Three-dimensional Framework Research Articles

Breaking Boundaries: Innovations in Two- and Three-Dimensional Metal-Organic Framework (MOF)-Based Mixed-Matrix Membranes for Effective Post-Combustion CO 2 Capture

Breaking Boundaries: Innovations in Two- and Three-Dimensional Metal-Organic Framework (MOF)-Based Mixed-Matrix Membranes for Effective Post-Combustion CO ₂ Capture

Synergy of modulating in-plane pores and zincophilic sites on the flexible graphene paper for efficient and dendrite-free hosted Zn anode

The practical advancement of Zn-ion batteries (ZIBs) in the portable/wearable electronics field is still hindered by the notorious Zn dendrites formation and the lack of an appropriate host to construct a highly effective flexible Zn anode. Herein, we present a three-dimensional (3D) N-doped graphene paper framework with abundant in-plane pores (rHGP-N) as an efficient Zn plating/stripping scaffold. Remarkably, the rHGP-N paper electrode exhibits an unprecedentedly low Zn nucleation overpotential of 5.2 mV and maintains a high average Coulombic efficiency (∼99.3%) over a superior long Zn plating/stripping cycling of 1400 h. DFT calculation results demonstrate that pyrrolic-nitrogen on graphene possesses the strongest adsorption energy for Zn2+, serving as zincophilic sites to guide Zn uniform nucleation. Moreover, the finite elements simulation results illustrate that flexible graphene paper with abundant in-plane pores can mitigate structural stress and inhibit the formation of Zn dendrites by spatially homogenizing Zn2+ ions flux throughout the entire electrode. The assembled ZIBs full cell (rHGP-N@Zn//rHGP-N@Mn3(PO4)2) demonstrates an impressive volumetric energy density of 77 mWh/cm3, as well as excellent flexibility and mechanical stability with negligible capacity decay under harsh deformation conditions. Our approach can be potentially utilized in designing dendrite-free metal-based flexible anodes for Mg, Ca, or Al-ion batteries.

Diamondoid Ni(II) Coordination Polymer as an Electrocatalyst for Hydrogen and Oxygen Evolution Reactions and Overall Water Splitting.

We have successfully synthesized a new Ni(II)-based coordination polymer (CP) [Ni2(cis-1,4-chdc)2(4,4'-bpy)3(H2O)2] (1); (cis-1,4- H2chdc=cis-1,4-cyclohexanedicarboxylic acid and 4,4'-bpy=4,4'-bipyridine) employing slow diffusion method in a single pot technique. The connectivity of Ni(II) ions and bridging cis-1,4-chdc ligand gives rise to a three-dimensional (3D) framework with 2-fold interpenetrated diamondoid topology. Interestingly, the synthesized CP acts as efficient catalyst for electrocatalytic water splitting. The water oxidation activity of compound 1 exhibits Tafel slope equivalent to 361.48 mV.dec-1 for hydrogen evolution reaction (HER) and 353.53 mV.dec-1 for oxygen evolution reaction (OER) in an alkaline medium while almost similar values of Tafel slope for HER and OER equivalent to 287.33 mV.dec-1 and 289.93 mV.dec-1 respectively in acidic medium. Thus, the compound 1 has excellent efficacy in catalyzing HER and OER in acidic as well as alkaline medium, which is ascribed to its distinctive 3D architecture.

Square-planar Tetranuclear Cluster-based Alkaline Earth Metal-organic Frameworks with Enhanced Proton Conductivity.

Alkaline earth (AE) metal complexes have garnered significant interest in various functional fields due to their nontoxicity, low density, and low cost. However, there is a lack of systematic investigation into the structural characteristics and physical properties of AE-metal-organic frameworks (MOFs). In this research, we synthesized isostructural MOFs consisting of AE4(μ4-Cl) clusters bridged by benzo-(1,2;3,4;5,6)-tris(thiophene-2'-carboxylic acid) (BTTC3-) ligands. The resulting structure forms a truncated octahedral cage denoted as [AE4(m4-Cl)]6(BTTC)8, which further linked to a porous three-dimensional framework. Among the investigated AE ions (Ca, Sr, and Ba), the Ca4-MOF demonstrated good chemical stability in water compared to Sr4-MOF and Ba4-MOF. The N2 adsorption and solid-state UV-vis-NIR absorption behaviors were evaluated for all AE4-MOFs, showing similar trends among the different metal ions. Additionally, the proton conduction study revealed that the Ca4-MOF exhibited ultra-high proton conductivity, reaching 3.52×10-2 S cm-1 at 343 K and 98 % RH. Notably, the introduction of LiCl via guest exchange resulted in an improved proton conduction of up to 6.36×10-2 S cm-1 under similar conditions in the modified LiCl@Ca4-MOF. The findings shed light on the regulation of physical properties and proton conductivity of AE-MOFs, providing valuable insights for their potential applications in various fields.

Convenient construction of electrocatalysts via combustion-assisted corrosion engineering for efficient water oxidation

Developing an efficient strategy for the universal synthesis of electrocatalysts is crucial for advancing the industrialization of water splitting, yet it remains a significant challenge. In this study, we propose combustion-assisted corrosion engineering as a rapid method to fabricate electrocatalysts for the oxygen evolution reaction (OER) within seconds. By utilizing a three-dimensional framework composed of nickel foam and the unique structure of the active species, we enable swift electrolyte diffusion and gas release. Consequently, the optimized S–NiO/NF exhibits remarkable OER catalytic activity, requiring a low overpotential of 236 mV to achieve a current density of 50 mA cm−2 in 1.0 M KOH solution. Notably, the reconfiguration during the OER process leads to the formation of actual catalytic active species, enhancing the number of active centers and thereby improving the catalyst's performance. This research presents a versatile method for industrially fabricating non-noble metal self-supporting electrodes with high efficiency, offering a practical solution for energy conversion and storage.

Enhanced photocatalytic removal of azo dye by the K3NaCo4(MoO4)6/H2O2 system

K3NaCo4(MoO4)6 photocatalyst has been prepared using a solid-state reaction method. First, its crystal structure is determined from single-crystal X-ray diffraction data. This material crystallizes in trigonal system, space group R3¯ (No.148) with cell parameters a = 14.434(3) Å and c = 19.811(6) Å. The crystal structure of the title compound can be described by the junction of ribbons and MoO4 tetrahedra by sharing vertices to give a three-dimensional framework in which Na+ and K+ cations are resided. Second, the as prepared sample has been characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman spectroscopy, UV–visible spectroscopy, scanning electron microscope (SEM) and EDX analysis. The SEM analysis demonstrates the presence of agglomerates with uniform nanoparticles having different crystallite sizes. FTIR and Raman spectra confirm the presence of characteristic MoO4 tetrahedra. Moreover, the optical band gap was found to be 3.5 eV. Finally, the photocatalytic removal of Acid Yellow 23 (AY-23) organic azo dye was investigated under solar light in the presence of K3NaCo4(MoO4)6 photocatalyst and H2O2. A good photocatalytic activity for the degradation of AY-23 dye has been noted with a removal rate reaching 98 % when adding H2O2 at optimum reaction. The elimination of AY-23 increased with the addition of 5 mM H2O2 concentration. The rate constant of the photocatalytic process in the K3NaCo4(MoO4)6/H2O2 system is about 1.2 × 10-1h−1.

A Comprehensive Review on Strategies for Enhancing the Performance of Polyanionic-Based Sodium-Ion Battery Cathodes.

The significant consumption of fossil fuels and the increasing pollution have spurred the development of energy-storage devices like batteries. Due to their high cost and limited resources, widely used lithium-ion batteries have become unsuitable for large-scale energy production. Sodium is considered to be one of the most promising substitutes for lithium due to its wide availability and similar physiochemical properties. Designing a suitable cathode material for sodium-ion batteries is essential, as the overall electrochemical performance and the cost of battery depend on the cathode material. Among different types of cathode materials, polyanionic material has emerged as a great option due to its higher redox potential, stable crystal structure, and open three-dimensional framework. However, the poor electronic and ionic conductivity limits their applicability. This review briefly discusses the strategies to deal with the challenges of transition-metal oxides and Prussian blue analogue, recent developments in polyanionic compounds, and strategies to improve electrochemical performance of polyanionic material by nanostructuring, surface coating, morphology control, and heteroatom doping, which is expected to accelerate the future design of sodium-ion battery cathodes.

Three-Dimensional Cell Culture Models to Investigate the Epithelial Barrier in Eosinophilic Esophagitis.

The squamous epithelium of the esophagus is directly exposed to the environment, continuously facing foreign antigens, including food antigens and microbes. Maintaining the integrity of the epithelial barrier is critical for preventing infections and avoiding inflammation caused by harmless food-derived antigens. This article provides simplified protocols for generating human esophageal organoids and air-liquid interface cultures from patient biopsies to study the epithelial compartment of the esophagus in the context of tissue homeostasis and disease. These protocols have been significant scientific milestones in the last decade, describing three-dimensional organ-like structures from patient-derived primary cells, organoids, and air-liquid interface cultures. They offer the possibility to investigate the function of specific cytokines, growth factors, and signaling pathways in the esophageal epithelium within a three-dimensional framework while maintaining the phenotypic and genetic properties of the donor. Organoids provide information on tissue microarchitecture by assessing the transcriptome and proteome after cytokine stimulation. In contrast, air-liquid interface cultures allow the assessment of the epithelial barrier integrity through transepithelial resistance (TEER) or macromolecule flux measurements. Combining these organoids and air-liquid interface cultures is a powerful tool to advance research in impaired esophageal epithelial barrier conditions.

Targeted synthesis of a 3D covalent organic framework with fjh topology exhibiting high photoluminescence: A robust platform for sensitive detection of furantoin

The inappropriate use of antibiotics poses significant risks to both the environment and human health, necessitating the development of accurate and sensitive detection methods. Fluorescence detection, particularly utilizing three-dimensional (3D) covalent organic frameworks (COFs), stands out as a promising avenue. Unlike two-dimensional COFs, 3D COFs can mitigate fluorescence quenching resulting from non-radiative energy loss, primarily attributed to π-π interlayer stacking. In this study, by carefully selecting and designing the building blocks, we synthesized a 3D COF named PyTTA-TTFB-COF with fjh topology and remarkable photoluminescence. This was achieved through the combination of a 4-connected square chromophore, 1,3,6,8-Tetrakis(4-aminophenyl) pyrene, with a 3-connected triangle, 1,3,5-trimethyl-2,4,6-tris(4-formylphenyl) benzene, possessing a specific stereo conformation. Significantly, PyTTA-TTFB-COF exhibits a high photoluminescence quantum yield, notably reaching 60.1% in acetonitrile. Moreover, it displays substantial fluorescence quenching when exposed to furantoin, surpassing the performance observed with other antibiotics. Competitive experiments have confirmed that PyTTA-TTFB-COF can serve as a specific fluorescent probe for the interference-free detection of furantoin.

Power Relations in Ekegusii Gendered Proverbs

Language acts as a primary vehicle for transmitting cultural norms, values, and expectations, as well as thought paradigms, from one generation to another. This is despite language choices in Ekegusii proverbs being loaded with culturally stereotypical language choices about gender. This study investigated how power discourses are employed in Ekegusii proverbs. The study applied Critical Discourse Analysis (CDA) by Fairclough (1989, 1993 and 2001) and Van Dijk (2001). This research adopted a descriptive qualitative research design. The target population was eighty (80) ekegusii proverbs. Purposive sampling procedures were used to select eighty power-related proverbs. The study adopted the three-dimensional discourse framework as a method of data analysis. The findings of the study revealed that power relations are embedded in Ekegusii proverbs. The lexicalization and level of meaning of proverbs showed that these proverbs obtain their sexist and obscene connotations, which are construed as being laden with an impertinent reference that derogates womanhood. The study further revealed that linguistic features such as metaphors, negative syntactic structures, and vocabulary are used to enact power between genders. The study recommends that gendered proverbs be consciously improved to portray gender neutrality, equality and contemporariness.

Research on China's End-of-Life Care Policy from the Perspective of Aging Population: A Textual Analysis of 30 Policies from 2017 to 2022

As the proportion of elderly population increases and the level of social development continues to rise, the issue of end-of-life care for the elderly has gradually gained societal attention. End-of-life care, as an emerging field, relies crucially on optimizing top-level policy design for its healthy development. This study focuses on 30 national-level end-of-life care policy texts from 2017 to 2022. Utilizing analysis tools such as ROST CM 6 software, NLPIR Chinese word segmentation system, and SPSS, the research employs a three-dimensional framework of keyword frequency analysis, semantic network analysis, and "policy tools-policy time-policy intensity" to comprehensively explore the current state of China's end-of-life care policy. The study reveals existing issues in the policy's practical operability, uneven application of policy tools, neglected funding and information technology support, and weak regulatory aspects. It emphasizes the need to prioritize a people-centered approach, enhance the overall balance in policy tools, promote the standardization of end-of-life care, and improve a diversified service system. These findings broaden the research perspective in the field of end-of-life care, providing insights for optimizing policy design and advancing nationwide end-of-life care efforts.

Myth of empowerment of women migrants: Post-COVID scenario of returnee women migrants in Bangladesh

This article explores the complex interactions that affect women migrants in Bangladesh with a focus on their experiences as return migrants during the post-COVID. Worldwide migration patterns have been significantly impacted by the COVID-19 pandemic, and Bangladesh is no exception. It is critical to comprehend the difficulties and opportunities experienced by women migrants during this time, as the pandemic disrupted businesses and compelled many migrant workers to return home. Due to economic reasons and the search for better employment prospects, female migration has significantly increased in Bangladesh in recent decades. However, the COVID-19 outbreak and the subsequent migrant repatriation have brought to light the numerous difficulties faced by women who have traveled overseas as workers. The article investigates how their migrating experiences and contributions have been viewed in Bangladeshi culture in terms of empowerment by analyzing Naila Kabeer’s three-dimensional framework (Resource, Agency, and Achievement). This research also contributes to the ongoing conversation on migration, gender, and empowerment scenarios by shedding light on the post-COVID environment for returnee women migrants to support inclusive sustainable development in the sphere of women empowerment in Bangladesh.

Western US intraplate deformation controlled by the complex lithospheric structure

The western United States is one of Earth’s most tectonically active regions, characterized by extensive crustal deformation through intraplate earthquakes and geodetic motion. Such intracontinental deformation is usually ascribed to plate boundary forces, lithospheric body forces, and/or viscous drag from mantle flow. However, their relative importance in driving crustal deformation remains controversial due to inconsistent assumptions on crustal and mantle structures in prior estimations. Here, we utilize a fully dynamic three-dimensional modeling framework with data assimilation to simultaneously compute lithospheric and convective mantle dynamics within the western United States. This approach allows for quantitative estimations of crustal deformation while accounting for the realistic three-dimensional lithospheric structure. Our results show the critical role of the complex lithospheric structure in governing intraplate deformation. Particularly, the interaction between the asthenospheric flow and lithospheric thickness step along the eastern boundary of the Basin and Range represents a key driving mechanism for localized crustal deformation and seismicity.

Assessing the Current State of Microtia Reconstruction in the United States.

Microtia is a congenital ear deformity with variability in surgical techniques and tools across surgeons pursuing an autologous reconstruction. Different techniques have emerged over time, and surgeons opt for various tools to aid in creating the complex three-dimensional cartilaginous ear framework. The purpose of this study was to understand the current state of microtia reconstruction in the United States. Microtia surgeons affiliated with the nonprofit, Ear Community, were invited to complete a 20-item survey. Data were collected on demographic information regarding surgeons, considerations when approaching microtia repair in patients, and techniques and comfort levels. Additional data were collected on materials, tools, flaps, and skin grafts used for reconstruction. Twenty-two surgeons responded to the survey reporting 3 different techniques learned and utilized in practice including the Brent, Nagata, and Firmin techniques. About two-thirds of surgeons were "extremely comfortable" with their techniques and one-third were "extremely uncomfortable" or "somewhat uncomfortable." Most respondents reported using a tunneled temporoparietal fascial flap or a posterior fascial flap along with a full-thickness skin graft for the second stage (ear elevation). Most surgeons utilized a combination of scalpels and gouges when carving the ear framework along with sutures or wire. This study highlights the current state of autogenous microtia reconstruction underscoring the variability in approaches and preferences. These data may guide future directions that aim to improve patient outcomes. Surgeons may gain insight into different practices and choose to adopt different aspects to enhance their surgical approach.

URANYL IODOACETATES OF MAGNESIUM, MANGANESE AND NICKEL

Syntheses, IR spectroscopic and X-ray diffraction studies of new uranyl iodoacetate complexes with divalent metals were carried out: R[UO2(CH2ICOO)3]2·6H2O (R = Mg2+ (I), Mn2+ (II), Ni2+ (III)). It was established that isostructural I–III crystallize in the cubic crystal system and contain octahedral aqua complexes [R(H2O)6]2+, which connect hexagonal-bipyramidal complexes [UO2(CH2ICOO)3]– into a three-dimensional framework by hydrogen bonds. Using molecular Voronoi–Dirichlet polyhedra, it was found that bifurcate halogen bonds O⋅⋅⋅I−C are also involved in the interconnection of anionic complexes. On the example of two series of stoichiometrically similar compounds dependence of the ratio of sizes of carboxylate ligands and counter cations on crystal system was observed and crystal systems for the compounds that have not yet been structurally characterized were assumed.

A novel composite solid electrolyte with ultrahigh ion transference number and stability for solid-state sodium metal batteries

The combination of a Na-ion conducting filler and polymer matrix in composite solid electrolyte (CSE) presents a promising and attractive strategy for improving the energy density and safety of the sodium-metal batteries. The agglomeration and precipitation of inorganic ceramic fillers in the polymer matrix present a major challenge leading to the decreased Na ion conductivity property and transference number, increased interfacial resistance, and worsened mechanical properties of CSEs. Herein, we introduce a novel composite solid electrolyte (denoted as 3D-15PNZSPP), comprising a three-dimensional interconnected porous Na3Zr2Si2PO12 framework integrated with an asymmetric polymer electrolyte layer, which not only offers continuous conductive pathways and high mechanical strength for Na ions transfer, but also enhances the interfacial compatibility and expands the electrochemical stability window. The 3D-15PNZSPP CSE shows a high Na+ conductivity of 7.6 × 10−4 S cm−1 and an outstanding transference number of 0.82 at temperature of 30 °C. These characteristics enable the Na/3D-15PNZSPP/Na symmetric cell to cycle for over 700 h with a small overpotential. More importantly, the assembled all solid-state Na0.67Li0.24Mn0.76O2/3D-15PNZSPP/Na batteries demonstrate remarkable cycling stability and high rate capability, indicating a promising and facile strategy for designing ultra-safe and high-performance solid-state sodium metal batteries.

Executive Compensation and the Three-Dimensional Reference Framework: Insights from Data Analysis of Chinese Publicly Traded Firms

Executive Compensation and the Three-Dimensional Reference Framework: Insights from Data Analysis of Chinese Publicly Traded Firms

An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding.

In this work, a novel organodiphosphate-containing inorganic-organic hybrid polyoxoniobate (PONb) ring {(PO3CH2CH2PO3H)4Nb8O16}4- (Nb8P8) has been achieved by a one-pot hydrothermal method. The ring is constructed from a tetragonal {Nb8O36} motif and four {PO3CH2CH2PO3H} ligands. Interestingly, Nb8P8 can be joined together via K-H2O clusters {K2(H2O)4(OH)2} to form one-dimensional chains {[K2(H2O)4(OH)2]Nb8P8}n and further linked by {Cu(en)2}2+ (en = ethylenediamine) complexes, resulting in a three-dimensional supramolecular framework {[Cu(en)2]2[K2(H2O)4(OH)2]Nb8P8}·3en·H2O (1). 1 exhibits good chemical and thermal stability and has a high water vapor adsorption capacity of ≤224 cm3 g-1 (22.71 mol·mol-1) at 298 K, outperforming most of the known polyoxometalate-based materials. Impedance measurements prove that 1 can transfer protons with moderate conductivity. This study not only contributes to the structural diversity of organodiphosphate-containing PONbs and PONb rings but also provides a reference for the development of PONb-based materials with unique performance.

Supramolecular frameworks assembled by [EuL2]3+ units with different coordination configurations

Self-assembly is an important strategy to construct supramolecular frameworks. Small change in the assembling units often leads to significant variations in the self-assembly structures. In the work, we obtain two supramolecular frameworks assembled by different [EuL2]3+ units (L = tris((5,6-dimethyl-1H-benzo[d]imidazol-2-yl)methyl) amine). One meso compound {[EuⅢL2]·(H2O)6·Cl3} (Meso-EuL2) is assembled by an achiral meso-[EuL2]3+ unit, forming a supramolecular three-dimensional framework through six-fold intermolecular π‒π interactions. The other is a racemic compound {[EuⅢL2]·(CH3OH)5·Cl3} (Rac-EuL2), assembled by two chiral rac-[EuL2]3+ units predominantly via hydrogen bonding, leading to a layered supramolecular framework. The luminescent properties are different between Meso-EuL2 and Rac-EuL2, with Meso-EuL2 exhibiting more excimer-like emissions, which is likely caused by its stronger π‒π interactions in the structure.

Two-dimensional Ti3C2Tx anchored on three-dimensional SiC honeycomb framework for efficient and cyclic photocatalytic degradation of organic pollutants

The excellent recyclability of SiC foam renders it an ideal catalyst in the field of photocatalytic degradation, however to further improve its photocatalytic efficiency remains a major challenge in current research. In this regard, a honeycomb-like porous SiC foam was successfully constructed through freeze-drying and polymer-to-ceramic derivation method, with two-dimensional Ti3C2Tx nanosheets anchored on its three-dimensional framework. Their photocatalytic performances were evaluated by the degradation of methylene blue (MB) under visible-light irradiation. All Ti3C2Tx/SiC hybrid foams show superior photocatalytic degradation capability compared with SiC foam, with a highest removal rate (adsorption and degradation) reaching 94.4% for TSF-4, denoting an increasement of 50.4%. Even after five cycles, the removal rate remained at 91.4% with only a slightly loss of 3%, suggesting its excellent recycling performance. These desirable results stem from the unique structural design, in which the porous structure facilitates the contact between catalyst and pollutant, while the Ti3C2Tx/SiC heterojunction promotes effective separation of photogenerated carriers. This work paves the way for the development of lightweight, efficient and easily recyclable photocatalyst for wastewater purification.