Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Ju Mei,†,‡,∥ Nelson L. C. Leung,†,‡,∥ Ryan T. K. Kwok,†,‡ Jacky W. Y. Lam,†,‡ and Ben Zhong Tang*,†,‡,§ †HKUST-Shenzhen Research Institute, Hi-Tech Park, Nanshan, Shenzhen 518057, China ‡Department of Chemistry, HKUST Jockey Club Institute for Advanced Study, Institute of Molecular Functional Materials, Division of Biomedical Engineering, State Key Laboratory of Molecular Neuroscience, Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China Guangdong Innovative Research Team, SCUT-HKUST Joint Research Laboratory, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China

Aggregation-Induced Emission: Together We Shine, United We Soar!

Metal–organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas A very interesting and well-investigated topic is their optical emission properties and related applications Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011 This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection

Luminescent metal–organic frameworks for chemical sensing and explosive detection

Over the past few decades, researchers have established artificial enzymes as highly stable and low-cost alternatives to natural enzymes in a wide range of applications. A variety of materials including cyclodextrins, metal complexes, porphyrins, polymers, dendrimers and biomolecules have been extensively explored to mimic the structures and functions of naturally occurring enzymes. Recently, some nanomaterials have been found to exhibit unexpected enzyme-like activities, and great advances have been made in this area due to the tremendous progress in nano-research and the unique characteristics of nanomaterials. To highlight the progress in the field of nanomaterial-based artificial enzymes (nanozymes), this review discusses various nanomaterials that have been explored to mimic different kinds of enzymes. We cover their kinetics, mechanisms and applications in numerous fields, from biosensing and immunoassays, to stem cell growth and pollutant removal. We also summarize several approaches to tune the activities of nanozymes. Finally, we make comparisons between nanozymes and other catalytic materials (other artificial enzymes, natural enzymes, organic catalysts and nanomaterial-based catalysts) and address the current challenges and future directions (302 references).

Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes

This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis

A facile preparation of a mesoporous Cr-MOF, PCN-333(Cr) with functional group, has been demonstrated through a dual exchange strategy, involving a sequential ligand exchange and metal metathesis process. After optimization of the exchange system, the functionalized PCN-333(Cr), N3–PCN-333(Cr) shows well maintained crystallinity, porosity, as well as much improved chemical stability. Because of the exceptionally large pores (∼5.5 nm) in PCN-333(Cr), a secondary functional moiety, Zn-TEPP with a size of 18 A × 18 A, has been successfully clicked into the framework. In this article, we have also analyzed kinetics and thermodynamics during dual exchange process, showing our attempts to interpret the exchange event in the PCN-333. Our findings not only provide a highly stable mesoporous Cr-MOF platform for expanding MOF-based applications, but also suggest a route to functionalized Cr-MOF which may have not been achievable through conventional approaches.

Dual Exchange in PCN-333: A Facile Strategy to Chemically Robust Mesoporous Chromium Metal-Organic Framework with Functional Groups.

The escalating atmospheric CO2 concentration is one of the most urgent environmental concerns of our age. To effectively capture CO2, various materials have been studied. Among them, alkylamine-modified metal–organic frameworks (MOFs) are considered to be promising candidates. In most cases, alkylamine molecules are integrated into MOFs through the coordination bonds formed between open metal sites (OMSs) and amine groups. Thus, the alkylamine density, as well as the corresponding CO2 uptake in MOFs, are severely restricted by the density of OMSs. To overcome this limit, other approaches to incorporating alkylamine into MOFs are highly desired. We have developed a new method based on Bronsted acid–base reaction to tether alkylamines into Cr-MIL-101-SO3H for CO2 capture. A systematic optimization of the amine tethering process was also conducted to maximize the CO2 uptake of the modified MOF. Under the optimal amine tethering condition, the obtained tris(2-aminoethyl)amine-functionalized Cr-MIL-101-SO3H (Cr-MIL-101-SO3H-TAEA) has a cyclic CO2 uptake of 2.28 mmol g−1 at 150 mbar and 40 °C, and 1.12 mmol g−1 at 0.4 mbar and 20 °C. The low-cost starting materials and simple synthetic procedure for the preparation of Cr-MIL-101-SO3H-TAEA suggest that it has the potential for large-scale production and practical applications.

Incorporation of Alkylamine into Metal–Organic Frameworks through a Brønsted Acid–Base Reaction for CO2 Capture

Three-dimensional hierarchical porous carbon materials with flower-like superstructures are of great interest for energy applications since their unique shape not only provides high accessible surface area and consequently more exposed active sites but also facilitates ion transport for high-rate capability. However, finding a controllable way to make porous carbons with such specific shapes has been challenging. Herein, we report a tunable and simple method for one-pot synthesis of polyacrylonitrile and its copolymer nanostructured particles with various superstructures (flower, pompom, hairy leave, and petal shapes) controlled by employing various solvents or by the incorporation of different co-monomers. The correlation between polymer particle shapes and solvent properties has been identified through Hansen solubility parameters analysis. The obtained uniform polyacrylonitrile particles could be readily converted into porous carbons by high-temperature gas treatment while maintaining the original shap...

Highly Tunable and Facile Synthesis of Uniform Carbon Flower Particles

A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications.

Structure-Assisted Functional Anchor Implantation in Robust Metal–Organic Frameworks with Ultralarge Pores

Kinetic labilization of the Fe(III)–O coordination bond in a mesoporous metal–organic framework, PCN-333-Fe(III), is realized by the reduction of Fe(III) by Cr(II). The Fe(II)–Cr(II) metathesis is thus completely achieved followed by this reductive labilization process that generates PCN-333-Cr(III). The kinetic inertness of Cr(III) provides PCN-333-Cr(III) with enhanced chemical stability as well as a broader range of applications compared to those of PCN-333-Fe(III). For instance, alkylamine incorporated PCN-333-Cr(III) demonstrated significant carbon dioxide uptake while PCN-333-Fe(III) lost its crystallinity after alkylamine treatment.

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Dawei Feng

Papers

Dual Exchange in PCN-333: A Facile Strategy to Chemically Robust Mesoporous Chromium Metal-Organic Framework with Functional Groups.

Incorporation of Alkylamine into Metal–Organic Frameworks through a Brønsted Acid–Base Reaction for CO2 Capture

Highly Tunable and Facile Synthesis of Uniform Carbon Flower Particles

Structure-Assisted Functional Anchor Implantation in Robust Metal–Organic Frameworks with Ultralarge Pores

The preparation of an ultrastable mesoporous Cr(III)-MOF via reductive labilization