Structural Transformation Research Articles

Structure Transformation of Methylammonium Polyoxomolybdates via In-Solution Acidification and Solid-State Heating from Methylammonium Monomolybdate and Application as Negative Staining Reagents for Coronavirus Observation.

We prepared polyoxomolybdates with methylammonium countercations from methylammonium monomolybdate, (CH3NH3)2[MoO4], through two dehydrative condensation methods, acidifying in the aqueous solution and solid-state heating. Discrete (CH3NH3)10[Mo36O112(OH)2(H2O)14], polymeric ((CH3NH3)8[Mo36O112(H2O)14])n, and polymeric ((CH3NH3)4[γ-Mo8O26])n were selectively isolated via pH control of the aqueous (CH3NH3)2[MoO4] solution. The H2SO4-acidified solution of pH < 1 produced "sulfonated α-MoO3", polymeric ((CH3NH3)2[(MoO3)3(SO4)])n. The solid-state heating of (CH3NH3)2[MoO4] in air released methylamine and water to produce several methylammonium polyoxomolybdates in the sequence of discrete (CH3NH3)8[Mo7O24-MoO4], discrete (CH3NH3)6[Mo7O24], discrete (CH3NH3)8[Mo10O34], and polymeric ((CH3NH3)4[γ-Mo8O26])n, before their transformation into molybdenum oxides such as hexagonal-MoO3 and α-MoO3. Notably, some of their polyoxomolybdate structures were different from polyoxomolybdates produced from ammonium molybdates, such as (NH4)2[MoO4] or (NH4)6[Mo7O24], indicating that countercation affected the polyoxomolybdate structure. Moreover, among the tested polyoxomolybdates, (CH3NH3)6[Mo7O24] was the best negative staining reagent for the observation of the SARS-CoV-2 virus using transmission electron microscopy.

Comparative Analysis for the Behavior of Beryllium and Magnesium Crystals at Ultrahigh Pressures

The article presents ab initio calculation results on the structural‐phase stability of beryllium and magnesium crystals under high and ultrahigh pressures (multiterapascal regime). Magnesium is shown to undergo a number of structural transformations which markedly reduce the crystal packing factor. As for beryllium, its high‐pressure body‐centered cubic phase remains stable even under ultrahigh pressures. Changes in the electronic structure of Be and Mg crystals under compression are analyzed and some interesting effects are revealed. Specifically, a narrow bandgap appears in the electronic structure of magnesium under pressures above 2.5 TPa. For the metals of interest, pressure‐temperature diagrams are constructed and compared with available experimental and theoretical results from other investigations.

Intelligent Magnetic Microrobots with Fluorescent Internal Memory for Monitoring Intragastric Acidity

AbstractThis study investigates the dynamic fluctuations of pH caused by gastric acid secretion, a process of both biological and clinical significance, with microrobots. Abnormal patterns of acidity often indicate gastrointestinal diseases, underlying the importance of precise intragastric pH monitoring. Traditional methods using fluorescent probes face challenges due to their faint solid‐state fluorescence, limited target specificity, and accuracy. To overcome these obstacles, pH‐responsive fluorescent organic microparticles decorated with magnetite (Fe3O4) nanoparticles are engineered. These microrobots exhibit a unique fluorescence switching capability at a critical pH, enabling the monitoring of gastric acidity. The magnetic part of these microrobots ensures magnetic maneuverability to enable targeted navigation. The microrobots’ fluorescence switching mechanism is elucidated through comprehensive spectroscopy, microscopy, and X‐ray diffraction analyses, revealing molecular‐level structural transformations upon interaction with gastric acid and antacids. These transformations, specifically protonation and deprotonation of the microrobots’ fluorescent components, prompt a distinct fluorescence response correlating with pH shifts. In vitro and ex vivo experiments, simulating stomach conditions, confirm the microrobots’ efficacy in pH‐responsive imaging. The results showcase the promising diagnostic potential of microrobots for gastrointestinal tract diseases, marking a significant advancement in imaging‐based medical diagnostics at targeted locations.

Local electronic structure constructing of layer‐structured oxide cathode material for high‐voltage sodium‐ion batteries

AbstractAs the cyclable sodium ions' primary suppliers, O3‐type layer‐structured manganese‐based oxides are recognized as one of the most competitive cathode candidates for sodium‐ion batteries. Suffering from complex structural transformations and transition metal migration during the sodium intercalation/deintercalation process, particularly at high voltage, the energy density and lifespan cannot satisfy the increasing demand. The orbital and electronic structure of the octahedral center metal element plays an important role in maintaining the octahedral structural integrity and improving the Na+ diffusivity by the introduced heterogeneous [Me–O] (Me: transition metals) chemical bonding. Herein, inspired by the 4f and 5d orbital bonding possibility from the abundant configuration of extranuclear electrons and large ion radius, O3‐type Na[La0.01Ni0.3Mn0.54Cu0.1Ti0.05]O2 was synthesized with a nearly single crystal structure. Based on the experimental and computational results, the introduced heterogeneous [La–O] chemical bond with larger bond strength can not only ensure the stability of the lattice oxygen framework and the reversibility of oxygen redox but also optimize the oxygen local electronic structure resulting from La 5d and O 2p orbital mixing due to O 2p → La 5d charge transfer. It delivers an optimal electrochemical performance with a high energy density and cycling lifespan.

Influence of pH on Room-Temperature Synthesis of Zinc Oxide Nanoparticles for Flexible Gas Sensor Applications

This research contributes to work on synthesizing zinc oxide nanoparticles (ZnO NPs) at room temperature (RT) and their utilization in flexible gas sensors. RT ZnO NP synthesis with a basicity solution (pH ≈ 13) demonstrates an efficient method for synthesizing well-crystalline ZnO NPs (RT.pH13) comparable to those synthesized by the hydrothermal method (hyd.C). The RT.pH13 achieved a high thermal stability with minimal organic reside impurities (~4.2 wt%), 30–80 nm particle size distribution, and a specific surface area (14 m2 g−1). The synthesized pre- and post-calcinated RT.pH13 NPs were then incorporated into flexible sensors for gas sensing applications at ambient conditions (RT and relative humidity of 30–50%). The pre-calcinated ZnO-based sensor (RT.pH13) demonstrated superior sensitivity to styrene and acetic acid and lower sensitivity to dimethyl-6-octenal. The calcinated ZnO-based sensor (RT.pH13.C) exhibited lower sensitivity to styrene and acetic acid, but heightened sensitivity to benzene, acetone, and ethanol. This suggests a correlation between sensitivity and structural transformations following calcination. The investigation of the sensing mechanisms highlighted the role of surface properties in the sensors’ affinity for specific gas molecules and temperature and humidity variations. The study further explored the sensors’ mechanical flexibility, which is crucial for flexible Internet of Things (IoT) applications.

Atomically Resolved Phase Coexistence in VO2 Thin Films.

Concurrent structural and electronic transformations in VO2 thin films are of 2-fold importance: enabling fine-tuning of the emergent electrical properties in functional devices, yet creating an intricate interfacial domain structure of transitional phases. Despite the importance of understanding the structure of VO2 thin films, a detailed real-space atomic structure analysis in which the oxygen atomic columns are also resolved is lacking. Moreover, intermediate atomic structures have remained elusive due to the lack of robust atomically resolved quantitative analysis. Here, we directly resolve both V and O atomic columns and discover the presence of intermediate monoclinic (M2) phase nanolayers (less than 2 nm thick) in epitaxially grown VO2 films on a TiO2 (001) substrate, where the dominant part of VO2 undergoes a transition from the tetragonal (rutile) phase to the monoclinic M1 phase. Strain analysis suggests that the presence of the M2 phase is related to local strain gradients near the TiO2/VO2 interface. We unfold the crucial role of imaging the spatial configurations of the oxygen anions (in addition to V cations) by utilizing atomic-resolution electron microscopy. Our approach can be used to unravel the structural transitions in a wide range of correlated oxides, offering substantial implications for, e.g., optoelectronics and ferroelectrics.

Solvent-Responsive Nonporous Adaptive Crystals Derived from Pyridinium Hydrochloride and the Application in Iodine Adsorption.

Nonporous adaptive crystals (NACs) are crystalline nonporous materials that can undergo a structural adaptive phase transformation to accommodate specific guest via porous cavity or lattice voids. Most of the NACs are based on pillararenes because of their flexible backbone and intrinsic porous structure. Here we report a readily prepared organic hydrochloride of 4-(4-(diphenylamino)phenyl)pyridin-1-ium chloride (TPAPyH), exhibiting the solvent dimension-dependent adaptive crystallinity. Wherein it forms a nonporous α crystal in a solvent with larger dimensions, while forming two porous β and γ crystals capable of accommodating solvent molecules in solvent with small size. Furthermore, the thermal-induced single-crystal-to-single-crystal (SCSC) transition from the β to α phase can be initiated. Upon exposure to iodine vapor or immersion in aqueous solution, the nonporous α phase transforms to porous β phase by adsorbing iodine molecules. Owing to the formation of trihalide anion I2Cl- within the crystal cavity, TPAPyH exhibits remarkable performance in iodine storage, with a high uptaking capacity of 1.27 g·g-1 and elevated iodine desorption temperature of up to 110 and 82°C following the first and second adsorption stage. The unexpected adaptivity of TPAPyH inspired the design of NACs for selective adsorption and separation of volatile compound from organic small molecules. This article is protected by copyright. All rights reserved.

Impact investing: A study of structural transformations of a macroregion's social services

Subject. This article discusses the issues of investment policy and support for the social sphere. Objectives. The article aims to analyze changes in the sectoral and territorial structures of investments in the subjects of the Ural economic region (macroregion) for the period from 2005 to 2021. Methods. For the study, I used the economic and mathematical research methods. Results. The article finds that despite the increase in investment in education and healthcare in the Ural macroregion, in general, there have been no significant structural changes in favor of these sectors. Noticeable changes in the sectoral structure of the economy are recorded in the Orenburg Oblast and the Udmurt Republic. Relevance. The research results can be used to develop regional programmes to support economic sectors.

The Belt and Road Initiative and Dynamics of Structural Transformation

AbstractStructural transformation is among the core questions in development economics, but in recent decades, the discipline has shifted its focus away from production and transformation in favour of analyses on exchange, growth and productivity. Yet, the structural transformation question remains central, and needs to be confronted with the main changes in the global economic and political landscape, such as the emergence of the Belt and Road Initiative (BRI). With its emphasis on an infrastructure-based connectivity agenda, the BRI opens the space for a paradigm shift in development, and for a renewed emphasis on structural transformation. This article introduces a special issue that explores the role of the BRI in promoting structural transformation in low- and middle-income countries, to understand if and under which conditions the BRI creates pathways that can change the structure of the economies. Through an explicit focus on the role of BRI on transformation in low- and middle-income countries, this special issue examines how domestic institutions regulate and coordinate production diversification, national and international sectoral specificities, and drivers and barriers to technological innovation and trade. In this sense, the special issue sheds light on new conceptualisations and empirical examples of industrial policies.

NMR study of nitrate ionic liquids confined between micrometer-spaced plates

This review paper presents the results of a study conducted using nuclear magnetic resonance (NMR) methods to investigate the dynamic behaviour of ionic liquid-based compositions in micrometre-spaced confinement. Ethylammonium nitrate (EAN) and other ionic liquid (IL) systems with nitrate anion in glass or quartz spaced confinement demonstrate anomalous cation dynamics that differ from those observed in bulk and in nano-confinement. It was demonstrated that the principal axis of the nitrate anion exhibits preferential orientation to the surface, akin to that in liquid crystals. It was shown that the cation translational mobility reversibly changes during exposure to a static magnetic field. This phenomenon was interpreted as a result of intermolecular structure transformations occurring in the confined ILs. The mechanisms of these transformations were discussed.

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO2 Cathodes

AbstractThe O‐type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na+ ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg2+) or trivalent (Al3+ or Co3+) ions for Ni3+ to alleviate Na+ion ordering and perturb the Jahn–Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na+ ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg2+ substitution. Long‐range (operandoX‐ray diffraction) and short‐range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg‐substitution results in a high‐capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium‐ion batteries.

Macroscale Ultradurable Anti‐wear Achieved on Graphene‐based Films via Multiphase Combination

Excellent anti‐wear performance, high bearing capacity, and long service life are essential prerequisites for the reliability and durability of Si‐based micro/nano device operation. To improve the anti‐wear property and prolong service life of Si‐based micro/nano devices under high loads, graphene oxide (GO) nanosheets, graphene quantum dots (GQDs) and ionic liquid‐capped GQDs (IL‐GQDs) were used to create three kinds of multilayer films as solid lubricant, that is, single‐component (GO)5, (GO/GQDs)5 and (GO/IL‐GQDs)5 multilayer films. The results showed that (GO/IL‐GQDs)5 composite multilayer possessed excellent wear resistance under a high load of 4 N with the wear rate of 4.9×10‐7 mm3·N‐1·m‐1. The superior anti‐wear performance of (GO/IL‐GQDs)5 composite film is mainly due to the unique 3D structure composed of GO nanosheets alternating with IL‐GQDs. The rigid GO nanosheets play the role in load‐carrying capacity, and the IL‐GQDs could delay the time of structure transformation and reduce the loss rate of transfer film, thereby effectively extending the service life of (GO/IL‐GQDs)5 composite multilayer. Such multilayers are expected to be good solid lubricating films suitable for Si‐based micro/nano devices.This article is protected by copyright. All rights reserved.

Spatiotemporal Effects and Optimization Strategies of Land-Use Carbon Emissions at the County Scale: A Case Study of Shaanxi Province, China

Land use, as one of the major sources of carbon emissions, has profound implications for global climate change. County-level land-use systems play a critical role in national carbon emission management and control. Consequently, it is essential to explore the spatiotemporal effects and optimization strategies of land-use carbon emissions at the county scale to promote the achievement of regional dual carbon targets. This study, focusing on Shaanxi Province, analyzed the spatiotemporal characteristics of land use from 2000 to 2020. By establishing a carbon emission evaluation model, the spatiotemporal effects of county-level carbon emissions were clarified. Utilizing Geodetector and K-means clustering methods, the driving mechanisms and clustering characteristics of county-level carbon emissions were elucidated, and optimization strategies for land use carbon emission were explored. The results showed that during 2000–2020, land use in Shaanxi Province underwent significant spatiotemporal changes, with constructed land increasing by 97.62%, while cultivated land and grassland were substantially reduced. The overall county-level carbon emissions exhibited a pattern of North &gt; Central &gt; South. The total carbon emissions within the province increased nearly fourfold over 20 years, reaching 1.00 × 108 tons. Constructed land was the primary source of emissions, while forest land contributed significantly to the carbon sink of the study area. Interactions among factors had significant impacts on the spatial differentiation of total county-level carbon emissions. For counties with different types of carbon emissions, differentiated optimization strategies were recommended. Low-carbon emission counties should intensify ecological protection and rational utilization, medium-carbon emission counties need to strike a balance between economic development and environmental protection, while high-carbon emission counties should prioritize profound emission reduction and structural transformation.

Dual Nonradical Catalytic Pathways Mediated by Nanodiamond-Derived sp2/sp3 Hybrids for Sustainable Peracetic Acid Activation and Water Decontamination.

Peracetic acid (PAA) oxidation catalyzed by metal-free carbons is promising for advanced water decontamination. Nevertheless, developing reaction-oriented and high-performance carbocatalysts has been limited by the ambiguous understanding of the intrinsic relationship between carbon chemical/molecular structure and PAA transformation behavior. Herein, we comprehensively investigated the PAA activation using a family of well-defined sp2/sp3 carbon hybrids from annealed nanodiamonds (ANDs). The activity of ANDs displays a volcano-type trend, with respect to the sp2/sp3 ratio. Intriguingly, sp3-C-enriched AND exhibits the best catalytic activity for PAA activation and phenolic oxidation, which is different from persulfate chemistry in which the sp2 network normally outperforms sp3 hybridization. At the electron-rich sp2-C site, PAA undergoes a reduction reaction to generate a reactive complex (AND-PAA*) and induces an electron-transfer oxidation pathway. At the sp3-C site adjacent to C═O, PAA is oxidized to surface-confined OH* and O* successively, which ultimately evolves into singlet oxygen (1O2) as the primary reactive species. Benefiting from the dual nonradical regimes on sp2/sp3 hybrids, AND mediates a sustainable redox recycle with PAA to continuously generate reactive species to attack water contaminants, meanwhile maintaining structural/chemical integrity and exceptional reusability in cyclic runs.

Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics

Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability and distinctive luminescent characteristics. However, their inherent instability, prone to decomposition upon exposure to moisture and light, hinders their broader ferroelectric applications. Herein, for the first time, we present a series of isoreticular metal‐organic framework (MOF)‐type lead halide luminescent ferroelectrics, demonstrating exceptional robustness under ambient conditions for at least 15 months and even when subjected to aqueous boiling conditions. Unlike conventional metal‐oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited structural distortion, our lead halide‐based MOFs occupy structurally deformable [Pb2X]+ (X=Cl−/Br−/I−) SBUs that facilitate a c‐axis‐biased displacement of Pb2+ centers and substantially contribute to thermoinducible structural transformation. Importantly, this class of MOF‐type lead halide ferroelectrics undergo ferroelectric‐to‐paraelectric phase transitions with remarkably high Curie temperature of up to 505 K, superior to most of molecular ferroelectrics. Moreover, the covalent bonding between phosphorescent organic component and the light‐harvesting inorganic component achieves efficient spin‐orbit coupling and intersystem crossing, resulting in long‐lived afterglow emission. The compelling combination of high stability, ferroelectricity and afterglow emission exhibited by lead halide MOFs opens up many potential opportunities in energy‐conversion applications.

Surface structural transformation and adsorption performance of Poly(triazine imide)

Surface structural transformation and adsorption performance of Poly(triazine imide)

Highly Stable MOF-Type Lead Halide Luminescent Ferroelectrics.

Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability and distinctive luminescent characteristics. However, their inherent instability, prone to decomposition upon exposure to moisture and light, hinders their broader ferroelectric applications. Herein, for the first time, we present a series of isoreticular metal-organic framework (MOF)-type lead halide luminescent ferroelectrics, demonstrating exceptional robustness under ambient conditions for at least 15 months and even when subjected to aqueous boiling conditions. Unlike conventional metal-oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited structural distortion, our lead halide-based MOFs occupy structurally deformable [Pb2X]+ (X=Cl-/Br-/I-) SBUs that facilitate a c-axis-biased displacement of Pb2+ centers and substantially contribute to thermoinducible structural transformation. Importantly, this class of MOF-type lead halide ferroelectrics undergo ferroelectric-to-paraelectric phase transitions with remarkably high Curie temperature of up to 505 K, superior to most of molecular ferroelectrics. Moreover, the covalent bonding between phosphorescent organic component and the light-harvesting inorganic component achieves efficient spin-orbit coupling and intersystem crossing, resulting in long-lived afterglow emission. The compelling combination of high stability, ferroelectricity and afterglow emission exhibited by lead halide MOFs opens up many potential opportunities in energy-conversion applications.

Amino Functionality Enables Aqueous Synthesis of Carboxylic Acid-Based MOFs at Room Temperature by Biomimetic Crystallization.

Enzyme immobilization within metal-organic frameworks (MOFs) is a promising solution to avoid denaturation and thereby utilize the desirable properties of enzymes outside of their native environments. The biomimetic mineralization strategy employs biomacromolecules as nucleation agents to promote the crystallization of MOFs in water at room temperature, thus overcoming pore size limitations presented by traditional postassembly encapsulation. Most biomimetic crystallization studies reported to date have employed zeolitic imidazole frameworks (ZIFs). Herein, we expand the library of MOFs suitable for biomimetic mineralization to include zinc(II) MOFs incorporating functionalized terephthalic acid linkers and study the catalytic performance of the enzyme@MOFs. Amine functionalization of terephthalic acids is shown to accelerate the formation of crystalline MOFs enabling new enzyme@MOFs to be synthesized. The structure and morphology of the enzyme@MOFs were characterized by PXRD, FTIR, and SEM-EDX, and the catalytic potential was evaluated. Increasing the linker length while retaining the amino moiety gave rise to a family of linkers; however, MOFs generated with the 2,2'-aminoterephthalic acid linker displayed the best catalytic performance. Our data also illustrate that the pH of the reaction mixture affects the crystal structure of the MOF and that this structural transformation impacts the catalytic performance of the enzyme@MOF.

Study on the photodegradation behaviors of thermal-aged silk

In museums, silk cultural relics are highly sensitive to light. However, lighting is inevitable due to the exhibition needs, despite any light would pose irreversible damage to silk. Although the solution of eliminating UV radiation was widely achieved in museum lighting environment, long-time accumulation of other light sources still would induce photodegradation of silk. This work therefore established the simulated light ageing experiments to assess the degradation behaviors of silk samples with different ageing degrees. The variation of color values and structure transformation of each sample group were determined by the means of scanning electron microscopy (SEM), colorimeter, Fourier Transform infrared spectroscopy (FTIR) and 13C CPMAS NMR. The results indicated that silk samples with different initial ageing degrees presented different discoloration tendency and structural variation in experimental lighting environment, suggesting the higher disordered structure makes the silk more vulnerable to light damage. It is of great significance to understand the long-time impacts of illumination on degraded silk and further provide methodology for predicting the duration of exhibited silk cultural relics.

Design and performance evaluation of hierarchical ZnCo2S4@PANI core-shell nanorod arrays for high-efficiency supercapacitor applications

Ternary transition metal sulfides (TMS) have gained significant attention due to their excellent energy and power density as Faradaic electrode materials to be utilized in supercapacitors (SCs). Among various conducting polymers, polyaniline (PANI) has rapidly evolved as a valuable pseudo-capacitor material. Though it deprived cycling stability due to instability in structural transformation, which is the major obstacle to its practical level utilization in energy related applications. Herein, the synthesis of an efficient and reliable ZnCo2S4@PANI nonorod arrays (NRAs) anode with structure-to-performance hierarchical morphology is designed to achieve excellent performance. Heterostructured, extremely porous ZnCo2S4 nanorods have acted as a conductive core, which has provided the strain-buffer-support, along with nanoscaled PANI layer to act as an electrochemical active counterpart, and has demonstrated outstanding specific capacitance while retaining the remarkable cyclic performance and rate capability. Implementing the perfectly uniform and compactly coated PANI, the synthesized anode has demonstrated a high specific capacitance of ∼815 F g−1 at a current density of 1 A g−1 and exceptional ∼91 % capacitance retention even after 4000 cycles at high 2 A g−1 current density. Such outcomes are much superior to the most reported electrochemical performances of PANI-related pseudo-capacitors in the literature. The enhanced electrochemical properties of the as synthesized ZnCo2S4@PANI NRAs anode demonstrate the ability of the stable componential structure as a hybrid electrode design to provide a new direction for researchers to utilize such porous framework as an operative support for proficient energy storage devices.