Crystalline Porous Materials Research Articles

Selective Xenon Recovery Using Aluminum-Based Metal-Organic Frameworks with Conserved Pore Topology.

Xenon (Xe) is a commercially valuable element found in trace amounts in the off-gas from used nuclear fuel. Recovering Xe from these streams provides a cost-effective means to increase its supply. However, achieving high-purity Xe recovery is challenging due to the need for separation from nearly identical krypton (Kr). Metal-organic frameworks (MOFs), a class of crystalline porous materials, show potential to separate Xe and Kr by utilizing differences in their kinetic diameters, allowing for selective separation. In this work, we study the impact of pore aperture and volume on selective Xe recovery using four robust aluminum MOFs: Al-PMOF, Al-PyrMOF, Al-BMOF and MIL-120, all with conserved structural topology. The pore topology in each MOF is dictated by the dimensions of the tetracarboxylate ligand employed, with larger ligands leading to MOFs with increased pore size and volume. Our experimental and computational investigations revealed that MIL-120 exhibits the highest affinity (21.94 kH(Xe) = 21.94 mmol g-1 bar-1) for Xe among all MOFs, while Al-BMOF demonstrates the highest Xe/Kr selectivity of 14.34. We evaluated the potential of both MIL-120 and Al-BMOF for Xe recovery through breakthrough analysis using a mixture of 400 ppm Xe:40 ppm Kr. Our results indicate that due to its larger pore volume, Al-BMOF captured more Xe than MIL-120, demonstrating superior Xe/Kr separation efficiency.

Encapsulation of InP/ZnS Quantum Dots into MOF-5 Matrices for Solid-State Luminescence: Ship in the Bottle and Bottle around the Ship Methodologies.

The utilization of InP-based quantum dots (QDs) as alternative luminescent nanoparticles to cadmium-based QDs is actively pursued. However, leveraging their luminescence for solid-state applications presents challenges due to the sensitivity of InP QDs to oxidation and aggregation-caused quenching. Hence, an appealing strategy is to protect and disperse InP QDs within hybrid materials. Metal-organic frameworks (MOFs) offer a promising solution as readily available crystalline porous materials. Among these, MOF-5 (composed of {Zn4O}6+ nodes and terephthalate struts) can be synthesized under mild conditions (at room temperature and basic pH), making it compatible with InP QDs. In the present work, luminescent InP/ZnS QDs are successfully incorporated within MOF-5 by two distinct methods. In the bottle around the ship (BAS) approach, the MOF was synthesized around the QDs. Alternatively, in the ship in the bottle (SIB) strategy, the QDs were embedded via capillarity into a specially engineered, more porous variant of MOF-5. Comparative analysis of the BAS and SIB approaches, evaluating factors such as operational simplicity, photoluminescence properties, and the resistance of the final materials to leaching were carried out. This comparative study provides insights into the efficacy of these strategies for the integration of InP/ZnS QDs within MOF-5 for potential solid-state applications in materials chemistry.

Rapid synthesis of aminal-linked covalent organic frameworks for CO2/CH4 separation.

As an emerging category of crystalline porous materials, covalent organic frameworks (COFs) are primarily synthesized via solvothermal methods. However, achieving rapid synthesis of COFs through this approach poses a significant challenge. To address the issue of slow synthesis, we studied the crystallization process of aminal-linked COFs via the condensation of a cost-effective aldehyde and secondary amine, and successfully expedited the synthesis of COFs within a one-hour duration. Furthermore, gram-scale aminal-linked COFs with abundant ultra-microporous channels demonstrated promising potential for CO2/CH4 separation. This study enables the rapid synthesis of aminal-linked COFs from cheap raw materials, which lays a foundation for their practical applications.

Metal-Organic-Frameworks Based Mixed-Matrix Membranes for CO2 Separation: An Applicable-Conceptual Approach.

A promising class of porous crystalline materials, metal-organic frameworks (MOFs), have recently emerged as a potential material in fabricating mixed matrix membranes (MMMs) for gas separation applications. Their unique chemistry and structural versatility offer substantial advantages over conventional fillers. This review gives an in-depth exploration of MOF chemistry, focusing on strategies to manipulate their adsorption behavior to enhance separation properties. We scrutinize the impact of various MOF-based MMM components, including polymer matrix, MOFs fillers and polymer/filler interface, on the overall gas separation performance. This involves a detailed analysis of key parameters associated with MMM preparation. Additionally, we offer a comprehensive overview of the determining factors in MOF-based MMM development for gas separation, including MOF structure, synthesis, and chemistry. Moreover, the most advances in modification strategies of MOF for CO2 separation, such as a wide variety of hybrid MOFs will be outlined, which opens the door to an improved CO2 separation process. Finally, the gas transport mechanisms of MMMs are thoroughly discussed to understand the factors affecting the gas permeation through the polymer matrix, MOFs and interface between them.

Porous Crystalline Materials Based on Tetrathiafulvalene and Its Analogues: Assembly, Charge Transfer, and Applications.

ConspectusThe directed synthesis and functionalization of porous crystalline materials pose significant challenges for chemists. The synergistic integration of different functionalities within an ordered molecular material holds great significance for expanding its applications as functional materials. The presence of coordination bonds connected by inorganic and organic components in molecular materials can not only increase the structural diversity of materials but also modulate the electronic structure and band gap, which further regulates the physical and chemical properties of molecular materials. In fact, porous crystalline materials with coordination bonds, which inherit the merits of both organic and inorganic materials, already showcase their superior advantages in optical, electrical, and magnetic applications. In addition to the inorganic components that provide structural rigidity, organic ligands of various types serve as crucial connectors in the construction of functional porous crystalline materials. In addition, redox activity can endow organic linkers with electrochemical activity, thereby making them a perfect platform for the study of charge transfer with atom-resolved single-crystal structures, and they can additionally serve as stimuli-responsive sites in sensor devices and smart materials.In this Account, we introduce the synthesis, structural characteristics, and applications of porous crystalline materials based on the famous redox-active units, tetrathiafulvalene (TTF) and its analogues, by primarily focusing on metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). TTF, a sulfur-rich conjugated molecule with two reversible and easily accessible oxidation states (i.e., radical TTF•+ cation and TTF2+ dication), and its analogues boast special electrical characteristics that enable them to display switchable redox activity and stimuli-responsive properties. These inherent properties contribute to the enhancement of the optical, electrical, and magnetic characteristics of the resultant porous crystalline materials. Moreover, delving into the charge transfer phenomena, which is key for the electrochemical process within these materials, uncovers a myriad of potential functional applications. The Account is organized into five main sections that correspond to the different properties and applications of these materials: optical, electrical, and magnetic functionalities; energy storage and conversion; and catalysis. Each section provides detailed discussions of synthetic methods, structural characteristics, the physical and chemical properties, and the functional performances of highlighted examples. The Account also discusses future directions by emphasizing the exploration of novel organic units, the transformation between radical cation TTF•+ and dication TTF2+, and the integration of multifunctionalities within these frameworks to foster the development of smart materials for enhanced performance across diverse applications. Through this Account, we aim to highlight the massive potential of TTF and its analogues-based porous crystals in chemistry and material science.

Thickness-Driven Synthesis and Applications of Covalent Organic Framework Nanosheets.

Covalent organic frameworks (COFs) are two-dimensional, crystalline porous framework materials with numerous scopes for tunability, such as porosity, functionality, stability and aspect ratio (thickness to length ratio). The manipulation of π-stacking in COFs results in truly 2D materials, namely covalent organic nanosheets (CONs), adds advantages in many applications. In this Minireview, we have discussed both top-down (COFs→CONs) and bottom-up (molecules→CONs) approaches with precise information on thickness and lateral growth. We have showcased the research progress on CONs in a few selected applications, such as batteries, catalysis, sensing and biomedical applications. This Minireview specifically highlights the reports where the authors compare the performance of CONs with COFs by demonstrating the impact of the thickness and lateral growth of the nanosheets. We have also provided the possible scope of exploration of CONs research in terms of inter-dimensional conversion, such as graphene to carbon nanotube and future technologies.

Thickness‐Driven Synthesis and Applications of Covalent Organic Framework Nanosheets

AbstractCovalent organic frameworks (COFs) are two‐dimensional, crystalline porous framework materials with numerous scopes for tunability, such as porosity, functionality, stability and aspect ratio (thickness to length ratio). The manipulation of π‐stacking in COFs results in truly 2D materials, namely covalent organic nanosheets (CONs), adds advantages in many applications. In this Minireview, we have discussed both top‐down (COFs→CONs) and bottom‐up (molecules→CONs) approaches with precise information on thickness and lateral growth. We have showcased the research progress on CONs in a few selected applications, such as batteries, catalysis, sensing and biomedical applications. This Minireview specifically highlights the reports where the authors compare the performance of CONs with COFs by demonstrating the impact of the thickness and lateral growth of the nanosheets. We have also provided the possible scope of exploration of CONs research in terms of inter‐dimensional conversion, such as graphene to carbon nanotube and future technologies.

Metal–Organic Framework‐Based Hetero‐Phase Nanostructure Photocatalysts with Molecular‐Scale Tunable Energy Levels

AbstractAs an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero‐phase, plays an important role in developing high‐performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero‐phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal–organic frameworks (MOFs) might be the appropriate candidate, but the MOF‐based hetero‐phase is rarely reported. Herein, we developed a secondary building unit (SBU) regulating strategy to prepare two crystal phases of Ti‐MOFs constructed by titanium and 1,4‐dicarboxybenzene, i.e., COK and MIL‐125. Besides, COK/MIL‐125 hetero‐phase was further constructed. In the photocatalytic hydrogen evolution reaction, COK/MIL‐125 possessed the highest H2 yield compared to COK and MIL‐125, ascribing to the Z‐Scheme homojunction at hetero‐phase interface. Furthermore, by decorating with amino groups (i.e., NH2‐COK/NH2‐MIL‐125), the light absorbing capacity was broadened to visible‐light region, and the visible‐light‐driven H2 yield was greatly improved. Briefly, the MOF‐based hetero‐phase possesses periodic channel structures and molecularly adjustable band structures, which is scarce in traditional organic or inorganic materials. As a proof of concept, our work not only highlights the development of MOF‐based hetero‐phase nanostructures, but also paves a novel avenue for designing high‐performance photocatalysts.

Metal-Organic Framework-Based Hetero-Phase Nanostructure Photocatalysts with Molecular-Scale Tunable Energy Levels.

As an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero-phase, plays an important role in developing high-performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero-phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal-organic frameworks (MOFs) might be the appropriate candidate, but the MOF-based hetero-phase is rarely reported. Herein, we developed a secondary building unit (SBU) regulating strategy to prepare two crystal phases of Ti-MOFs constructed by titanium and 1,4-dicarboxybenzene, i.e., COK and MIL-125. Besides, COK/MIL-125 hetero-phase was further constructed. In the photocatalytic hydrogen evolution reaction, COK/MIL-125 possessed the highest H2 yield compared to COK and MIL-125, ascribing to the Z-Scheme homojunction at hetero-phase interface. Furthermore, by decorating with amino groups (i.e., NH2-COK/NH2-MIL-125), the light absorbing capacity was broadened to visible-light region, and the visible-light-driven H2 yield was greatly improved. Briefly, the MOF-based hetero-phase possesses periodic channel structures and molecularly adjustable band structures, which is scarce in traditional organic or inorganic materials. As a proof of concept, our work not only highlights the development of MOF-based hetero-phase nanostructures, but also paves a novel avenue for designing high-performance photocatalysts.

Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages

AbstractA novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B−O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3‐based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π–π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions. Significantly, the CPOFs can be synthesized on a gram‐scale using cost‐effective monomers. In addition, the numerous acidic sites endow the CPOFs with high NH3 capacity, surpassing most porous organic materials and commercial materials.

Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages.

A novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B-O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3-based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π-π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions. Significantly, the CPOFs can be synthesized on a gram-scale using cost-effective monomers. In addition, the numerous acidic sites endow the CPOFs with high NH3 capacity, surpassing most porous organic materials and commercial materials.

Covalent-Organic-Framework-Modified Quartz Crystal Microbalance Sensor for Selective Detection of Hazardous Formic Acid.

Covalent organic frameworks (COFs) are a novel family of porous crystalline materials utilized in various advanced applications. However, applying COFs as a hazardous organic acid gas sensor is substantial but still challenging. Herein, a phenylenediamine-based covalent organic framework (TPDA-TPB COF) featuring excellent crystallinity, ultrastable thermal stability, and high surface area was successfully constructed. Then, the TPDA-TPB COF-modified quartz crystal microbalance (QCM) sensor is fabricated by immobilizing the TPDA-TPB COF thin film on the gold-QCM chip. The fabricated TPDA-TPB COF-modified QCM sensor demonstrates a rapid response, excellent reproducibility, high selectivity, and sensitivity to formic gas, arising from hydrogen-bonding interactions between formic acid and the outermost layer of the TPDA-TPB COF, as determined by extensive analysis and density functional theory calculations. The basic sites of the TPDA-TPB COF, which are numerous due to its high nitrogen content, and the carboxylic acid groups present in formic acid exhibit efficient interactions. The sensitivity of the TPDA-TPB COF-modified QCM sensor was found to be 7.75 Hz ppm-1 at standard room temperature and pressure conditions, with a limit of detection (LOD) of formic acid down to 1.18 ppm, which is significantly below the workplace olfactory threshold limit of 5.0 ppm established by the Occupational Safety and Health Administration. The TPDA-TPB COF-modified QCM sensor exhibits remarkable detecting capabilities, making it highly attractive for detecting organic acid vapors in diverse applications that require superior performance.

A hydroxyl-rich covalent organic framework for the precisely selective fluorescence sensing of explosives with high sensitivity

Covalent organic Frameworks (COFs) have become a new platform for functional research and material design. A novel covalent organic skeleton (DHB-TFP COF) was synthesized from 2-hydroxybenzene-1,3,5-tricarbaldehyde and 3,3′-dihydroxybenzidine using Schiff base reaction. DHB-TFP COF is a highly stable porous crystalline material and exhibits exceptional thermal and chemical resistance. DHB-TFP COF exhibited a selective and sensitive “turn-off” fluorescence response to 4-NP in ethanol, and TNP not only significantly quenched the fluorescence of DHB-TFP COF but also caused the obvious red-shift. The fluorescence intensity of DHB-TFP COF exhibited a linear correlation with the concentration of 4-NP with a detection limit of 0.40 μM. Furthermore, the maximum fluorescence peak observed for DHB-TFP COF demonstrated a linear relationship with TNP concentration with a detection limit of 11.15 μM. DHB-TFP COF exhibited satisfactory recovery in the detection of 4-NP and TNP in actual water sample indicating its practical application potential. The O atoms of rich hydroxyl and N atoms of C = N present on the surface of DHB-TFP COF scaffold can establish strong hydrogen bonds with 4-NP and TNP, facilitating their mutual interaction. The spectra studies indicated that the fluorescence quenching mechanism can be attributed to the absorption competitive quenching (ACQ) and fluorescence resonance energy transfer (FRET) mechanism. This study not only proposed the approach for synthesizing novel structured organic frameworks, but also developed a highly selective and sensitive fluorescence chemical sensor for identifying and detecting 4-NP and TNP.

Isomeric Porous Cu(I) Triazolate Frameworks Showing Periodic and Aperiodic Flexibility for Efficient CO Separation.

Guest-induced (crystal-to-crystal) transformation, i.e., periodic flexibility, is a typical feature of molecule-based crystalline porous materials, but its role for adsorptive separation is controversial. On the other hand, aperiodic flexibility is rarely studied. This work reports a pair of isomeric Cu(I) triazolate frameworks, namely, α-[Cu(fetz)] (MAF-2Fa) and β-[Cu(fetz)] (MAF-2Fb), which show typical periodic and aperiodic flexibility for CO chemical adsorption, respectively. Quantitative mixture breakthrough experiments show that, while MAF-2Fa exhibits high adsorption capacity at high pressures but negligible adsorption below the threshold pressure and with leakage concentrations of 3-8%, MAF-2Fb exhibits relatively low adsorption capacity at high pressures but no leakage (residual CO concentration <1 ppb). Tandem connection of MAF-2Fa and MAF-2Fb can combine their advantages of high CO adsorption capacities at high and low pressures, respectively. MAF-2Fa and MAF-2Fb can both keep the separation performances unchanged at high relative humidities, but only MAF-2Fb shows a unique coadsorption behavior at a relative humidity of 82%, which can be used to improve purification performances.

Cryo-EM combined with image deconvolution to determine ZIF-8 crystal structure

Abstract Metal–organic frameworks (MOFs) are crystalline porous materials with tunable properties, exhibiting great potential in gas adsorption, separation and catalysis.[1,2] It is challenging to visualize MOFs with transmission electron microscopy (TEM) due to their inherent instability under electron beam irradiation. Here, we employ cryo-electron microscopy (cryo-EM) to capture images of MOF ZIF-8, revealing inverted-space structural information at a resolution of up to about 1.7 Å and enhancing its critical electron dose to around 20 e −/Å2. In addition, it is confirmed by electron-beam irradiation experiments that the high voltage could effectively mitigate the radiolysis, and the structure of ZIF-8 is more stable along the [100] direction under electron beam irradiation. Meanwhile, since the high-resolution electron microscope images are modulated by contrast transfer function (CTF) and it is difficult to determine the positions corresponding to the atomic columns directly from the images. We employ image deconvolution to eliminate the impact of CTF and obtain the structural images of ZIF-8. As a result, the heavy atom Zn and the organic imidazole ring within the organic framework can be distinguished from structural images.

Synthesis of Stable 2D Conductive Lanthanide Organic Frameworks (Lu‐HHTP) for High‐Performance Humidity Sensors

Two‐dimensional conductive metal‐organic frameworks (MOFs) featuring structural diversity and high porosity represent promising platforms for chemiresistive humidity sensing. The precise control of the structure of lanthanide‐based MOFs and an exploration of its impact on charge transport and sensing applications have consistently been focal points for researchers. In this study, we present the synthesis and characterization of Lu‐HHTP (HHTP = 2,3,6,7,10,11‐hexahydroxytriphenylene) as highly crystalline and conductive porous materials. The polymeric framework of Lu‐HHTP encompasses 1D hexagonal channels and exhibits interlayer π‐π stacking, resulting in a material with a high surface area and uniform rod‐like microstructure. Benefiting from its elevated electrical conductivity, the Lu‐HHTP‐based humidity sensor exhibited commendable sensing properties within the relative humidity range of 33% to 95% at room temperature (25°C), achieving a response value as high as 19 at 95% relative humidity. Furthermore, the sensor displayed superior repeatability, characterized by rapid response and recovery speeds in the presence of moisture. These findings indicate that Lu‐HHTP holds substantial promise as a material for humidity sensors.

Photochemical and Patternable Synthesis of 2D Covalent Organic Framework Thin Film Using Dynamic Liquid/Solid Interface.

2D covalent organic frameworks (COFs) are highly porous crystalline materials with promising applications in organic electronics. Current methods involve either on-surface synthesis (solid surface) or interfacial synthesis (liquid/liquid, liquid/gas interface) to create thin films for these applications, each with its drawbacks. On-surface synthesis can lead to contamination from COF powder or unreacted chemicals, while interfacial synthesis risks damaging the film during post-transfer processes. These challenges necessitate the development of alternative synthesis methods for high-quality 2D COF films. This study presents a novel approach for synthesizing homogeneous 2D COF thin films by combining photochemistry and a liquid-flowing system. Leveraging previous work on liquid flow systems to prevent contamination during solvothermal synthesis, this approach to the photochemical method, resulting in the synthesis of high-crystalline 2D COF films with tunable thickness is adopted. The photochemical approach offers spatially controllable energy sources, enabling patternable COF synthesis. Notably, it is successfully fabricated ultrasmooth patterned 2D COF films on hexagonal boron nitride, offering a streamlined process for optoelectronic device fabrication without additional pre, post-processing steps.

Constructing ordered and tunable extrinsic porosity in covalent organic frameworks via water-mediated soft-template strategy

As one of the most attractive methods for the synthesis of ordered hierarchically porous crystalline materials, the soft-template method has not appeared in covalent organic frameworks (COFs) due to the incompatibility of surfactant self-assembly and guided crystallization process of COF precursors in the organic phase. Herein, we connect the soft templates to the COF backbone through ionic bonds, avoiding their crystallization incompatibilities, thus introducing an additional ordered arrangement of soft templates into the anionic microporous COFs. The ion exchange method is used to remove the templates while maintaining the high crystallinity of COFs, resulting in the construction of COFs with ordered hierarchically micropores/mesopores, herein named OHMMCOFs (OHMMCOF-1 and OHMMCOF-2). OHMMCOFs exhibit significantly enhanced functional group accessibility and faster mass transfer rate. The extrinsic porosity can be adjusted by changing the template length, concentration, and ratio. Cationic guanidine-based COFs (OHMMCOF-3) are also constructed using the same method, which verifies the scalability of the soft-template strategy. This work provides a path for constructing ordered and tunable extrinsic porosity in COFs with greatly improved mass transfer efficiency and functional group accessibility.

Theoretical screening of corrole-based covalent organic framework metal single-atom catalysts for ORR and OER

Corrole-based covalent organic frameworks (COFs) are newly developing porous crystalline materials in the catalysis field due to their thermal stability, and ease of being functionalized by high-valent metal at the corrole center. In this work, based on the monolayer TPAPC-COF (m-TPAPC-COF), a series of stable metal corrole-based 2D monolayer SACs M1@TPAPC-COFs (M = Fe, Co, Ni, Cu, Ru, Rh, Os, Ir, Pt, Au) have been obtained by screening using density functional theory (DFT) calculations. As O2 can be adsorbed and activated on M1@TPAPC-COFs (M = Fe, Co, Ru, Rh, Os, Ir), we predicted two types of non-noble metal corrole-based COFs SACs, one is a bifunctional SAC Fe1@TPAPC-COF with high electrocatalytic activity for ORR/OER and the other is a Co1@TPAPC-COF with high electrocatalytic activity for OER, respectively. This work demonstrates that corrole-based COF is a promising 2D material for constructing high-performance SACs for the ORR and OER.

Densification and shaping of pure Cu-BTC powders using a solid-state chemical transformation

MOFs are a class of porous crystalline materials whose unique properties have led to applicability in several fields ranging from gas adsorption to drug delivery. Despite their high potential, MOFs are usually found as fine powders, a property that can limit their use in industrial applications. Here, a novel approach is proposed to form densified Cu-MOF (Cu-BTC) powders and monoliths using 1,2-ethanedisulfonic acid (EDSA) as a densification agent. A MOF/EDSA mixture was heated to ∼150 °C; the molten EDSA not only promotes the growth of larger MOF crystallites, but also stimulates condensation reactions between the carboxylate-based MOF ligands, further binding the particles together. When this reaction was done in a stainless-steel die under pressure MOF-based monoliths could also be formed. Notably, using this approach, the MOF had a higher density, significantly improving the volumetric CO2 adsorption capacity. We believe this contribution provides the basis for future work wherein the intrinsic MOF particle surfaces can be selectively engineered to improve their properties towards shaping for industrial applications.