Inorganic Structures Research Articles

Complexity Parameters for Molecular Solids

Structural complexity measures based on Shannon information entropy are widely used for inorganic crystal structures. However, the application of these parameters for molecular crystals requires essential modification since atoms in inorganic compounds usually possess more degrees of freedom. In this work, a novel scheme for the calculation of complexity parameters (HmolNet, HmolNet,tot) for molecular crystals is proposed as a sum of the complexity of each molecule, the complexity of intermolecular contacts, and the combined complexity of both. This scheme is tested for several molecular crystal structures.

Enantioselective Recognition of Racemic Amino Alcohols in Aqueous Solution by Chiral Metal-Oxide Keplerate {Mo132 } Cluster Capsules.

Determining the relative configuration or enantiomeric excess of a substance may be achieved using NMR spectroscopy by employing chiral shift reagents (CSRs). Such reagents interact noncovalently with the chiral solute, resulting in each chiral form experiencing different magnetic anisotropy; this is then reflected in their NMR spectra. The Keplerate polyoxometalate (POM) is a molybdenum‐based, water‐soluble, discrete inorganic structure with a pore‐accessible inner cavity, decorated by differentiable ligands. Through ligand exchange from the self‐assembled nanostructure, a set of chiral Keplerate host molecules has been synthesised. By exploiting the interactions of analyte molecules at the surface pores, the relative configuration of chiral amino alcohol guests (phenylalaninol and 2‐amino‐1‐phenylethanol) in aqueous solvent was establish and their enantiomeric excess was determined by 1H NMR using shifts of ΔΔδ=0.06 ppm. The use of POMs as chiral shift reagents represents an application of a class that is yet to be well established and opens avenues into aqueous host‐guest chemistry with self‐assembled recognition agents.

Preparation and Characterization of Narrow Size Distribution PMSQ Microspheres for High-Frequency Electronic Packaging

Polymethylsilsesquioxane (PMSQ) has become a kind of widely studied filler used in the electronic circuit board substrates due to its organic–inorganic hybrid structure, low dielectric constant, and good thermal stability, among other factors. Herein, the PMSQ microspheres were prepared by a two-step acid–base-catalyzed sol–gel method; the influences of reaction conditions including the ratio of water/methyltrimethoxysilane (MTMS), reaction temperature, concentration of the catalyst, and stirring time were systematically investigated; and the optimized reaction condition was then obtained towards a narrow particle size distribution and good sphericity. The microstructure of PMSQ microspheres was analyzed by the infrared spectrum and X-ray diffraction (XRD), which indicated that the as-prepared PMSQ had a ladder-dominant structure. The thermogravimetric analysis (TGA) demonstrated an excellent thermal stability of as-prepared PMSQ microspheres. More specifically, the dielectric constants at high frequency (1~20 GHz) of as-prepared PMSQ microspheres were measured to be about 3.7, which turned out a lower dielectric constant compared to SiO2 powder (≈4.0). This study paves the way to further improve the performance of the electronic circuit board substrates for the application of high-frequency electronic packaging.

Comparative study of polymer based novel organic–inorganic hetero-junctions with n-GaN and AlGaN/GaN epi-structures

The present study reports the fabrication and characterization of organic–inorganic hetero-junctions based on π-conjugated polymers on n-GaN and Al0.24Ga0.76N/GaN epi-structures. The polymer contact properties were investigated with n-GaN and AlGaN/GaN epi-structures. The PNA/n-GaN and PNA/AlGaN/GaN samples exhibited better diode characteristics with low ideality factor values of 3.15 and 2.79, respectively in comparison to PANI based n-GaN and AlGaN/GaN diodes. Also a reasonably good Schottky barrier height was achieved with PNA polymer for n-GaN (0.52 eV) and AlGaN/GaN (0.70 eV) samples. Low reverse leakage current ~10−12 A and 10−9 A at a reverse bias voltage of −10 V was observed for PNA/n-GaN and PNA/AlGaN/GaN samples, respectively. PNA is a promising candidate in comparison to PANI for π-conjugated polymer contact on n-GaN and AlGaN/GaN epitaxial hetero-structure. The studies also confirmed that the performance of the diode could be improved by using AlGaN/GaN inorganic structure than GaN.

Stabilization Effects of Natural Compounds and Polyhedral Oligomeric Silsesquioxane Nanoparticles on the Accelerated Degradation of Ethylene-Propylene-Diene Monomer.

In this work the analysis on the stabilization activities of some natural antioxidants (rosemary extract, capsaicin, quercetin or oleanolic acid) is presented. A similar contribution of an inorganic structure—polyhedral oligomeric silsesquioxane (POSS) nanoparticles—is also evaluated. The stabilization effects on the oxidation protection were investigated for several formulations based on ethylene-propylene-diene-terpolymer (EPDM). The samples were examined in pristine state or after γ-irradiation, when the accelerated degradation scission of polymer macromolecules followed by the mitigation of oxidation. Three evaluation procedures: chemiluminescence, FTIR spectroscopy and thermal analysis were applied for the characterization of stability efficiency. The delaying effect of oxidative aging in EPDM matrix is illustrated by the values of activation energy, which are correlated with the type and concentration of embedded compounds. The durability of studied EPDM formulations is discussed for the assessment of material life. The improved behavior of structured hybrids useful for the optimization application regimes is essentially based on the antioxidant properties of polyphenolic components in the cases of natural antioxidants or on the penetration of free radical intermediates into the free volumes of POSS.

Zhijun Ning

Angewandte ChemieVolume 133, Issue 31 p. 16887-16887 Introducing …Free Access Zhijun Ning First published: 01 July 2021 https://doi.org/10.1002/ange.202107321AboutSectionsPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract “My favorite thing about my lab group is interdisciplinary research atmosphere. … My biggest inspiration is walking along the grand gallery in ShanghaiTech campus …” Find out more about Zhijun Ning in his Introducing … Profile. Zhijun Ning The author presented on this page has published his first article as a submitting corresponding author in Angewandte Chemie: “Low-Dimensional Inorganic Tin Perovskite Solar Cells Prepared by Templated Growth”: H. Li, X. Jiang, Q. Wei, Z. Zang, M. Ma, F. Wang, W. Zhou, Z. Ning, Angew. Chem. Int. Ed. 2021, 60, doi.org/10.1002/anie.202104958; Angew. Chem. 2021, 133, doi.org/10.1002/ange.202104958. Position: Associate Professor (Tenured), School of Physical Science and Technology, ShanghaiTech University Homepage: https://spst.shanghaitech.edu.cn/2018/0301/c2349a52605/page.htm ORCID: orcid.org/0000-0002-9130-3490 Education: 2000–2004 Undergraduate studies, Liaoning Shihua University (China) 2009 PhD with He Tian, East China University of Science and Technology 2009–2011 Postdoc with Hans Ågren and Ying Fu, Royal Institute of Technology (Sweden) 2011–2014 Postdoc with Edward H. Sargent, University of Toronto (Canada) Research: Solution-processed optoelectronic materials and devices, especially tin perovskite solar cells and quantum dot infrared photodetectors Hobbies: Basketball, music The greatest scientific advance of the next decade will be a performance leap of clean energy materials and system. Science is fun because there are lots of surprise. The most exciting thing about my research is the development of low-dimensional tin perovskite solar cells. I chose my current career path because of strong curiosity for an unknown world. I advise my students to stay curious and be persistent. A turning point in my career was joining ShanghaiTech University. My long-term goal is real applications of solution-processed optoelectronic materials and devices. My group has fun by having parties. My not-so-secret passion is to develop new materials and devices. I lose track of time when traveling. A good day at work starts with a cup of tea. My biggest inspiration is walking along the grand gallery in the campus. If I had one year of paid leave I would read and travel. The most important quality of a mentor is self-discipline. My favorite thing about my lab group is interdisciplinary research atmosphere. My favorite structure type is the cubic. My favorite place on earth is my hometown, a village at Hunan, central part of China. My favorite food is a home-made dried bean curd in my hometown. My favorite drink is green tea. My favorite music is rock. Behind the Science References 1The tin perovskite solar cell is emerging as an important thin-film photovoltaic technology. The improvement of its stability is an urgent task nowadays for which the combination of low-dimensional and inorganic scaffold structures is a promising approach. However, films based on low-dimensional inorganic tin perovskite structure usually show high defect density and inhomogeneous orientation. We spent a lot of time to address this problem without success. Accidentally, my student Hansheng discovered that a special reagent can help to grow a high-quality film. We then revealed the intermediate structure and clarified the kinetics of crystal growth. Google Scholar Volume133, Issue31July 26, 2021Pages 16887-16887 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. ReferencesRelatedInformation

The theoretical evaluation of new promising solid ion conductors for zinc-ion batteries

Recently, we have screened the Inorganic Crystal Structure Database (ICSD, version 2020/1) to find new Zn2+-ion conductors. After a stepwise selection procedure, we have identified five most promising Zn-ion conductors ZnFe2O4, ZnV2O4, ZnCr2O4, ZnP2O6 and Zn3S2O9. In this work we describe the ion conductivity in the selected structures in detail by using of a set of methods: analysis of free space in crystals (geometrical-topological analysis, based on the Voronoi partitioning approach), calculation of the Zn2+-ion migration energy barrier within the bond valence site energy method, and calculation of the Zn2+-ion energy barriers within the density functional theory approach.

Crystal structure of silver carbonate iodide Ag10(CO3)3I4.

The title silver carbonate iodide, Ag10(CO3)3I4, deca-silver(I) tris-(carbonate) tetra-iodide, was recently reported as a precursor of the new superionic conductor Ag17(CO3)3I11. Ag10(CO3)3I4, was prepared by heating a stoichiometric powder mixture of AgI and Ag2CO3 at 430 K. A single-crystal suitable for X-ray diffraction analysis was obtained by slow cooling of a melt with an AgI-rich composition down from 453 K. Ag10(CO3)3I4 exhibits a layered crystal structure packed along [10], in which Ag atoms are inter-calated between the layers of hexa-gonally close-packed I atoms, and CO3 groups. Up to now, Cs3Pb2(CO3)3I is the only other compound containing carbonate groups and iodide ions registered in the Inorganic Crystal Structure Database.

Single-Crystal Inorganic Helical Architectures Induced by Asymmetrical Defects in Sub-Nanometric Wires.

Constructing single-crystal inorganic helical structures is a fascinating subject for a large variety of research fields. However, the driving force of self-coiling, particularly in helical architectures, still remains a major challenge. Here, using MoO3-x sub-nanometric wires (SNWs) as an example, we identified that spontaneous helical architecture with different dimensional features is closely related with their surface asymmetrical defects. Specifically, the surface defects of SNWs are critical to produce the self-coiling process, thereby achieving the ordered helical conformations. Theoretical calculations further suggest that the formation of in-plane and out-of-plane coiling structures is determined by the asymmetrical distribution of the surface defects, and the inhomogeneous charge separation with strong Coulomb attraction dominates the different structural configurations. The resulting MoO3-x SNW exhibits excellent photothermal behaviors in both aqueous solutions and hydrogel matrixes. Our study provides a novel protocol to achieve helical structure design for their future applications.

Well-defined organic–inorganic core–shell structure IPN-P(AA-co-AM) polymer spheres by modified suspension polymerization

Well-defined organic–inorganic core–shell structure IPN-P(AA-co-AM) polymer spheres by modified suspension polymerization

JAMIP: an artificial-intelligence aided data-driven infrastructure for computational materials informatics

Materials informatics has emerged as a promisingly new paradigm for accelerating materials discovery and design. It exploits the intelligent power of machine learning methods in massive materials data from experiments or simulations to seek new materials, functionality, and principles, etc. Developing specialized facilities to generate, collect, manage, learn, and mine large-scale materials data is crucial to materials informatics. We herein developed an artificial-intelligence-aided data-driven infrastructure named Jilin Artificial-intelligence aided Materials-design Integrated Package (JAMIP), which is an open-source Python framework to meet the research requirements of computational materials informatics. It is integrated by materials production factory, high-throughput first-principles calculations engine, automatic tasks submission and monitoring progress, data extraction, management and storage system, and artificial intelligence machine learning based data mining functions. We have integrated specific features such as an inorganic crystal structure prototype database to facilitate high-throughput calculations and essential modules associated with machine learning studies of functional materials. We demonstrated how our developed code is useful in exploring materials informatics of optoelectronic semiconductors by taking halide perovskites as typical case. By obeying the principles of automation, extensibility, reliability, and intelligence, the JAMIP code is a promisingly powerful tool contributing to the fast-growing field of computational materials informatics.

Role of soil microbiota in soil fertility

Long- term adoption of total agricultural approach which negatively influences the soil prolificacy, soil microbiome and may compromise the feature and amount of crop mass production. In agriculture, soil is a critical part, in which the original sources of nutrients for grow crops and the microorganisms is very important to improve soil texture or soil health for healthy growing crops. Soil microbiota are an energetic component of soil and showed varieties useful activities in the soil system. Soil richness is the characteristic limit of a soil to give the fundamental plant supplements in sufficient sums and legitimate extents for plant development. There is an enormous chance to upgrade soil ripeness through microorganisms, as organisms are “inherent” soil controllers and impetuses adding to reusing of supplements into accessible inorganic structures and give early admonition of land corruption. The core interest of this part is on the possibility of utilizing organisms as decomposers of (cellulose, protein and lignin), formers (humus, nitrate and nitrite), nitrogen fixers, ammonifiers, oxidizers (iron, hydrogen and sulfur), phosphorus solubilizers and denitrifiers. In this specific circumstance, the components viz., natural toxins and environmental change that limit the improvement of soil richness. Today’s, there is great trial for the agricultural system in which growing the human population is a great problem in the land breakdown and decrease the microbial population that’s why enhance the soil fertility and plant growth rate decreases. Therefore, in this review we describe the benefits of soil microbiota to maintain soil fertility.

Combination of recommender system and single-particle diagnosis for accelerated discovery of novel nitrides.

Discovery of new compounds from wide chemical space is attractive for materials researchers. However, theoretical prediction and validation experiments have not been systematically integrated. Here, we demonstrate that a new combined approach is powerful in significantly accelerating the discovery rate of new compounds, which should be useful for exploration of a wide chemical space in general. A recommender system for chemically relevant composition is constructed by machine learning of Inorganic Crystal Structure Database using chemical compositional descriptors. Synthesis and identification experiments are made at the chemical compositions with high recommendation scores by the single-particle diagnosis method. Two new compounds, La4Si3AlN9 and La26Si41N80O, and two new variants (isomorphic substitutions) of known compounds, La7Si6N15 and La4Si5N10O, are successfully discovered. Finally, density functional theory calculations are conducted for La4Si3AlN9 to confirm the energetic and dynamical stability and to reveal its atomic arrangement.

Evaluation of density functional theory for a large and diverse set of organic and inorganic equilibrium structures.

Density functional theory (DFT) has been extensively benchmarked for energetic properties; however, less attention has been given to equilibrium structures and the effect of using a certain DFT geometry on subsequent energetic properties. We evaluate the performance of 52 contemporary DFT methods for obtaining the structures of 122 species in the W4-11-GEOM database. This dataset includes a total of 246 unique bonds: 117 H─X, 65 X─Y, 49 X═Y, and 15 XY bonds (where X and Y are first- and second-row atoms) and 133 key bond angles: 96 X-Y-H, 22 X-Y-Z, and 15 H-X-H angles. The reference geometries are optimized at the CCSD(T)/jul-cc-pV(n+d)Z level of theory (n= 5, 6). The performance of DFT is evaluated in conjunction with the Def2-nZVPP (n= T, Q), cc-pV(T+d)Z, and jul-cc-pV(T+d)Z basis sets. The root-mean-square deviations (RMSDs) over the bond distances of the best performing functionals from each rung of Jacob's Ladder are 0.0086 (SOGGA11), 0.0088 (τ-HCTH), 0.0059 (B3LYP), 0.0054 (TPSSh), and 0.0032 (DSD-PBEP86) Å. We evaluate the effect of the choice of the DFT geometry on subsequent molecular energies calculated with W1-F12 theory. Geometries obtained with GGA and MGGA methods result in large RMSDs in the subsequent W1-F12 energies; however, six hybrid GGA functionals (B3LYP, B3P86, mPW3PBE, B3PW91, mPW1LYP, and X3LYP) result in an excellent performance with RMSDs between 0.25 and 0.30 kJ mol-1 relative to the CCSD(T)/CBS reference geometries. The B2GP-PLYP and mPW2-PLYP DHDFT methods result in near-CCSD(T) accuracy with RMSDs of 0.11 and 0.10kJ mol-1 , respectively.

Microstructures, mechanical properties and tribological behaviors of amorphous carbon coatings in-situ grown on polycarbonate surfaces

Pure amorphous carbon (a-C) coating, chromium doped amorphous carbon (a-C/Cr) coating and silicon doped amorphous carbon (a-C/Si) coating were synthesized on Polycarbonate (PC) plastic substrates by continuous treatment of different plasma combinations. Microstructures, mechanical properties and tribological behaviors of the as-presented coatings were systematically investigated. As a result, the in-situ growth mechanisms were demonstrated for all of these carbonaceous coatings. This in-situ growth meant an in-situ transformation from the polymer structure into inorganic structure from the surface or subsurface of the substrate followed by an epitaxial growth on the transformed inorganic layer. Cr and Si dopant generated a bulky microstructure, leading to a higher density of in-situ grown a-C/Cr and a-C/Si coatings than the a-C coating on PC substrates. The hardness and elastic modulus of PC substrate were significantly improved by these in-situ grown carbonaceous coatings. Pure a-C coating showed the best protective effect on PC substrate under sliding-friction condition, with scaly protection mechanism, among these different coatings. The fundamental for good protective effect of pure a-C coating on PC was the in-situ growth mechanism, which endowed reliable adhesion of hard a-C coating on soft PC substrate even if there were cracks under sliding condition.

Bright Near-Infrared to Visible Upconversion Double Quantum Dots Based on a Type-II/Type-I Heterostructure

Upconverting semiconductor quantum dots (QDs) combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Here, we present upconverting type-II/type-I colloidal double QDs that enable enhancement of the performance of near-infrared to visible photon upconversion in QDs and broadening the range of relevant materials used. The resulting ZnTe/CdSe@CdS@CdSe/ZnSe type-II/type-I double QDs possess a very high photoluminescence quantum yield, monoexponential decay dynamics, and a narrow line width, approaching those of state-of-the-art upconverting QDs. We quantitatively characterize the upconversion cross section by direct comparison with two-photon absorption when varying the pump frequency across the absorption edge. Finally, we show that these upconversion QDs maintain their optical performance in a much more demanding geometry of a dense solid film and can thus be incorporated in devices as upconversion films. Our design provides guidance for fabricating highly efficient upconverting QDs with potential applications such as security coding and bioimaging.

Layered Hybrid Formamidinium Lead Iodide Perovskites: Challenges and Opportunities.

ConspectusHybrid halide perovskite materials have become one of the leading candidates for various optoelectronic applications. They are based on organic-inorganic structures defined by the AMX3 composition, were A is the central cation that can be either organic (e.g., methylammonium, formamidinium (FA)) or inorganic (e.g., Cs+), M is a divalent metal ion (e.g., Pb2+ or Sn2+), and X is a halide anion (I-, Br-, or Cl-). In particular, FAPbI3 perovskites have shown remarkable optoelectronic properties and thermal stabilities. However, the photoactive α-FAPbI3 (black) perovskite phase is not thermodynamically stable at ambient temperature and forms the δ-FAPbI3 (yellow) phase that is not suitable for optoelectronic applications. This has stimulated intense research efforts to stabilize and realize the potential of the α-FAPbI3 perovskite phase. In addition, hybrid perovskites were proven to be unstable against the external environmental conditions (air and moisture) and under device operating conditions (voltage and light), which is related to various degradation mechanisms. One of the strategies to overcome these instabilities has been based on low-dimensional hybrid perovskite materials, in particular layered two-dimensional (2D) perovskite phases composed of organic layers separating hybrid perovskite slabs, which were found to be more stable toward ambient conditions and ion migration. These materials are mostly based on SxAn-1PbnX3n+1 composition with various mono- (x = 1) or bifunctional (x = 2) organic spacer cations that template hybrid perovskite slabs and commonly form either Ruddlesden-Popper (RP) or Dion-Jacobson (DJ) phases. These materials behave as natural quantum wells since charge carriers are confined to the inorganic slabs, featuring a gradual decrease in the band gap as the number of inorganic layers (n) increases from n = 1 (2D) to n = ∞ (3D). While various layered 2D perovskites have been developed, their FA-based analogues remain under-represented to date. Over the past few years, several research advances enabled the realization of FA-based layered perovskites, which have also demonstrated a unique templating effect in stabilizing the α-FAPbI3 phase. This, for instance, involved the archetypical n-butylammonium and 2-phenylethylammonium organic spacers as well as guanidinium, 5-ammonium valeric acid, iso-butylammonium, benzylammonium, n-pentylammonium, 2-thiophenemethylammonium, 2-(perfluorophenyl)ethylammonium, 1-adamantylmethanammonium, and 1,4-phenylenedimethanammonium. FAPbBr3-based layered perovskites have also demonstrated potential in various optoelectronic applications, yet the opportunities associated with FAPbI3-based perovskites have attracted particular attention in photovoltaics, stimulating further developments. This Account provides an overview of some of these recent developments, with a particular focus on FAPbI3-based layered perovskites and their utility in photovoltaics, while outlining challenges and opportunities for these hybrid materials in the future.

Machine-learned potentials for next-generation matter simulations.

The choice of simulation methods in computational materials science is driven by a fundamental trade-off: bridging large time- and length-scales with highly accurate simulations at an affordable computational cost. Venturing the investigation of complex phenomena on large scales requires fast yet accurate computational methods. We review the emerging field of machine-learned potentials, which promises to reach the accuracy of quantum mechanical computations at a substantially reduced computational cost. This Review will summarize the basic principles of the underlying machine learning methods, the data acquisition process and active learning procedures. We highlight multiple recent applications of machine-learned potentials in various fields, ranging from organic chemistry and biomolecules to inorganic crystal structure predictions and surface science. We furthermore discuss the developments required to promote a broader use of ML potentials, and the possibility of using them to help solve open questions in materials science and facilitate fully computational materials design.

Highly sensitive acetone sensor based on WO3 nanosheets derived from WS2 nanoparticles with inorganic fullerene-like structures

Metal oxide semiconductor (MOS) gas sensors are promising for applications in environmental monitoring, dangerous gas detection, and disease diagnosis. Seeking for advanced MOS sensing materials that possess high sensitivity and low limit of detection (LOD) at sub-ppm level is a great challenge. Here, we report the first creation of two-dimensional (2D) WO3 nanosheets by annealing of the inorganic fullerene (IF)-like WS2 nanoparticles that were prepared via sulfurization of WO3 nanoparticles. Transformation of WS2 to WO3 was realised during the annealing process, simultaneously accompanied by the collapse of the hollow IF-WS2 structures and the formation of tiny 2D WO3 nanosheets with a lateral size of 40−80 nm. The resulting 2D WO3 nanosheets exhibited highly enhanced acetone-sensing performance in terms of sensitivity, selectivity, and response/recovery rates compared with the WO3 nanoparticles used as precursor for the synthesis of the IF-WS2 nanoparticles. The nanosheets also demonstrated great repeatability, reliable long-term stability, and very low LOD, making them a promising candidate as gas sensor to detect breath acetone.

Double Free: A Promising Route toward Moisture-Stable Hypotoxic Hybrid Perovskites

Double Free: A Promising Route toward Moisture-Stable Hypotoxic Hybrid Perovskites