Crystalline Materials Research Articles

Machine learning descriptors for crystal materials: applications in Ni-rich layered cathode and lithium anode materials for high-energy-density lithium batteries

Lithium batteries have revolutionized energy storage with their high energy density and long lifespan, but challenges such as energy density limitations, safety, and cost still need to be addressed. Crystalline materials, including Ni-rich cathodes and lithium anodes, play pivotal roles in the performance of high-energy-density lithium batteries. Understanding the micro-scale behavior and degradation mechanisms of these materials is crucial for improving macro-scale battery performance. Simulation methods, particularly machine learning (ML) techniques, have become indispensable tools in elucidating these intricate processes because of great efficiency and acceptable accuracy. ML methods depend on descriptors, which bridge the gap between crystal structures and input matrices of models. These descriptors encode essential atomic-level details in crystal structures, enabling predictions of material properties and behaviors relevant to lithium batteries. This paper reviews and discusses the diverse array of descriptors employed in the simulation of crystalline materials for lithium batteries with high energy density. Case studies highlight the effectiveness of different descriptors in simulating cathode behaviors such as Li/Ni disordering, screening of stable LiNi0.8Co0.1Mn0.1O2 (NMC811) configurations, and lithium deposition behaviors at the anode interface. The discussed descriptors can also be applied to other crystalline cathode, anode, and electrolyte materials in lithium batteries and advance the development of lithium batteries with superior energy density.

Elastic properties of Fe95-yNb2Mo2Cu1Siy-xBx (x=5-8, y=20-26) at % amorphous alloys

Amorphous materials exhibit complex atomic structures characterized by the absence of long-range order, in contrast to the well-defined periodicity of crystalline materials. This structural complexity is further pronounced in compositions such as FeMCuSiB (M = Nb, Mo, W and Ta), which incorporate elements with varying atomic radii and valencies. The Young's modulus of structures generated using traditional methods, such as melt-quenching and random packing, shows poor agreement with experimental data. In this study, we employ hybrid methods for generating the structures, which involve randomly packing elements without overlap, followed by thermalization at room temperature using Ab-initio Molecular Dynamics simulations. The Young's modulus evaluated from these structures aligns well with values measured using Dynamic Mechanical Analysis. Additionally, we utilize these structures to determine other elastic moduli including the bulk modulus and tetragonal shear modulus and find that the obtained values are consistent with the expected range for these compounds. We attribute the improved accuracy to a more representative approximation of the amorphous structure and the direct application of energy-strain relationships, rather than stress-strain relationships, for elastic moduli determination. Our methodology facilitates reliable predictions of the physical properties of amorphous materials and contributes to the design of FeMCuSiB (M = Nb, Mo, W and Ta) alloys with enhanced mechanical properties.

Nonalkaline Fabrication of Al-Based Metal-Organic Frameworks with Tailored Water Sorption Properties via Polymeric Hydroxy-Aluminum Basicity Modulation.

Metal-organic frameworks (MOFs) are porous crystalline materials composed of metallic nodes and organic ligands, demonstrating increasing potential in water harvesting in arid and semiarid regions. This study presents a nonalkaline, water-based, and scalable synthesis strategy designed to adjust the water sorption properties of aluminum-based MOFs (Al-MOFs), specifically, AlFum and MOF-303, by modifying the basicity of the metal source, polymeric hydroxy-aluminum, as an alternative. Characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA), confirmed the successful synthesis of Al-MOFs. The results revealed that high-basicity polymeric hydroxy-aluminum introduced additional mesoscopic intraparticle defects, interparticle voids, and hydrophilic surface sites to the primary microporous Al-MOFs. This led to an enhanced external surface area and uniformity in the particle size. Consequently, the water sorption performance of basicity-modulated Al-MOFs was significantly improved. Specifically, within the typical working humidity between 0.05 and 0.3, using polymeric hydroxy-aluminum of the highest basicity resulted in a 23% and 68% increase in water uptake for AlFum and MOF-303, respectively, achieving capacities of 0.43 and 0.37 g·g-1. Cyclic water adsorption-desorption tests further indicated the hydrolytic stability of prepared Al-MOFs. This study offers a novel approach to engineering MOF properties through metal source modulation, with important implications for applications in water harvesting and heat transfer.

Bidirectional enhancement of output performance of nanogenerators by M-COFs materials

The emergence of nanogenerators, which have the ability to capture mechanical energy from the environment and to collect and transmit tiny energy, is rapidly becoming a hot research topic. The performance of electrode materials is the key to the efficiency of nanogenerators. Covalent organic skeletons (COFs), a class of crystalline organic porous materials with the advantages of large specific surface area, high porosity, tunable structure, and flexible tailorability, have very significant advantages in being used as nanogenerator materials. In this paper, we synthesised two COF materials to investigate the effect of the introduction of active metals on the friction power generation performance of COFs without changing their topology, COF-2 containing zinc ions is capable of generating a short-circuit current of 107.5 µA during friction. The porous structure increases the effective contact area to form a larger charge density, and the introduction of metal ions can accelerate the charge separation and transport. The two bidirectional synergistic effects of the materials significantly improve the output performance of the nanogenerator, and a simple and efficient method is explored for the enhancement of the output performance of COF-based triboelectric nanogenerators.

Novel Strategy of Treating 2-Nitrobenzoic Acid Crystals with Energetic N2 Neutrals Using Cold Plasma

The organic adduct compounds of 2-nitrobenzoic acid crystals were grown as optically transparent crystals using the conventional slow evaporation solution technique. The crystals were powdered and irradiated with cold plasma. Cell parameter analysis confirmed the formation of a new crystalline material that resides in the triclinic P crystal system with space group P1. Fourier transform infrared spectra were recorded using the KBr pellet technique to determine the vibrational functional groups in the compound. Powder X-ray diffraction analysis was used to reveal the crystalline orientation of the powdered samples of the grown crystals. The obtained full width at half maximum for the (001) plane in the XRD spectrum indicates the excellent crystalline quality of the 2-nitrobenzoic acid crystals. The recorded UV–Vis absorption spectra reveal that the grown powdered crystal samples possess cut-off edges wavelengths at 428 and 428 nm and 353 and 354 nm for pure and plasma-treated samples, respectively. The optical energy bandgaps were found to be 2.0, 2.25, 4.06, and 4.02 eV for the pure and plasma-treated samples, respectively. The photoluminescence spectra show the blue emissions of the crystal. The FE-SEM images show the morphological modifications in which rounded platelets appear on the surfaces of the treated crystals.

Directional Transport in Hierarchically Aligned ZSM-5 Zeolites with High Catalytic Activity.

Zeolites, the most technically important crystalline microporous materials, are indispensable cornerstones of chemical engineering because of their remarkable catalytic properties and adsorption capabilities. Numerous studies have demonstrated that the hierarchical engineering of zeolites can maximize accessible active sites and improve mass transport, which significantly decreases the internal diffusion limits to achieve the desired performance. However, the construction of hierarchical zeolites with ordered alignments and size-controlled substructures in a convenient way is highly challenging. Herein, we develop a facile procedure using two common structure-directing agents, tetrapropylammonium hydroxide (TPAOH) and tetraethylammonium hydroxide (TEAOH), to synthesize hierarchically aligned ZSM-5 (Hie-ZSM-5) crystals with a-axis alignment substructures of controllable size. The control of the substructure size (α) in the range of 10-60 nm and the corresponding similarity (r = α/β, where β is the size of Hie-ZSM-5) ranging from 0.004 to 0.033 can be tuned by varying the Si/Al ratios (40-120). A systematic investigation of the overall crystallization process, using time-dependent XRD, SEM, TEM, and solid-state magic-angle spinning NMR (13C, 27Al, 29Si) methods, enable us to construct a solid mechanism for the generation of Hie-ZSM-5. Most importantly, directional transport in the unique structures of Hie-ZSM-5 efficiently enhances mass diffusion, as well as catalytic activity and stability. These findings improve our understanding of the zeolite crystallization process and inspire novel methods for the rational design of hierarchical zeolites.

Recent Advances in the Utilization of Chiral Covalent Organic Frameworks for Asymmetric Photocatalysis

The use of light energy to drive asymmetric organic transformations to produce high-value-added organic compounds is attracting increasing interest as a sustainable strategy for solving environmental problems and addressing the energy crisis. Chiral covalent organic frameworks (COFs), as porous crystalline chiral materials, have become an important platform on which to explore new chiral photocatalytic materials due to their precise tunability, chiral structure, and function. This review highlights recent research progress on chiral COFs and their crystalline composites, evaluating their application as catalysts in asymmetric photocatalytic organic transformations in terms of their structure. Finally, the limitations and challenges of chiral COFs in asymmetric photocatalysis are discussed, with future opportunities for research being identified.

Disentangling thermal birefringence and strain in the all-optical switching of ferroelectric polarization

Recent works have demonstrated that the optical excitation of crystalline materials with intense narrow-band infrared pulses, tailored to match the frequencies at which the crystal’s permittivity approaches close to zero, can drive a permanent reversal of magnetic and ferroelectric ordering. However, the physical mechanism that microscopically underpins this effect remains unclear, as well as the precise role of laser-induced heating and macroscopic strains. Here, we explore how infrared pulses can simultaneously give rise to strong temperature-dependent birefringence and strain in ferroelectric barium titanate. We develop a model of these two coexisting effects, allowing us to use polarization microscopy to disentangle them through their spatial distributions, temporal evolutions and spectral dependencies. We experimentally observe strain-induced patterns that are an order of magnitude larger than that which can be accounted for by laser-induced heating alone, suggesting that non-thermal effects must also play a role. Our results reveal the distinct fingerprints of heat- and strain-induced birefringence, shedding new light on the process of all-optical switching of order parameters in the epsilon-near-zero regime.

Forecast of electric transport property via two models

Temperature and synthesis condition-dependent resistivity are critical parameters for determining the electrical properties of materials. Modeling serves as a powerful tool for predicting the electrical transport characteristics of materials. The first objective of this work was to conduct a quantitative analysis of the reported metallic and insulating resistivity behaviors in double-phase materials. Using non-linear regression, both a phenomenological model and an Asym2sig asymmetric peak model were employed to quantitatively analyze the temperature-dependent resistivity. The fitting results align closely with the observed resistivity-temperature curves. The second objective of this work was to establish a method linking chemical composition (synthesis conditions) to the parameters derived from the two models, calculation on the principle of non-linear curve fitting, two numerical equations are highlighted for quantitatively analyzing chemical composition-dependent parameters. The observed effects of chemical composition on the shift in the temperature-resistive curve, which are fundamental to understanding resistivity behavior, are discussed quantitatively for the first time to our knowledge for resistive-temperature behavior. Hence, the resistivity of both crystalline and non-crystalline materials can be forecasted across various compositions and temperatures using the methods presented, even without experimental data.

Unraveling the Pathogenesis of Calcinosis in Systemic Sclerosis: A Molecular and Clinical Insight.

Dystrophic calcinosis, which is the accumulation of insoluble calcified crystalline materials within tissues with normal circulating calcium and phosphorus levels, is a frequent finding in systemic sclerosis (SSc) and represents a major burden for patients. In SSc, calcinosis poses significant challenges in management due to the associated risk of severe complications such as infection, ulceration, pain, reduction in functional capacity and quality of life, and lack of standardized treatment choices. The exact pathogenesis of calcinosis is still unknown. There are multifaceted factors contributing to calcinosis development, including osteogenic differentiation of cells, imbalance between promoter and inhibitors of mineralization, local disturbance in calcium and phosphate levels, and extracellular matrix as a template for mineralization. Several pathophysiological changes observed in SSc such as ischemia, exacerbated production of excessive reactive oxygen species, inflammation, production of inflammatory cytokines, acroosteolysis, and increased extracellular matrix production may promote the development of calcinosis in SSc. Furthermore, mitochondrial dynamics, particularly fission function through the activity of dynamin-related protein-1, may have an effect on the dystrophic calcinosis process. In-depth investigations of cellular mechanisms and microenvironmental influences can offer valuable insights into the complex pathogenesis of calcinosis in SSc, providing potential targeting pathways for calcinosis treatment.

Structure prediction of stable sodium germanides at 0 and 10 GPa

In this paper we used random structure searching (AIRSS) to carry out a systematic search for crystalline Na-Ge materials at both 0 and 10 GPa. The high-throughput structural relaxations were accelerated using a machine-learned interatomic potential (MLIP) fit to density-functional theory (DFT) reference data, allowing ∼1.5 million structures to be relaxed. At ambient conditions we predict three new Zintl phases, Na3Ge2,Na2Ge, and Na9Ge4, to be stable and a number of Ge-rich layered structures to lie in close proximity to the convex hull. The known NaδGe34 clathrate and Na4Ge13 host-guest structures are found to be relatively stabilized at higher temperature by vibrational contributions to the free energy. Overall, the low-energy phases exhibit exceptional structural diversity, with the expected mixture of covalent and ionic bonding confirmed using the electron-localization function (ELF). The local Ge structural motifs present at each composition were determined using smooth overlap of atomic positions (SOAP) descriptors and the Ge-K edge was simulated for representatives of each motif, providing a direct link to experimental x-ray absorption spectroscopy (XAS). Two Ge-rich phases are predicted to be stable at 10 GPa; NaGe3 and NaGe2 have simple kagome and simple hexagonal Ge lattices respectively with Na contained in the pores. NaGe3 is isostructural with the MgB3 and MgSi3 family of kagome superconductors and remains dynamically stable at 0 GPa. Removing the Na from NaGe2 results in the hexagonal lonsdalite Ge allotrope, which has a direct band gap. Published by the American Physical Society 2024

Thermal conductivity in modified sodium silicate glasses is governed by modal phase changes.

The thermal conductivity of glasses is well-known to be significantly harder to theoretically describe compared to crystalline materials. Because of this fact, the fundamental understanding of thermal conductivity in glasses remain extremely poor when moving beyond the case of simple glasses, e.g., glassy SiO2, and into so-called "modified" oxide glasses, that is, glasses where other oxides (e.g., alkali oxides) have been added to break up the network and alter, e.g., elastic and thermal properties. This lack of knowledge is apparent despite how modified glasses comprise the far majority of known glasses. In the present work, we study an archetypical series of sodium silicate [xNa2O-(100 - x)SiO2] glasses. Analyses of modal contributions reveal how increasing Na2O content induces increasing vibrational localization with a change of vibrations to be less ordered and a related general decrease in modal contributions to thermal conductivity. We find the vibrational phases (acoustic vs optical) of sodium vibrations to be relatively disordered compared to the network-forming silicon and oxygen species, explaining how increasing Na2O content decreases thermal conductivity. Our work sheds new light on the fundamentals of glassy heat transfer as well as the interplay between thermal conduction and modal characteristics in glasses.

NiMOF-Derived MoSe2/NiSe Hollow Nanoflower Structures as Electrocatalysts for Hydrogen Evolution Reaction in Alkaline Medium.

Metal-organic frameworks (MOFs) are crystalline porous materials for storage and energy conversion applications with three-dimensional pore structure, high porosity, and specific surface area, which are widely utilized in electrocatalysis. Herein, MoSe2/NiSe composites were synthesized by selenization reaction using NiMOF as the precursor. The composites were hollow nanoflower structures with a synergistic effect between MoSe2 and NiSe to promote rapid electron transfer, which exhibited good hydrogen evolution reaction performance in an alkaline medium. At a current density of 10 mA/cm2, the HER overpotential reaches 80 mV, the Tafel slope is 33.86 mV/dec, and the material has good stability, with polarization curves remaining essentially unchanged after 3000 cycles. These results indicate that the method has a promising application in the preparation of efficient and sustainable catalysts for hydrogen production in alkaline medium.

Precisely Regulating Photoactivated Dynamic Room Temperature Phosphorescence by Alkyl Chain‐Induced Lattice‐Softening

AbstractDynamic response room temperature phosphorescence (RTP) is a hot topic in smart materials research due to its unique RTP‐response characteristics under external stimuli. However, its precisely control are currently challenging. Here, an alkyl chain‐induced lattice‐softening strategy is proposed to precisely regulate photoactivated dynamic RTP (PDRTP). By adjusting the alkyl chain flexibility of hybrid metal halide matrices, oxygen permeability can be adjusted, thereby achieving finely manipulate of the photoactivation equilibrium time, RTP lifetime, and RTP wavelength of the resulted host–guest doped materials within the ranges of 10–600 s, 0.05‐1.62 s, and 405–595 nm, respectively. It is also demonstrated the potential application of the PDRTP materials in afterglow oxygen sensing and multi‐level information encryption. This study not only proposes an effective method for regulating the photosensitivity of PDRTP materials, but also points out a new direction for exploring gas permeability in dense‐packed crystalline materials.

Solution State-Like Reactivity of a Flexible Crystalline Werner-Type Metal Complex.

Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist in developing crystalline solids that have similar degrees of flexibility as in solution. Herein, we report the preparation of the new flexible crystalline metal complex [Cd(CF3SO3)2(4-spy)4] (4-spy=4-styrylpyridine), which contains photoreactive 4-spy ligand. Unlike traditional solids, this metal complex displays solution state-like [2+2] photocycloaddition reactivity. Specifically, UV irradiation of the crystalline material leads to formation of the same diverse array of dimers and cis isomer that are generated by photoreaction in the solution state. In addition, the photoresponsive flexibility of the solid leads to a photosalient effect and photo-induced formation of pores. The origin of the solution state-like photoreactivity of the solid is related to properties of the Cd(II) cation and fluorinated CF3SO3 anion, and the multi-orientational arrangement of the 4-spy ligands.

Ion‐Transport Kinetics and Interface Stability Augmentation of Zinc Anodes Based on Fluorinated Covalent Organic Framework Thin Films

AbstractZinc (Zn) emerges as an ideal anode for aqueous‐based energy storage devices because of its safety, non‐toxicity, and cost‐effectiveness. However, the reversibility of zinc anodes is constrained by unchecked dendrite proliferation and parasitic side reactions. To minimize these adverse effects, a highly oriented, crystalline 2D porous fluorinated covalent organic framework (denoted as TpBD‐2F) thin film is in situ synthesized on the Zn anode as a protective layer. The zincophilic and hydrophobic TpBD‐2F provides numerous 1D fluorinated nanochannels, which facilitate the hopping/transfer of Zn2+ and repel H2O infiltration, thus regulating Zn2+ flux and inhibiting interfacial corrosion. The resulting TpBD‐2F protective film enabled stable plating/stripping in symmetric cells for over 1200 h at 2 mA cm−2. Furthermore, assembled full cells (Zn‐ion capacitors) deliver an ultra‐long cycling life of over 100 000 cycles at a current density of 5 A g−1, outperforming nearly all reported porous crystalline materials.

Refined prediction of thermal transport performance in amorphous silica

Thermal transport in amorphous silica (a-SiO2) and silica aerogel is critically important for thermal protection and microelectronics applications. However, notable disparities exist between the predicted and measured thermal conductivity of a-SiO2. Inspired by the dual-phonon theory proposed by Luo et al. [Nat. Commun. 2020, 11, 2554] for crystalline materials, this work introduces a dual-diffuson transport method for amorphous materials. The criterion based on the thermal diffusivity is employed to differentiate between normal diffusons and phonon-like diffusons. Herein, the thermal conductivity of a-SiO2 is investigated by combining a modified Allen-Feldman (AF) theory with the dual-diffuson transport method. The present method is validated well by the measurement using the transient plane source (TPS) method. In addition, the results indicate that normal diffusons primarily govern the thermal transport in a-SiO2, with only a minor contribution from phonon-like diffusons. The temperature dependence of specific heat capacity and mode linewidth contributes to the positive temperature-dependent thermal conductivity. The quantum effect of specific heat capacity is the primary influencing factor in the temperature range of 100–1000 K, while the mode linewidth becomes dominant at higher temperatures. Finally, a theoretical framework for predicting the solid thermal conductivity of silica aerogel is introduced by including the temperature effect on the inherent thermophysical properties of the backbone. This work uncovers the physical mechanisms underlying temperature-dependent thermal transport in a-SiO2 and silica aerogels.

Photomechanical Crystals as Light-Activated Organic Soft Microrobots.

In the field of materials science, dynamic molecular crystals have attracted significant attention as a novel class of energy-transducing materials. However, their development into becoming fully functional actuators remains somewhat limited. This study focuses on one family of dynamic crystalline materials and delves into exploring the efficiency of conversion of light energy to mechanical work. A simple setup is designed to determine a set of performance indices of anthracene-based crystals as an exemplary class of dynamic molecular crystals. The ability of these crystals to reversibly bend due to dimerization is realistically assessed from the perspective of the envisaged soft robotics applications, where wireless photomechanical grippers manipulate and assemble microscopic objects driven and controlled by light instead of lines and motors. The approach described here not only guides the quantification of responsive molecular crystals' actuation potential but also aims to attract an interdisciplinary interest to further develop this class of materials into controllable all-organic actuating elements to be used in microrobotics for engineering or biomedicine.

Rich-N highly branched COF loaded with imidazolyl ionic liquids for highly efficient catalysis of CO2 conversion under atmospheric pressure

The highly loaded ionic active centers and carbon dioxide (CO2) affinity sites play pivotal roles in catalyzing the gas-solid-liquid three-phase reaction in CO2 cycloaddition. In this study, a kind of rich-N highly branched Covalent organic framework loaded with imidazolyl ionic liquids (DhaTat-COF-IL) was synthesized through a nucleophilic substitution reaction, which bridged the highly loaded imidazolyl ionic liquids (Im-IL) active centers (20.72 %) and strong CO2-philic sites, efficiently promoting the in-situ of CO2 conversion at catalyst interface. The rich-N highly branched Covalent organic framework (DhaTat-COF) benefits from its abundant CO2-philic groups (imine and triazine groups) and microporous properties, exhibiting excellent CO2 enrichment capacity, designed as a porous crystalline material for anchoring high active Im-IL. The resultant DhaTat-COF-IL achieved a quantitative yield of 95 % (selectivity > 99 %) in converting epichlorohydrin (ECH) under ambient pressure at 80 ℃, with a turnover frequency (TOF) value reaching 1582 h⁻¹ at 120 ℃. Additionally, yields of ≥ 94 % were obtained for various terminal-substituted epoxides. Density Functional Theory (DFT) analysis reveals a synergistic effect between −CH and Br− in the DhaTat-COF-IL during catalytic cycling. This work provides valuable insights into the targeted design and performance optimization of Im-IL-grafted COF-based catalysts, emphasizing high efficiency and sustainability in CO₂ conversion.

Metal Organic Frameworks Based Wearable and Point-of-Care Electrochemical Sensors for Healthcare Monitoring.

The modern healthcare system strives to provide patients with more comfortable and less invasive experiences, focusing on noninvasive and painless diagnostic and treatment methods. A key priority is the early diagnosis of life-threatening diseases, which can significantly improve patient outcomes by enabling treatment at earlier stages. While most patients must undergo diagnostic procedures before beginning treatment, many existing methods are invasive, time-consuming, and inconvenient. To address these challenges, electrochemical-based wearable and point-of-care (PoC) sensing devices have emerged, playing a crucial role in the noninvasive, continuous, periodic, and remote monitoring of key biomarkers. Due to their numerous advantages, several wearable and PoC devices have been developed. In this focused review, we explore the advancements in metal-organic frameworks (MOFs)-based wearable and PoC devices. MOFs are porous crystalline materials that are cost-effective, biocompatible, and can be synthesized sustainably on a large scale, making them promising candidates for sensor development. However, research on MOF-based wearable and PoC sensors remains limited, and no comprehensive review has yet to synthesize the existing knowledge in this area. This review aims to fill that gap by emphasizing the design of materials, fabrication methodologies, sensing mechanisms, device construction, and real-world applicability of these sensors. Additionally, we underscore the importance and potential of MOF-based wearable and PoC sensors for advancing healthcare technologies. In conclusion, this review sheds light on the current state of the art, the challenges faced, and the opportunities ahead in MOF-based wearable and PoC sensing technologies.