Metal–organic frameworks (MOFs) are porous crystalline materials constructed from metal ions or clusters and multidentate organic ligands. Recently, the use of MOFs or MOF composites as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention due to their tunable open metal centres, functional organic linkers, and active guest species in their pores. In this review, the applications of MOFs with multiple active sites in synergistic organic catalysis, photocatalysis and tandem reactions are discussed. These multifunctional MOFs can be categorized by the type of active centre as follows: (i) open metal centres and functional organic linkers in the MOF structure, (ii) active guest sites in the pores and active sites in the MOF structure, and (iii) bimetallic nanoparticles (NPs) on MOF supports. The types of synergistic catalysis and tandem reactions promoted by multifunctional MOFs and their proposed mechanisms are presented in detail. Here, catalytic MOFs with a single type of active site and MOFs that only serve as supports to enhance substrate adsorption are not discussed.

Multifunctional metal–organic framework catalysts: synergistic catalysis and tandem reactions

Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions.

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Metal–organic and covalent organic frameworks as single-site catalysts

The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ev...

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

Even though Fe-N/C electrocatalysts with abundant Fe-Nx active sites have been developed as one of the most promising alternatives to precious metal materials for oxygen reduction reaction (ORR), further improvement of their performance requires precise control over Fe-Nx sites at the molecular level and deep understanding of the catalytic mechanism associated with each particular structure. Herein, we report a host–guest chemistry strategy to construct Fe-mIm nanocluster (NC) (guest)@zeolite imidazole framework-8 (ZIF-8) (host) precursors that can be transformed into Fe-N/C electrocatalysts with controllable structures. The ZIF-8 host network exhibits a significant host–guest relationship dependent confinement effect for the Fe-mIm NCs during the pyrolysis process, resulting in different types of Fe-Nx sites with two- to five-coordinated configurations on the porous carbon matrix confirmed by X-ray absorption near edge structure (XANES) and Fourier transform (FT) extended X-ray absorption fine structure ...

Metal–Organic-Framework-Derived Fe-N/C Electrocatalyst with Five-Coordinated Fe-Nx Sites for Advanced Oxygen Reduction in Acid Media

Mixed-metal MOFs are metal–organic frameworks that contain at least 2 different metal ions as nodes of their frameworks. They are prepared relatively easily by either a one-pot synthesis with a synthesis mixture containing the different metals, or by a post-synthetic ion-exchange method by soaking a monometallic MOF in a concentrated solution of a different (but compatible) metal-ion. More difficult is the accurate characterization of these materials. Is the formed product a mixture of monometallic MOFs or indeed a MOF with different metallic nodes? Are the metals randomly distributed or do they form domains? What is the oxidation state of the metals? How do the metals mutually influence each other, and impact the material's performance? Advanced characterization techniques are required e.g. X-ray absorption spectroscopy, magnetic resonance and electron microscopy. Computational tools at multiple scales are also often applied. In almost every case, a judicious choice of several techniques is required to unambiguously characterize the mixed-metal MOF. Although still in their infancy, several applications are emerging for mixed-metal MOFs, that improve on conventional monometallic MOFs. In the field of gas sorption and storage, especially the stability and affinity towards the target gases can be largely improved by introducing a second metal ion. In the case of flexible MOFs, the breathing behavior, and in particular the pressure at which the MOF opens, can be tailored. In heterogeneous catalysis, new cascade and tandem reactions become possible, with particular focus on reactions where the two metals in close proximity truly form a mixed-metal transition state. The bimetallic MOF should have a clear benefit over a mixture of the respective monometallic MOFs, and bimetallic enzymes can be a huge source of inspiration in this field. Another very promising application lies in the fields of luminescence and sensing. By tuning the lanthanide metals in mixed-metal lanthanide MOFs and by using the organic linkers as antennae, novel smart materials can be developed, acting as sensors and as thermochromic thermometers. Of course there are also still open challenges, as also mixed-metal MOFs do not escape the typical drawbacks of MOFs, such as low stability in moisture and possible metal leaching in liquids. The ease of synthesis of mixed-metal MOFs is a large bonus. In this critical review, we discuss in detail the synthesis, characterization, computational work and applications of mixed-metal MOFs.

https://hal.archives-ouvertes.fr/hal-02307092/document

Mixed-metal metal-organic frameworks.

We report here a simple method for controlling the crystal size and morphology of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in methanol solution. ZIF-8 crystals were prepared by mixing 2-methylimidazole (Hmim) with various zinc salts for 1 h and using a Hmim/Zn(+2) salt molar ratio of 8/1. All products prepared were assigned to a sodalite-type structure and both particle size and morphology were found to be dependent on the reactivity of the Zn(+2) salt. Small ZIF-8 crystals with diameters varying between ca. 50 and 200 nm were obtained with reactive zinc salts like Zn(acac)2, Zn(NO3)2, ZnSO4 or Zn(ClO4)2 as demonstrated by SEM, TEM and DLS analyses. The use of ZnCl2, Zn(OAc)2 or ZnI2 afforded crystals with sizes varying between ca. 350 and 650 nm. Finally, the low reactive ZnBr2 salt was found to generate microsized crystals. Taking ZIF-8 crystals prepared from Zn(NO3)2, Zn(OAc)2 and ZnBr2 as representatives and through thermogravimetric analysis and BET measurements, we also demonstrated that changes in particle size induced changes in stability and adsorption properties. The small sized ZIF-8 crystals produced from Zn(NO3)2 were found to exhibit the highest surface area (1700 m2 g−1) and the best catalytic activity in Knoevenagel and Friedlander reactions.

Controlling ZIF-8 nano- and microcrystal formation and reactivity through zinc salt variations

Cu2+-doped zeolitic imidazolate frameworks (ZIF-8): efficient and stable catalysts for cycloadditions and condensation reactions

A simple methodology for encapsulating ca. 10 nm-sized superparamagnetic Fe3O4 nanoparticles in zeolitic imidazolate frameworks (ZIF-8) crystals was developed. The corresponding Fe3O4@ZIF-8 heterostructured material exhibits bifunctional properties with both high magnetization (Fe3O4) and high thermal stability, large specific surface, and catalytic properties (ZIF-8). The Fe3O4@ZIF-8 catalyst exhibits fair separation ability and reusability, which can be repeatedly applied for Knoevenagel condensations and Huisgen cycloadditions for at least ten successive cycles.

Fe3O4@ZIF-8: magnetically recoverable catalysts by loading Fe3O4 nanoparticles inside a zinc imidazolate framework.

In this paper, we report on a continuous-flow microreactor process to prepare ZnO quantum dots (QDs) with widely tunable particle size and photoluminescence emission wavelengths. X-ray diffraction, electron diffraction, UV–vis, photoluminescence and transmission electron microscopy measurements were used to characterize the synthesized ZnO QDs. By varying operating conditions (temperature, flow rate) or the capping ligand, ZnO QDs with diameters ranging from 3.6 to 5.2 nm and fluorescence maxima from 500 to 560 nm were prepared. Results obtained show that low reaction temperatures (20 or 35 °C), high flow rates and the use of propionic acid as a stabilizing agent are favorable for the production of ZnO QDs with high photoluminescence quantum yields (up to 30%).

https://iopscience.iop.org/article/10.1088/0957-4484/25/14/145606/pdf

Size-controlled synthesis of ZnO quantum dots in microreactors.

In this work, we developed a new process to covalently graft a thermoresponsive polymer on the surface of fluorescent nanocrystals in order to synthesize materials that combine both responsive and fluorescent properties. For the first time, poly(N-isopropylacrylamide) (PNIPAM) was grown by activator regenerated by electron transfer-atom transfer radical polymerization (ARGET-ATRP) from ZnO quantum dots (QDs) by surface-initiated polymerization. This process allowed the formation of fluorescent and responsive ZnO/PNIPAM core/shell QDs while only requiring the use of a ppm amount of copper for the synthesis. The influence of the nature of the silanized layer and the polymerization time on the properties of the final nanomaterials were investigated. Results clearly evidence that both the PNIPAM layer thickness and the temperature affected the luminescence properties of the core/shell nanoparticles, but also that the PNIPAM layer, when it is thick enough, could stabilize the QDs' optical properties.

http://iopscience.iop.org/article/10.1088/0957-4484/26/33/335605/pdf

Aleksandra Schejn

Papers

Controlling ZIF-8 nano- and microcrystal formation and reactivity through zinc salt variations

Cu2+-doped zeolitic imidazolate frameworks (ZIF-8): efficient and stable catalysts for cycloadditions and condensation reactions

Fe3O4@ZIF-8: magnetically recoverable catalysts by loading Fe3O4 nanoparticles inside a zinc imidazolate framework.

Size-controlled synthesis of ZnO quantum dots in microreactors.

Thermo-responsive and aqueous dispersible ZnO/PNIPAM core/shell nanoparticles