhibit excellent resilience and erosion resistance, thus finding extensive studies in lost circulation control. In this study, layered double hydroxide, Acrylic acid, 2-Acrylamido-2-methylpropane sulfonic acid, and CaCl2 were employed to synthesize organic-inorganic nanocomposite gel with self-healing properties. The chemical properties of nanocomposite gels were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, X-ray photoelectron spectroscopy and thermogravimetric analysis. layered double hydroxide could be dispersed and exfoliated in the mixed solution of Acrylic acid and 2-Acrylamido-2-methylpropane sulfonic acid, and the swelling behavior, self-healing time, rheological properties, and mechanical performance of the nanocomposite gels were influenced by the addition of layered double hydroxide and Ca2+. Optimized nanocomposite gel AC6L3, at 90 °C, exhibits only a self-healing time of 3.5 h in bentonite mud, with a storage modulus of 4176 Pa, tensile strength of 6.02 kPa, and adhesive strength of 1.94 kPa. In comparison to conventional gel, the nanocomposite gel with self-healing capabilities demonstrated superior pressure-bearing capacity. Based on these characteristics, the nanocomposite gel proposed in this work hold promise as a candidate lost circulation material.

A database of computed Raman spectra of inorganic compounds with accurate hybrid functionals

Raman spectroscopy is widely applied in identifying local structures in materials, but the interpretation of Raman spectra is non-trivial. An accurate computational database of reference spectra calculated with a consistent level of theory can significantly aid in interpreting measured Raman spectra. Here, we present a database of Raman spectra of inorganic compounds calculated with accurate hybrid functionals in density functional theory. Raman spectra were obtained by calculating dynamical matrices and polarizability tensors for structures from the Inorganic Crystal Structure Database. The calculated Raman spectra and other phonon properties (e.g., infrared spectra) are stored in a MongoDB database publicly shared through a web application. We assess the accuracy of our Raman calculations by statistically comparing ~80 calculated spectra with an existing experimental Raman database. To date, the database contains 161 compounds and is continuously growing as we add more materials computed with our automated workflow.

Candidate ferroelectrics via ab initio high-throughput screening of polar materials

Ferroelectrics are a class of polar and switchable functional materials with diverse applications, from microelectronics to energy conversion. Computational searches for new ferroelectric materials have been constrained by accurate prediction of the polarization and switchability with electric field, properties that, in principle, require a comparison with a nonpolar phase whose atomic-scale unit cell is continuously deformable from the polar ground state. For most polar materials, such a higher-symmetry nonpolar phase does not exist or is unknown. Here, we introduce a general high-throughput workflow that screens polar materials as potential ferroelectrics. We demonstrate our workflow on 1978 polar structures in the Materials Project database, for which we automatically generate a nonpolar reference structure using pseudosymmetries, and then compute the polarization difference and energy barrier between polar and nonpolar phases, comparing the predicted values to known ferroelectrics. Focusing on a subset of 182 potential ferroelectrics, we implement a systematic ranking strategy that prioritizes candidates with large polarization and small polar-nonpolar energy differences. To assess stability and synthesizability, we combine information including the computed formation energy above the convex hull, the Inorganic Crystal Structure Database id number, a previously reported machine learning-based synthesizability score, and ab initio phonon band structures. To distinguish between previously reported ferroelectrics, materials known for alternative applications, and lesser-known materials, we combine this ranking with a survey of the existing literature on these candidates through Google Scholar and Scopus databases, revealing ~130 promising materials uninvestigated as ferroelectric. Our workflow and large-scale high-throughput screening lays the groundwork for the discovery of novel ferroelectrics, revealing numerous candidates materials for future experimental and theoretical endeavors.

Preparation of strong soy protein composite materials with thermal conductivity and biodegradability by constructing nanophase enhanced organic-inorganic hybrid structure

The development of multifunctional films with high strength, biodegradability, and excellent thermal conductivity has drawn increasing interest. In this study, inspired by the unique hybrid structure of oysters, a nanophase-reinforced organic–inorganic hybrid structure was built using polydopamine modified boron nitride (BN@PDA), soy protein isolate (SPI), dialdehyde cellulose (DAC), and polyethylene glycol (PEG) to develop a strong soy protein film with multifunctionalities. The resultant films displayed excellent thermal diffusion ability and exhibited high tensile strength (24.03 MPa) and thermal conductivity (TC, 2.96 W·m−1·K−1) under low BN load (<0.5%). Meanwhile, the formation of non-covalent cross-linking and organic–inorganic hybrid structure endowed the films with superior flexibility. Importantly, owing to the selection of bio-based materials for preparation, the SPI-based films exhibited good biodegradability. It is believed that this study provides a creative perspective for the development of value-added multifunctional film materials and has good application prospects in advanced bio-based thermal conductive materials.

Exploiting the photophysical features of DMAN template in ITQ-51 zeotype in the search for FRET energy transfer.

The combination between photoactive molecules and inorganic structures is of great interest for the development of advanced materials in the field of optics. Particularly, zeotypes with extra-large pore size are attractive because they allow the encapsulation of bulky dyes. The microporous aluminophoshate Mg-ITQ-51 (IFO-type structure) represents an ideal candidate because of the synergic combination of two crucial features: the IFO framework itself, which is composed of non-interconnected one-dimensional extra-large elliptical channels with a diameter up to 11 Å able to host bulky guest species, and the particular organic structure-directing agent used for the synthesis (1,8-bis(dimethylamino)naphthalene, DMAN), which efficiently fills the IFO pores, and is itself a photoactive molecule with interesting fluorescence properties in the blue range of the visible spectrum, thus providing a densely-incorporated donor species for FRET processes. Besides, occlusion of DMAN dye in the framework triggers a notable improvement of its fluorescence properties by confinement effect. To extend the action of the material and to mimic processes such as photosynthesis in which FRET is essential, two robust laser dyes with bulky size, rhodamine 123 and Nile Blue, have been encapsulated for the first time in a zeolitic framework, together with DMAN, in a straightforward one-pot synthesis. Thus, photoactive systems with emission in the entire visible range have been achieved due to a partial FRET between organic chromophores protected in a rigid aluminophosphate matrix.

Dichotomy of π-stacking-directing noncovalent forces in organic–inorganic planar assemblies: the case of halo-substituted benzoquinones π-stacked with a platinum(ii) square-plane

The same organic–inorganic π-stacked structures of tetrahalo-1,4-benzoquinones QX (X = F, Cl, Br, I) with different interplanar holding forces have been investigated.

Engineering inorganic nanozyme architectures for decomposition of reactive oxygen species.

Enzyme-mimicking nanomaterials (nanozymes) with antioxidant activity are at the forefront of research efforts towards biomedical and industrial applications. The selection of enzymatically active substances and their incorporation into novel inorganic nanozyme structures is critically important for this field of research. To this end, the fabrication of composites can be desirable as these can either exhibit multiple enzyme-like activities in a single material or show increased activity compared to the nanozyme components. Conversely, by modifying the structure of a nanomaterial, enzyme-like activities can be induced in formerly inert particles. We identify herein the three main routes of composite nanozyme synthesis, namely, surface functionalization of a particle with another compound, heteroaggregation of individual nanozymes, and modification of the bulk nanozyme structure to achieve optimal antioxidant activity. We discuss in particular the different inorganic support materials used in the synthesis of nanozyme architectures and the advantages brought forth by the use of composites.

A novel class of multivalent ionic conductors with the La3CuSiS7 structure type: results of stepwise ICSD screening.

The results of high-throughput screening of the inorganic crystal structure database for new promising Ca2+-, Mg2+-, Zn2+- and Al3+-ion conducting ternary and quaternary sulfides, selenides, and tellurides are presented (∼1500 compounds). A geometrical-topological approach based on the Voronoi partition was initially used and yielded 104 compounds, which were unknown as conductors with possible cation migration. All compounds were passed through the bond valence site energy analysis to determine the migration energy Em. Furthermore, we established the logarithmic dependencies of Em on the geometrical parameters of the migration pathways. As a result, 16 out of 104 structures were filtered out as promising conductors. Finally, density functional theory simulations yielded the 11 most prospective compounds with Em < 1.0 eV. Among them, we found a novel class of ionic conductors with the La3CuSiS7 structure, for which ab initio molecular dynamic calculations were performed, revealing diffusion coefficients of ∼10-7 cm2 s-1 and ionic conductivity of ∼10-2 S cm-1 at 300 K.

Synthesis and properties of anhydrous rare-earth phosphates, monazite and xenotime: a review.

The synthesis methods, crystal structures, and properties of anhydrous monazite and xenotime (REPO4) crystalline materials are summarized within this review. For both monazite and xenotime, currently available Inorganic Crystal Structure Database data were used to study the effects of incorporating different RE cations on the unit cell parameters, cell volumes, densities, and bond lengths. Domains of monazite-type and xenotime-type structures and other AXO4 compounds (A = RE; X = P, As, V) are discussed with respect to cation sizes. Reported chemical and radiation durabilities are summarized. Different synthesis conditions and chemicals used for single crystals and polycrystalline powders, as well as first-principles calculations of the structures and thermophysical properties of these minerals are also provided.

Carbonate weakens the interactions between potassium and calcareous soil.

The ion interfacial transport driven by ion-surface interactions in calcareous soil has a profound impact on the nutrient storage and environmental buffer capacity of the main agricultural soils in dry and semi-arid areas. The roles that carbonate plays in preserving the soil's inorganic carbon pool and soil structure stability have been widely investigated, but its significance in the aforementioned microscopic processes, especially the influence of carbonate on the interfacial reaction kinetics of nutrient elements, is yet to be determined. In this study, potassium (K) was used as an indicator ion to investigate its affinity in carbonate-removed (CREM) and carbonate-reserved (CRES) calcareous soil using the general theory of ion diffusion in an external electric field. We discovered that (1) at a given initial K concentration, the carbonate in CRES soil retards the adsorption rate and diminishes the adsorption amount of K in calcareous soil, reducing the interfacial transport properties of nutrient ions at the solid-liquid interface of calcareous soils compared with CREM soil; and (2) this weakening of the interfacial transport effect on nutrient K originates from the soil carbonate, which prefers to weaken the electrostatic interaction intensity between K and the calcareous soil surface. Furthermore, this is due to the carbonate shielding effect on the surface adsorption sites of other soil components and the competitive relationship between K+ and cations released by carbonate dissolution. The influence of carbonate on the nutrient ion transport at the solid-liquid interface of calcareous soil has been investigated by soil electrochemistry theory-based ion adsorption kinetics, and the links between kinetic features and ion-surface binding energy have been clarified.

The empty world - a view from the free volume concept and Eyring's rate process theory.

The many-body problem is a common issue, irrespective of the scale of entities under consideration. From electrons to atoms, small molecules like simple inorganic or organic structures, large molecules like proteins or polymers, nanometer- or micrometer-sized particles, granular matter, and even galaxies, the precise determination or estimation of geometrical locations and momentum energy of individual entities, and interaction forces between these millions of entities, is impossible but unfortunately important for understanding the collective physical properties like mechanical and electrical characteristics of the whole system. Despite foreseeable difficulties and complexities, attempts to estimate "interparticle" forces have never stopped using traditional Newtonian models, quantum mechanical approaches, and density functional theory. In this review, a simple approach integrating the free volume and Eyring's rate process theory is summarized and its application across a wide range of scales from electrons to the universe is presented in a unified manner. The focus is on comparisons between theoretical predictions and experimental results.

Low viscosity and low temperature curing reactive POSS/epoxy hybrid resin with enhanced toughness and comprehensive thermal performance.

The mechanical and high-temperature resistance properties of epoxy resins cured at low temperatures (Tcuring ≤ 100 °C) are often inferior, and the most toughening modification methods for epoxy resins tend to compromise thermal resistance, which significantly limit the practical applications of it. Therefore, this work reported a low viscosity and low-temperature curing epoxy hybrid resin system (OPEP), adopting E-51 as a resin matrix, liquid anhydride (MHHPA) as a curing agent, tertiary amine (DMBA) as a curing accelerator, and reactive octa-epoxy terminated polyhedral oligomeric silsesquioxane (OG-POSS) as a toughening modifier. Results demonstrated that the OPEP system has excellent processability with low viscosity and long processing window period and satisfies the practical requirements of low-temperature curing. The OG-POSS exhibits superior compatibility and reactivity with the resin matrix, and its addition slightly reduces the Eα of the curing reaction and has a certain promotive effect on the curing of epoxy resin. In addition, the curing reaction rate of the OPEP resin complies with the Šesták-Berggren autocatalytic kinetics model. The impact strength, flexural strength, tensile strength, and elongation at break of the OPEP resin reached a maximum of 15.55 kJ m-2, 121.65 MPa, 90.36 MPa, and 2.48%, representing increases of 55.97%, 3.1%, 64.68%, and 26.51% compared to those of the pure resin, respectively. Notably, due to the heat-resistant inorganic silicon cage structure of OG-POSS, the thermal decomposition temperature (Td5), glass transition temperature (Tg), and heat distortion temperature (THDT) of the OPEP0.02 resin were 313.2 °C, 123.7 °C, and 102.0 °C, showing increases of 13.0 °C, 2.3 °C, and 6.8 °C compared to the pure resin, respectively, which is difficult to achieve for the general thermosetting resin toughening modification method. This research utilized organic-inorganic nanohybrid materials (POSS) to optimize the toughness and thermal stability of the resin in a coordinated manner, providing guidance for the preparation of high-performance epoxy resins that cure at low temperatures.

Efficient photocatalytic hydrogen production by organic–inorganic heterojunction structure in Chl@Cu2O/Ti3C2Tx

The idea of exploiting the solar energy-driven photocatalytic hydrogen evolution reaction (HER) to generate hydrogen energy, a sustainable clean energy source, to solve problems such as greenhouse gas emissions is believed to be a feasible strategy.

The effect of the use of the deproteinization agent hypochlorous acid and two different pit and fissure sealant self-adhesive flowable composites upon its bonding with the enamel.

This study evaluates the effect of the deproteinization agents hypochlorous acid and sodium hypochlorite upon the bonding of the two different pit and fissure sealant, self-adhesive flowable composites with the enamel. Thirty-six third molars were randomly divided into six different groups. The groups were formed as follows: Group 1: 37% phosphoric acid + VertiseTM Flow; Group 2: 200 ppm hypochlorous acid + 37% phosphoric acid VertiseTM Flow; Group 3: 5.25% sodium hypochlorite + 37% phosphoric acid + VertiseTM Flow; Group 4: 37% phosphoric acid + Constic; Group 5: 200 ppm hypochlorous acid + 37% phosphoric acid + Constic; Group 6: 5.25% sodium hypochlorite + 37% phosphoric acid + Constic. In each group, samples were obtained that were rectangular prisms in shape (n = 12). Groups to which a deproteinization agent was applied (Groups 2, 3 and 5, 6) showed statistically higher microtensile bonding strength than Group 1, Group 4. There was no statistically significant difference in terms of microtensile bonding strength values between the Groups 3 and the Group 6. The study found that the groups to which deproteinization agents were applied had statistically higher microtensile bonding strength values compared with those groups to which acid and fissure sealants were applied. In this study, it was concluded that the use of fissure-sealing self-adhesive flowable composites after acid application to permanent tooth enamel provides an acceptable bond strength given the limitations of in vitro studies. In line with the results obtained, it was observed that in addition to the removal of the inorganic structure with the application of acid, the removal of the organic structure with the use of deproteinization agent increased the bond strength to the enamel.