Three-dimensional porous bimetallic metal–organic framework/gelatin aerogels: A readily recyclable peroxymonosulfate activator for efficient and continuous organic dye removal

As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.

Three-dimensionally oriented organization of hexagonal MIL-96 microplates toward superior film microstructure

Preferential orientation control of metal—organic framework(MOF)films is advantageous for maximizing pore uniformity and minimizing grain-boundary defects.Nonetheless,the preparation of MOF films with both in-plane and out-of-plane orientations remains a grand challenge.In this study,we reported the preparation of three-dimensionally oriented MIL-96 layers through combining morphology control of MIL-96 seeds with addition of polyvinylpyrrolidone surfactants and arachidonic acids.The three-dimensionally oriented MIL-96 film was readily obtained through in-plane epitaxial growth.It is anticipated that the aforementioned protocol can be effective for obtaining diverse MOF films with a three-dimensionally oriented organization.

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction

Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.

[(n-C_4H_9)_3SnO_2C(CH_2)_2CO_2Sn(C_4H_9-n)_3]: A Novel Three-dimensional Framework Structure of Organotin Complex

The bis(tributyltin) ester of succinic acid was synthesized by the reaction of disodium salt of succinic acid with tributyltin chloride in a molar ratio of 1:2. The crystal structure was determined by X-ray single-crystal diffraction. It belongs to orthorhombic with space group Pccn, a = 20.949(3), b = 17.470(3), c = 20.345(3) Angstrom, V = 7446(2) Angstrom(3), Z = 8, D-c = 1.242 g/cm(3), mu = 1.365 mm(-1), F(000) = 2864, R = 0.0544 and wR = 0.1417. The tin atom is of five-coordination in a trigonal bipyramidal structure by bridging two carboxylate groups in different directions and the resulting structure which contains straight twist large ring channels along the axes of a, b and c is a three-dimensional framework polymer containing two different tin atoms.

A Dicyanamido-bridged Zinc(Ⅱ) Complex Based on the Bis(4-pyridyl)ethane with a Three-dimensional Framework

A novel dicyanamido-bridged 3D polymeric complex {[Zn2（bpa）2（dca）]dca}n （1） （dca = dicyanamide anion,bpa = 1,2-bis（4-pyridyl）ethane） has been synthesized by reacting 1,2-bis（4-pyridyl）ethane with zinc salt in the presence of sodium dicyanamide,and characterized by elemental analysis,IR spectra and X-ray diffraction. It crystallizes in the monoclinic system,space group C2/c with a = 18.587（3）,b = 20.070（3）,c = 8.7957（13） ,β = 100.611（2）o,V = 3225.0（8） 3,Mr = 539.92,μ = 0.789 mm-1,F（000） = 1116,Z = 4,ρ = 1.112 （g/cm3）,R = 0.0582 and wR = 0.1762. Complex 1 forms a 3D porous framework through the bpa and dca ligands,and gives 1-D coordination channels encapsulated by the guest dca molecules. Complex 1 also displays strong photo-luminescent properties in the solid state at room temperature.

Challenges and Opportunities in Preserving Key Structural Features of 3D-Printed Metal/Covalent Organic Framework

Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.

Parallel Light Fields: A Perspective and A Framework

Dear Editor,Light fields give relatively complete description of scenes from perspective of angles and positions of rays. At present time, most of the computer vision algorithms take 2D images as input which are simplified expression of light fields with depth information discarded. In theory, computer vision tasks may achieve better performance as long as complete light fields are acquired.

All‑Covalent Organic Framework Nanofilms Assembled Lithium‑Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Experimental Study on the Wavelengths of Two-Dimensional and Three-Dimensional Freak Waves

Freak waves are commonly characterized by strong-nonlinearity, and the wave steepness, which is calculated from the wavelength, is a measure of the degree of the wave nonlinearity. Moreover, the wavelength can describe the locally spatial characteristics of freak waves. Generally, the wavelengths of freak waves are estimated from the dispersion relations of Stokes waves. This paper concerns whether this approach enables a consistent estimate of the wavelength of freak waves. The two-(unidirectional, long-crested) and three-dimensional(multidirectional, shortcrested) freak waves are simulated experimentally through the dispersive and directional focusing of component waves, and the wavelengths obtained from the surface elevations measured by the wave gauge array are compared with the results from the linear, 3rd-order and 5th-order Stokes wave theories. The comparison results suggest that the 3rd-order theory estimates the wavelengths of freak waves with higher accuracy than the linear and 5th-order theories. Furthermore, the results allow insights into the dominant factors. It is particularly noteworthy that the accuracy is likely to depend on the wave period, and that the wavelengths of longer period freak waves are overestimated but the wavelengths are underestimated for shorter period ones. In order to decrease the deviation, a modified formulation is presented to predict the wavelengths of two-and three-dimensional freak waves more accurately than the 3rd-order dispersion relation, by regression analysis. The normalized differences between the predicted and experimental results are over 50% smaller for the modified model suggested in this study compared with the 3rd-order dispersion relation.

Three-dimensional paper-like graphene framework with highly orientated laminar structure as binder-free supercapacitor electrode

A free-standing paper-like three-dimensional graphene framework（3DGF） with orientated laminar structure and interconnected macropores, was obtained by the hard template-directed ordered assembly. As the sacrificial templates, polystyrene（PS） latex spheres were assembled with graphene oxide（GO） to build up a sandwich type composite film, followed by heat removal of which with a simultaneous reduction of GO. The 3DGF exhibited high specific surface area of 402.5 m2/g, controllable pores and mechanical flexibility, which was employed as the binder-free supercapacitor electrode and shows high specific gravimetric capacitance of 95 F/g at 0.5 A/g, with enhanced rate capability in 3 electrode KOH system.

A Three-dimensional Porous Metal-organic Framework Based on Cyano Unit and 1,4-Bis(1,2,4-triazol-1-yl)butane(btb):{[Cu_8(btb)_2(CN)_8].3H_2O}_n

The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Developing an Approach for a Three-Dimensional Hydrogeologic Framework to Find Water in Northern Ghana

The purpose of this study was to develop an approach for constructing a three-dimensional hydrogeologic framework using borehole driller logs. The ultimate goal is to increase drilling success rates via a better understanding of the regional hydrogeologic framework in northern Ghana. Groundwater development has increased in northern Ghana, but drilling successful boreholes is difficult due to complex geology and limited aquifer characteristic information. An approach was developed to construct a three-dimensional hydrogeologic framework of the basin using 900 borehole logs from World Vision International’s Ghana Integrated Water, Sanitation, and Hygiene Project, located in northern Ghana. The study’s approach consists of: evaluating potential software programs;collecting borehole drilling logs;data QA/QC;data standardization and normalization;analysis for trends and correlations;and creation of a three-dimensional hydrogeologic framework and two-dimensional cross sections. This approach can be used and adapted by others working to provide groundwater in developing countries.

Managing the surge:A comprehensive review of the entire disposal framework for retired lithium-ion batteries from electric vehicles

Anticipating the imminent surge of retired lithium-ion batteries(R-LIBs)from electric vehicles,the need for safe,cost-effective and environmentally friendly disposal technologies has escalated.This paper seeks to offer a comprehensive overview of the entire disposal framework for R-LIBs,encompassing a broad spectrum of activities,including screening,repurposing and recycling.Firstly,we delve deeply into a thorough examination of current screening technologies,shifting the focus from a mere enumeration of screening methods to the exploration of the strategies for enhancing screening efficiency.Secondly,we outline battery repurposing with associated key factors,summarizing stationary applications and sizing methods for R-LIBs in their second life.A particular light is shed on available reconditioning solutions,demonstrating their great potential in facilitating battery safety and lifetime in repurposing scenarios and identifying their techno-economic issues.In the realm of battery recycling,we present an extensive survey of pre-treatment options and subsequent material recovery technologies.Particularly,we introduce several global leading recyclers to illustrate their industrial processes and technical intricacies.Furthermore,relevant challenges and evolving trends are investigated in pursuit of a sustainable end-of-life management and disposal framework.We hope that this study can serve as a valuable resource for researchers,industry professionals and policymakers in this field,ultimately facilitating the adoption of proper disposal practices.

A New Heteropolyoxotungstate with a Three-dimensional All-inorganic Framework [(C_2H_4N_2)_4(P_4Co_3W_4O_(28)H_6)(H_2C_2O_4)]_n

A new heteropolyoxotungstate [（C2H4N2）4（P4Co3W4O28H6）（H2C2O4）]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006（17）,b = 17.1006（7）,c = 10.7525（5）,V = 3144.2（2）3,Z = 4,Dc = 3.795 g·cm-3,F（000） = 3300,MoKα（λ = 0.71073 ）,μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Achieving a highly robust zinc(Zn)metal anode is extremely important for improving the performance of aqueous Zn-ion batteries(AZIBs)for advancing“carbon neutrality”society,which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction,corrosion,and passivation,etc.Herein,an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups(COF-S-F)is developed on Zn metal(Zn@COF-S-F)as the artificial solid electrolyte interface(SEI).Sulfonic acid group(-SO_(3)H)in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions,and the three-dimensional channel with fluoride group(-F)can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects,endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions.Consequently,Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage(50.5 m V)at the current density of 1.5 m A cm^(-2).Zn@COF-S-F|Mn O_(2)cell delivers the discharge specific capacity of 206.8 m Ah g^(-1)at the current density of 1.2 A g^(-1)after 800 cycles with high-capacity retention(87.9%).Enlightening,building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Synthesis, Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4？-DPA)]·(DMF)}_n

The reaction of Cd（NO_3）_2·4H_2O with 4,4？-dipyridylacetylene（4,4？-DPA） and 2-nitroterephthalic acid（2-NO_2-H_2BDC） in DMF/H_2O mixed solvent has afforded a compound {[Cd（2-NO_2-BDC）（4,4？-DPA）]·（DMF）}_n（1）. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488（3）, b = 14.6689（3）, c = 13.1615（3） ？, β = 111.809（3）o, V = 2177.63（9） ？~3, Z = 4, C_（23）H_（18）N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^（-1）, F（000） = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s（I）. In compound 1, the Cd（Ⅱ） ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2（COO）_2 units, which are further connected by the 4,4？-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.

Systematic Security Guideline Framework through Intelligently Automated Vulnerability Analysis

This research aims to propose a practical framework designed for the automatic analysis of a product’s comprehensive functionality and security vulnerabilities,generating applicable guidelines based on real-world software.The existing analysis of software security vulnerabilities often focuses on specific features or modules.This partial and arbitrary analysis of the security vulnerabilities makes it challenging to comprehend the overall security vulnerabilities of the software.The key novelty lies in overcoming the constraints of partial approaches.The proposed framework utilizes data from various sources to create a comprehensive functionality profile,facilitating the derivation of real-world security guidelines.Security guidelines are dynamically generated by associating functional security vulnerabilities with the latest Common Vulnerabilities and Exposure(CVE)and Common Vulnerability Scoring System(CVSS)scores,resulting in automated guidelines tailored to each product.These guidelines are not only practical but also applicable in real-world software,allowing for prioritized security responses.The proposed framework is applied to virtual private network(VPN)software,wherein a validated Level 2 data flow diagram is generated using the Spoofing,Tampering,Repudiation,Information Disclosure,Denial of Service,and Elevation of privilege(STRIDE)technique with references to various papers and examples from related software.The analysis resulted in the identification of a total of 121 vulnerabilities.The successful implementation and validation demonstrate the framework’s efficacy in generating customized guidelines for entire systems,subsystems,and selected modules.

Metal–Organic Framework‑Based Photodetectors

The unique and interesting physical and chemical properties of metal–organic framework(MOF)materials have recently attracted extensive attention in a new generation of photoelectric applications.In this review,we summarized and discussed the research progress on MOF-based photodetectors.The methods of preparing MOF-based photodetectors and various types of MOF single crystals and thin film as well as MOF composites are introduced in details.Additionally,the photodetectors applications for X-ray,ultraviolet and infrared light,biological detectors,and circularly polarized light photodetectors are discussed.Furthermore,summaries and challenges are provided for this important research field.

Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.