羧酸类金属有机框架材料的合成及应用

金属-有机框架材料(Metal-Organic?Frameworks,简称MOFs)是由金属离子（簇）与有机桥接配体通过配位共价键或弱相互作用自组装形成的一类具有分子内孔隙的有机-无机杂化材料。羧酸类MOFs材料中金属中心和有机羧酸配体的可变性导致了其结构和功能的多样性,在气体的吸附与分离、荧光、传感、药物传输以及电催化等多个领域展现了独特的应用前景,并被认为是当今科学上最有前途的材料之一。对于有机配体的选择,从早期易坍塌的含氮杂环类配体过渡到了如今稳定性好的羧酸类配体,解决了不少以前出现的MOFs材料结构单一易坍塌问题。     

Separating Xylene Isomers with a Calcium Metal-Organic Framework

The purification of p-xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho- and meta- isomers by a microporous calcium-based metal–organic framework material (HIAM-203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o-xylene (oX) and m-xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor-phase/liquid-phase adsorption experiments have demonstrated the capability of HIAM-203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism.     

A Paramagnetic Compass Based on Lanthanide Metal-Organic Framework

Macroscopic compass-like magnetic alignment at low magnetic fields is natural for ferromagnetic materials but is seldomly observed in paramagnetic materials. Herein, we report a “paramagnetic compass” that magnetically aligns under ∼mT fields based on the single-crystalline framework constructed by lanthanide ions and organic ligands (Ln-MOF). The magnetic alignment is attributed to the Ln-MOF's strong macroscopic anisotropy, where the highly-ordered structure allows the Ln-ions’ molecular anisotropy to be summed according to the crystal symmetry. In tetragonal Ln-MOFs, the alignment is either parallel or perpendicular to the field depending on the easiest axis of the molecular anisotropy. Reversible switching between the two alignments is realized upon the removal and re-adsorption of solvent molecules filled in the framework. When the crystal symmetry is lowered in monoclinic Ln-MOFs, the alignments become even inclined (47°-66°) to the field. These fascinating properties of Ln-MOFs would encourage further explorations of framework materials containing paramagnetic centers.     

Electron Donor Coordinated Metal-Organic Framework to Enhance Photoelectrochemical Performance

To enhance photoelectrochemical (PEC) performance, additional electron donor/acceptor is generally required to inhibit the electron-hole recombination. However, the enhancement is limited due to the long-distance diffusion. Herein a self-supplying electron strategy is designed for PEC enhancement by coordinating an electron donor 1.4-diazabicyclo[2.2.2]octane (Dabco) in metal–organic framework (MOF). The intrareticular photoelectron transfer mechanism in mixed-ligand MOF (m-MOF) is experimentally revealed and verified by density functional theory calculations. The presence of Dabco efficiently inhibits the electron-hole recombination due to the self-supplying electrons and longer electron lifetime in the framework, and thus leads to 23.2-fold enhancement of photocurrent. As proof of concept, a simple PEC method is constructed with the designed m-MOF to demonstrate its application in sensitive bioanalysis. This work provides a new avenue for improving the PEC performance of nanomaterials.     

Highly-Efficient Ion Gating through Self-Assembled Two-Dimensional Photothermal Metal-Organic Framework Membrane

Biological ion channels regulate the ion flow across cell membrane via opening or closing of the pores in response to various external stimuli. Replicating the function of high ion gating effects with artificial porous materials has been challenging. Herein, we report that the self-assembled two-dimensional metal-organic framework (MOF) membrane can serve as an excellent nanofluidic platform for smart regulation of ion transport. The MOF membrane with good photothermal performance exhibits extremely high ion gating ratio (up to 10⁴), which is among the highest values in MOF membrane nanochannels for light-controlled ion gating reported so far. By repeatedly turning on and off the light, the nanofluidic device shows outstanding stability and reversibility that can be applied in the remote light-switching system. This work may spark promising applications of MOF membrane with variety of stimuli responsive properties in ion sieving, biosensing, and energy conversion.     

Pore Size Modulation in Flexible Metal-Organic Framework Enabling High Performance Gas Sensing

Pore size plays a critical role in determining the performance of metal-organic frameworks (MOFs) in catalysis, sensing, and gas storage or separation. However, revealing the pore-size/property relationship remains extremely challenging because ideal structure models possessing different pore sizes but having the same components are lacking. In this work, a solvent-coordination directed structure swelling method was developed for modulating the ratio between the large and narrow pore phases of a flexible MOF, MIL-88B . Pore-size-dependent gas sensitivity and selectivity were studied for the first time in the MIL-88B samples. The optimized MIL-88B-20 % sample showed one of the best sensing performances among all the reported MOF-based H₂S-sensing materials. This work not only provides a method to synthesize ideal structure models for revealing the relationship between pore-size and properties, but also may inspire the development of high-performance gas sensing materials.     

Multicomponent Metal-Organic Frameworks

Metal-organic frameworks (MOFs) are constructed from metal ions or clusters and organic linkers. Typical MOFs are rather simple, comprising just one type of joint and linker. An additional degree of structural complexity can be introduced by using multiple different components that are assembled into the same framework In the early days of MOF chemistry, conventional wisdom held that attempting to prepare frameworks starting from such a broad set of components would lead to multiple different phases. However, this review highlights how this view was mistaken and frameworks comprising multiple different components can be deliberately designed and synthesized. When coupled to structural order and periodicity, the presence of multiple components leads to exceptional functional properties that can be understood at the atomic level.     

Twisting of Porphyrin by Assembly in a Metal-Organic Framework yielding Chiral Photoconducting Films for Circularly-Polarized-Light Detection

While materials based on organic molecules usually have either superior optoelectronic or superior chiral properties, the combination of both is scarce. Here, a crystalline chiroptical film based on porphyrin with homochiral side groups is presented. While the dissolved molecule has a planar, thus, achiral porphyrin core, upon assembly in a metal–organic framework (MOF) film, the porphyrin core is twisted and chiral. The close packing and the crystalline order of the porphyrin cores in the MOF film also results in excellent optoelectronic properties. By exciting the Soret band of porphyrin, efficient photoconduction with a high On-Off-ratio is realized. More important, handedness-dependent circularly-polarized-light photoconduction with a dissymmetry factor g of 4.3×10⁻⁴ is obtained. We foresee the combination of such assembly-induced chirality with the rich porphyrin chemistry will enable a plethora of organic materials with exceptional chiral and optoelectronic properties.     

Cooperative and Orthogonal Switching in the Solid State Enabled by Metal-Organic Framework Confinement Leading to a Thermo-Photochromic Platform

Cooperative behavior and orthogonal responses of two classes of coordinatively integrated photochromic molecules towards distinct external stimuli were demonstrated on the first example of a photo-thermo-responsive hierarchical platform. Synergetic and orthogonal responses to temperature and excitation wavelength are achieved by confining the stimuli-responsive moieties within a metal–organic framework (MOF), leading to the preparation of a novel photo-thermo-responsive spiropyran-diarylethene based material. Synergistic behavior of two photoswitches enables the study of stimuli-responsive resonance energy transfer as well as control of the photoinduced charge transfer processes, milestones required to advance optoelectronics development. Spectroscopic studies in combination with theoretical modeling revealed a nonlinear effect on the material electronic structure arising from the coordinative integration of photoresponsive molecules with distinct photoisomerization mechanisms. Thus, the reported work covers multivariable facets of not only fundamental aspects of photoswitch cooperativity, but also provides a pathway to modulate photophysics and electronics of multidimensional functional materials exhibiting thermo-photochromism.     

Frontispiece: Induced-Fit-Identification in a Rigid Metal-Organic Framework for ppm-Level CO2 Removal and Ultra-Pure CO Enrichment

Removing CO₂ from crude syngas via physical adsorption is an effective method to yield eligible syngas. However, the bottleneck in trapping ppm-level CO₂ and improving CO purity at higher working temperatures are major challenges. Here we report a thermoresponsive metal–organic framework ( 1 a-apz ), assembled by rigid Mg₂(dobdc) ( 1 a ) and aminopyrazine (apz), which not only affords an ultra-high CO₂ capacity (145.0/197.6 cm³ g⁻¹ (0.01/0.1 bar) at 298 K) but also produces ultra-pure CO (purity ≥99.99 %) at a practical ambient temperature (T_A). Several characterization results, including variable-temperature tests, in situ high-resolution synchrotron X-ray diffraction (HR-SXRD), and simulations, explicitly unravel that the excellent property is attributed to the induced-fit-identification in 1 a-apz that comprises self-adaption of apz, multiple binding sites, and complementary electrostatic potential (ESP). Breakthrough tests suggest that 1 a-apz can remove CO₂ from 1/99 CO₂/CO mixtures at practical 348 K, yielding 70.5 L kg⁻¹ of CO with ultra-high purity of ≥99.99 %. The excellent separation performance is also revealed by separating crude syngas that contains quinary mixtures of H₂/N₂/CH₄/CO/CO₂ (46/18.3/2.4/32.3/1, v/v/v/v/v).     

Fiber Integrated Metal-Organic Frameworks as Functional Components in Smart Textiles

Owing to high modularity and synthetic tunability, metal–organic frameworks (MOFs) on textiles are poised to contribute to the development of state-of-the-art wearable systems with multifunctional performance. While these composite materials have demonstrated promising functions in sensing, filtration, detoxification, and biomedicine, their applicability in multifunctional systems is only beginning to materialize. This review highlights the multifunctionality and versatility of MOF-integrated textile systems. It summarizes the operational goals of MOF@textile composites, encompassing sensing, filtration, detoxification, drug delivery, UV protection, and photocatalysis. Building upon these recent advances, this review concludes with an outlook on emerging opportunities for the diverse applications of MOF@textile systems in the realm of smart wearables.     

Overcoming Diffusion Limitation of Faradaic Processes: Property-Performance Relationships of 2D Conductive Metal-Organic Framework Cu3(HHTP)2 for Reversible Lithium-Ion Storage

Faradaic reactions including charge transfer are often accompanied with diffusion limitation inside the bulk. Conductive two-dimensional frameworks (2D MOFs) with a fast ion transport can combine both—charge transfer and fast diffusion inside their porous structure. To study remaining diffusion limitations caused by particle morphology, different synthesis routes of Cu-2,3,6,7,10,11-hexahydroxytriphenylene (Cu₃(HHTP)₂), a copper-based 2D MOF, are used to obtain flake- and rod-like MOF particles. Both morphologies are systematically characterized and evaluated for redox-active Li⁺ ion storage. The redox mechanism is investigated by means of X-ray absorption spectroscopy, FTIR spectroscopy and in situ XRD. Both types are compared regarding kinetic properties for Li⁺ ion storage via cyclic voltammetry and impedance spectroscopy. A significant influence of particle morphology for 2D MOFs on kinetic aspects of electrochemical Li⁺ ion storage can be observed. This study opens the path for optimization of redox active porous structures to overcome diffusion limitations of Faradaic processes.     

Size- and Emission-Controlled Synthesis of Full-Color Luminescent Metal-Organic Frameworks for Tryptophan Detection

The development of nanoscaled luminescent metal–organic frameworks (nano-LMOFs) with organic linker-based emission to explore their applications in sensing, bioimaging and photocatalysis is of great interest as material size and emission wavelength both have remarkable influence on their performances. However, there is lack of platforms that can systematically tune the emission and size of nano-LMOFs with customized linker design. Herein two series of fcu - and csq -type nano-LMOFs, with precise size control in a broad range and emission colors from blue to near-infrared, were prepared using 2,1,3-benzothiadiazole and its derivative based ditopic- and tetratopic carboxylic acids as the emission sources. The modification of tetratopic carboxylic acids using OH and NH₂ as the substituent groups not only induces significant emission bathochromic shift of the resultant MOFs, but also endows interesting features for their potential applications. As one example, we show that the non-substituted and NH₂-substituted nano-LMOFs exhibit turn-off and turn-on responses for highly selective and sensitive detection of tryptophan over other nineteen natural amino acids. This work sheds light on the rational construction of nano-LMOFs with specific emission behaviours and sizes, which will undoubtedly facilitate their applications in related areas.     

Turning on Asymmetric Catalysis of Achiral Metal-Organic Frameworks by Imparting Chiral Microenvironment

The development of heterogeneous asymmetric catalysts has attracted increasing interest in synthetic chemistry but mostly relies on the immobilization of homogeneous chiral catalysts. Herein, a series of chiral metal–organic frameworks (MOFs) have been fabricated by anchoring similar chiral hydroxylated molecules (catalytically inactive) with different lengths onto Zr-oxo clusters in achiral PCN-222(Cu). The resulting chiral MOFs exhibit regulated enantioselectivity up to 83 % ee in the asymmetric ring-opening of cyclohexene oxide. The chiral molecules furnished onto the catalytic Lewis sites in the MOF create multilevel microenvironment, including the hydrogen interaction between the substrate and the chiral −OH group, the steric hindrance endowed by the benzene ring on the chiral molecules, and the proximity between the catalytic sites and chiral molecules confined in the MOF pores, which play crucial roles and synergistically promote chiral catalysis. This work nicely achieves heterogeneous enantioselective catalysis by chiral microenvironment modulation around Lewis acid sites.     

Back Cover: Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions (Angew. Chem. Int. Ed. 21/2023)

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.     

金属-有机骨架材料的合成及其在荧光传感器中的应用

金属-有机框架材料（MOFs）,是一类由金属节点或者是次级构筑单元与有机配体通过配位键自主装形成的材料。由于其丰富的拓扑结构及在多领域的潜在应用,已被广泛研究。最近关于块状和纳米颗粒形式的发光MOFs 的研究表明,这些材料具有优异的发光性质,可用来检测识别溶剂分子、重金属离子、黄曲霉素、硝基苯类爆炸物以及碘离子等。并且开发高灵敏度,高选择性,快速响应和完全可逆的有毒物质和爆炸物检测传感器,在国土安全,环境安全及其他人道主义关切问题上有着极大的需求。在这篇文章中,我们主要讨论MOF材料作为荧光传感器的应用研究和发展前景。     

Modular Functionalization of Metal-Organic Frameworks for Nitrogen Recovery from Fresh Urine**

Nitrogen recovery from wastewater represents a sustainable route to recycle reactive nitrogen (Nr). It can reduce the demand of producing Nr from the energy-extensive Haber-Bosch process and lower the risk of causing eutrophication simultaneously. In this aspect, source-separated fresh urine is an ideal source for nitrogen recovery given its ubiquity and high nitrogen contents. However, current techniques for nitrogen recovery from fresh urine require high energy input and are of low efficiencies because the recovery target, urea, is a challenge to separate. In this work, we developed a novel fresh urine nitrogen recovery treatment process based on modular functionalized metal–organic frameworks (MOFs). Specifically, we employed three distinct modification methods to MOF-808 and developed robust functional materials for urea hydrolysis, ammonium adsorption, and ammonia monitoring. By integrating these functional materials into our newly developed nitrogen recovery treatment process, we achieved an average of 75 % total nitrogen reduction and 45 % nitrogen recovery with a 30-minute treatment of synthetic fresh urine. The nitrogen recovery process developed in this work can serve as a sustainable and efficient nutrient management that is suitable for decentralized wastewater treatment. This work also provides a new perspective of implementing versatile advanced materials for water and wastewater treatment.     

Metal-Organic Frameworks for Photocatalytic Water Splitting and CO2 Reduction

Photocatalytic water splitting and carbon dioxide (CO₂) reduction provide promising solutions to global energy and environmental issues. In recent years, metal-organic frameworks (MOFs), a class of crystalline porous solids featuring well-defined and tailorable structures as well as high surface areas, have captured great interest toward photocatalytic water splitting and CO₂ reduction. In this review, the semiconductor-like behavior of MOFs is first discussed. We then summarize the recent advances in photocatalytic water splitting and CO₂ reduction over MOF-based materials and focus on the unique advantage of MOFs for clarifying the structure-property relationship in photocatalysis. In addition, some representative characterization techniques have been presented to unveil the photocatalytic kinetics and reaction intermediates in MOF-based systems. Finally, the challenges, and perspectives for future directions are proposed.     

Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO2 Reduction

Traditional MOF e-CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi-electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e-CRR systems, CoPc@NU-1000 and TPP(Co)@NU-1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU-1000 MOF. For CoPc@NU-1000, the e-CRR responsive Co^I/0 potential is close to that of NU-1000 reduction compared to the TPP(Co)@NU-1000. Efficient charge delivery, defined by a higher diffusion (D_hop=4.1×10⁻¹² cm² s⁻¹) and low charge-transport resistance ( =59.5 Ω) in CoPC@NU-1000 led FE_CO=80 %. In contrast, TPP(Co)@NU-1000 fared a poor FE_CO=24 % (D_hop=1.4×10⁻¹² cm² s⁻¹ and =91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.     

Highly Luminescent Lanthanide Metal-Organic Frameworks with Tunable Color for Nanomolar Detection of Iron(III), Ofloxacin and Gossypol and Anti-counterfeiting Applications

Solvothermal reaction of 5,5′-(pyridine-2,6-diylbis(oxy))diisophthalic acid (H₄L) with europium(III) or terbium(III) nitrates in acetonitrile-water (1 : 1) at 120 °C gave rise to isostructural 2D coordination polymers, [Ln(HL)(H₂O)₃]_∞ ( NIIC-1-Eu and NIIC-1-Tb ), the layers of which are composed by eight-coordinated lanthanide(III) ions interconnected by triply deprotonated ligands HL³⁻. The layers are packed in the crystal without any specific intermolecular interactions between them, allowing the facile preparation of stable water suspensions, in which NIIC-1-Tb exhibited top-performing sensing properties through luminescence quenching effect with exceptionally low detection limits towards Fe³⁺ (LOD 8.62 nM), ofloxacin (OFX) antibiotic (LOD 3.91 nM) and cotton phytotoxicant gossypol (LOD 2.27 nM). In addition to low detection limit and high selectivity, NIIC-1-Tb features fast sensing response (within 60–90 seconds), making it superior to other MOF-based sensors for metal cations and organic toxicants. The photoluminescence quantum yield of NIIC-1-Tb was 93 %, one of the highest among lanthanide MOFs. Mixed-metal coordination polymers NIIC-1-Eu_xTb_1−x demonstrated efficient photoluminescence, the color of which could be modulated by the excitation wavelength and time delay for emission monitoring (within 1 millisecond). Furthermore, an original 2D QR-coding scheme was designed for anti-counterfeiting labeling of goods based on unique and tunable emission spectra of NIIC-1-Ln coordination polymers.