ConspectusMetal–organic frameworks (MOFs) possess an important advantage over other candidate classes for chemosensory materials because of their exceptional structural tunability and properties. Luminescent sensing using MOFs is a simple, intuitive, and convenient method to recognize species, but the method has limitations, such as insufficient chemical selectivity and signal loss. MOFs contain versatile building blocks (linkers or ligands) with special chemical reactivity, and postsynthetic modification (PSM) provides an opportunity to exploit and expand their unique properties. The linkers in most MOFs contain aromatic subunits that can readily display luminescence after ultraviolet or visible (typically blue) excitation, and this is the main luminescent nature of most MOFs. The introduction of photoactive lanthanide ions (Ln3+) into the MOF hosts may produce new luminescent signals at different positions from that of the MOF linker, but this depends on the intramolecular energy transfer (antenna effec...

Lanthanide-Functionalized Metal–Organic Framework Hybrid Systems To Create Multiple Luminescent Centers for Chemical Sensing

Metal-organic frameworks (MOFs) are a class of porous materials with unprecedented chemical and structural tunability. Their synthetic versatility, long-range order, and rich host–guest chemistry make MOFs ideal platforms for identifying design features for advanced functional materials. This review addresses synthetic approaches to control MOF attributes for realizing material properties such as charge conductivity, stability, surface area, and flexibility. Along with an updated account on MOFs employed in batteries and supercapacitors, new directions are outlined for advancing MOF research in emergent technologies such as solid-state electrolytes and battery operation in extreme environments. Synthetic tenability of metal organic frameworks renders them versatile platform for next-generation energy storage technologies. Here the authors provide an overview of selected MOF attributes for applications in solid-state electrolytes and battery operation in extreme environments.

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Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices

In this review, we highlight how recent advances achieved in the fields of photochemistry and photophysics of metal–organic frameworks (MOFs) could be applied towards the engineering of next generation MOF-based sensing devices. In addition to high surface area and structural tunability, which are crucial for efficient sensor development, progress in the field of MOF-based sensors could rely on the combination of MOF light-harvesting ability, understanding energy transfer processes within a framework, and application of MOF-based photocatalysis towards sensing enhancement. All photophysical concepts could be integrated within one material to improve efficiency and selectivity of sensing devices. Thus, the focus of this review is shifted towards a “beyond the pores” approach, which could foreshadow new guidelines for sensor engineering.

Photochemistry and photophysics of MOFs: steps towards MOF-based sensing enhancements.

Metal-organic frameworks (MOFs) with multiple emission centers are newly emerging as ratiometric sensors owing to their high sensitivity and high selectivity toward a wide range of targeted functional species. Energy transfer between the light-absorbing group and emission centers and between different emission centers is the key to rationally design and synthesize MOF-based ratiometric sensors. A good match between the energy levels of the light-absorbing groups and emission centers is the prerequisite for MOF-based sensors to exhibit multiple emissions, and a good match of the MOF-based sensors and those of the targeted species can increase the sensitivity and selectivity, but this match is highly challenging to obtain via synthesis. MOFs with multiple emission centers can be produced by functionalizing MOFs with multiple lanthanide centers, organic luminophores, dyes, carbon dots, and other such emissive groups. In this progress report, recent advances in the strategies for synthesizing MOFs with multiple emission centers and their applications for ratiometric sensing of solution conditions, including the pH value, and ion, organic molecule, and biomolecule concentrations, are summarized, as are the related sensing mechanisms.

Multicenter Metal-Organic Framework-Based Ratiometric Fluorescent Sensors.

Beyond conventional porous materials, metal-organic frameworks (MOFs) have aroused great interest in the construction of nanocatalysts with the characteristics of catalytically active nanoparticles (NPs) confined into the cavities/channels of MOFs or surrounded by MOFs. The advantages of adopting MOFs as the encapsulating matrix are multifold: uniform and long-range ordered cavities can effectively promote the mass transfer and diffusion of substrates and products, while the diverse metal nodes and tunable organic linkers may enable outstanding synergy functions with the encapsulated active NPs. Herein, some key issues related to MOFs for catalysis are discussed. Then, state-of-the art progress in the encapsulation of catalytically active NPs by MOFs as well as their synergy functions for enhanced catalytic performance in the fields of thermo-, photo-, and electrocatalysis are summarized. Notably, encapsulation-structured nanocatalysts exhibit distinct advantages over conventional supported catalysts, especially in terms of the catalytic selectivity and stability. Finally, challenges and future developments in MOF-based encapsulation-structured nanocatalysts are proposed. The aim is to deliver better insight into the design of well-defined nanocatalysts with atomically accurate structures and high performance in challenging reactions.

Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives.

Unsafe food is a huge threat to human health and the economy, and detecting food spoilage early is an ongoing and imperative need. Herein, a simple and effective strategy combining a fluorescence sensor and one-to-two logic operation is designed for monitoring biogenic amines, indicators of food spoilage. Sensors (methyl red@lanthanide metal-organic frameworks (MR@EuMOFs)) are created by covalently modifying MR into NH2 -rich EuMOFs, which have a high quantum yield (48%). A double-stimuli-responsive fluorescence center is produced via energy transfer from the ligands to Eu3+ and MR. Portable sensory hydrogels are obtained by dispersing and solidifying MR@EuMOFs in water-phase sodium salt of carboxy methyl cellulose (CMC-Na). The hydrogels exhibit a color transition upon "smelling" histamine (HI) vapor. This transition and shift in the MR-based emission peak are closely related to the HI concentration. Using the HI concentration as the input signal and the two fluorescence emissions as output signals, an advanced analytical device based on a one-to-two logic gate is constructed. The four output combinations, NOT (0, 1), YES (1, 0), PASS 1 (1, 1), and PASS 0 (0, 0), allow the direct analysis of HI levels, which can be used for real-time food-freshness evaluation. The novel strategy suggested here may be a new application for a molecular logic system in the sensing field.

A Double‐Stimuli‐Responsive Fluorescent Center for Monitoring of Food Spoilage based on Dye Covalently Modified EuMOFs: From Sensory Hydrogels to Logic Devices

Metal-organic frameworks (MOFs) are intriguing platforms with multiple functionalities. Additional functionalization of MOFs generates novel materials for various applications. Here, three main topics are examined regarding the functionalization of MOFs for use as photoactive materials. The first is chemical approaches for postsynthetic modification of the metal clusters and organic linkers in MOFs; that is, sites on pore surfaces and chemical trapping of photoactive moieties within the pores, which create materials with chemical functionalities for water splitting and CO2 reduction by light. The second topic focuses on the functionalization of MOFs for photochemical response and the versatile applications of such materials. State-of-the-art research on functionalizing MOFs through photochemical reactions on the pore surface and within the pores as guests is also summarized. The third topic introduces the functionalization of MOFs for photofunctional materials, including photoluminescent tuning and integration, photoluminescent LED devices and barcodes, and photophysical applications for chemical sensing. Finally, conclusions and perspectives on the fields are given.

Functionalization of Metal–Organic Frameworks for Photoactive Materials

Eu3+ functionalized Sc-MOFs: Turn-on fluorescent switch for ppb-level biomarker of plastic pollutant polystyrene in serum and urine and on-site detection by smartphone

A wearable glove-based sensor has been developed for non-invasive organophosphorus pesticide (OP) monitoring via the fluorescent detection technology. The new "lab-on-a-glove" device integrates a flexible host material (CMC aerogel) and two fluorescent centers (EuMOFs for red and nanosized CDs for blue emissons). After characterizing the performance and stability of the sensor, qualitative and quantitative OP detections are successfully conducted on the surfaces of different agricultural products using swipe collection. The real-time detection system offers considerable advantages such as rapid response (30 s) due to the porous structures of CMC aerogel and MOFs, detection with the naked eye (the red to blue emission transition corresponds to an increase in the OP concentration) and high sensitivity (R2 = 0.99529, LOD = 89 nM) owing to the double-signal sensing strategy in which EuMOFs are the working fluorescence center and CDs are the reference fluorescence center. Compared with other OP detection methods, our strategy of using wearable device with the ratiometric fluorescence method leads to a convenient and reliable detection process for OP analysis. Also, considering its cost advantage, the glove-based sensor holds promise for practical applications in food safety and security.

Wearable glove sensor for non-invasive organophosphorus pesticide detection based on a double-signal fluorescence strategy

A luminescent nanoprobe based on a lanthanide-transition heterometallic metal–organic framework (MOF) is first designed for specific detection of urinary thiodiglycolic acid (TDGA) which is the biomarker of carcinogenic vinyl chloride monomer (VCM) and represents the internal dose of human exposure to VCM. The nanoprobe demonstrates high selectivity to TDGA with about 27.5-fold luminescence enhancement. It also displays excellent sensitivity with a detection limit as low as 89 ng·mL–1 and fast response to TDGA within 4 min, while refraining from the interference of other coexisting species in urine. Such good sensing performance enables the nanoprobe to practically monitor TDGA levels in human urine. Moreover, a portable urine dipstick based on the sensor is developed to conveniently evaluate individuals’ intoxication degree of VCM. This fast, sensitive, and selective nanoprobe has promising potential to be a useful tool for point-of-care diagnosis of disease associated with VCM exposure.

Xiao-Yu Xu

Papers

A Double‐Stimuli‐Responsive Fluorescent Center for Monitoring of Food Spoilage based on Dye Covalently Modified EuMOFs: From Sensory Hydrogels to Logic Devices

Functionalization of Metal–Organic Frameworks for Photoactive Materials

Eu3+ functionalized Sc-MOFs: Turn-on fluorescent switch for ppb-level biomarker of plastic pollutant polystyrene in serum and urine and on-site detection by smartphone

Wearable glove sensor for non-invasive organophosphorus pesticide detection based on a double-signal fluorescence strategy

A Luminescent 3d-4f-4d MOF Nanoprobe as a Diagnosis Platform for Human Occupational Exposure to Vinyl Chloride Carcinogen