Jenny Schneider,*,† Masaya Matsuoka,‡ Masato Takeuchi,‡ Jinlong Zhang, Yu Horiuchi,‡ Masakazu Anpo,‡ and Detlef W. Bahnemann*,† †Institut fur Technische Chemie, Leibniz Universitaẗ Hannover, Callinstrasse 3, D-30167 Hannover, Germany ‡Faculty of Engineering, Osaka Prefecture University, 1 Gakuen-cho, Sakai Osaka 599-8531, Japan Key Lab for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237, China

Understanding TiO2 photocatalysis: mechanisms and materials.

Metal–organic frameworks (MOFs), also known as porous coordination polymers (PCPs), synthesized by assembling metal ions with organic ligands have recently emerged as a new class of crystalline porous materials. The amenability to design as well as fine-tunable and uniform pore structures makes them promising materials for a variety of applications. Controllable integration of MOFs and functional materials is leading to the creation of new multifunctional composites/hybrids, which exhibit new properties that are superior to those of the individual components through the collective behavior of the functional units. This is a rapidly developing interdisciplinary research area. This review provides an overview of the significant advances in the development of diverse MOF composites reported till now with special emphases on the synergistic effects and applications of the composites. The most widely used and successful strategies for composite synthesis are also presented.

Metal–organic framework composites

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Bronsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications.

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

Metal–organic frameworks (MOFs), established as a relatively new class of crystalline porous materials with high surface area, structural diversity, and tailorability, attract extensive interest and exhibit a variety of applications, especially in catalysis. Their permanent porosity enables their inherent superiority in confining guest species, particularly small metal nanoparticles (MNPs), for improved catalytic performance and/or the expansion of reaction scope. This is a rapidly developing interdisciplinary research field. In this review, we provide an overview of significant progress in the development of MNP/MOF composites, including various preparation strategies and characterization methods as well as catalytic applications. Special emphasis is placed on synergistic effects between the two components that result in an enhanced performance in heterogeneous catalysis. Finally, the prospects of MNP/MOF composites in catalysis and remaining issues in this field have been indicated.

Metal–organic frameworks meet metal nanoparticles: synergistic effect for enhanced catalysis

The present article describes the hydrogen production from an aqueous medium over amino-functionalized Ti(IV) metal–organic framework (Ti-MOF-NH2) under visible-light irradiation. Ti-MOF-NH2, which employs 2-amino-benzenedicarboxylic acid as an organic linker, has been synthesized by a facile solvothermal method. Pt nanoparticles as cocatalysts are then deposited onto Ti-MOF-NH2 via a photodeposition process (Pt/Ti-MOF-NH2). The XRD and N2 adsorption measurements reveal the successful formation of a MOF framework structure and its remaining structure after deposition of Pt nanoparticles. The observable visible-light absorption up to ∼500 nm can be seen in the DRUV–vis spectrum of Ti-MOF-NH2, which is associated with the chromophore in the organic linker. Ti-MOF-NH2 and Pt/Ti-MOF-NH2 exhibit efficient photocatalytic activities for hydrogen production from an aqueous solution containing triethanolamine as a sacrificial electron donor under visible-light irradiation. The longest wavelength available for the ...

Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework

Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst

https://www.rsc.org/suppdata/cc/c4/c4cc02397h/c4cc02397h1.pdf

Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation

The present article deals with Pt complex construction within Zr-based MOF having bipyridine units in the framework (Zr-MOF-bpy-PtCl2) and its photocatalytic activity for hydrogen production under visible-light irradiation (λ > 420 nm). Zr-MOF-bpy-PtCl2 is prepared by the construction of a Zr-based MOF using 2,2′-bipyridine-5,5′-dicarboxylic acid (Zr-MOF-bpy), and subsequent complexation reaction with K2PtCl4. XRD and N2 adsorption–desorption measurements have revealed that both Zr-MOF-bpy and Zr-MOF-bpy-PtCl2 have a UiO-type structure. From the results of UV–Vis and XAFS measurements, the incorporated Pt species has been proven to be in square planar geometry involving two N atoms and two Cl atoms as a result of the Pt coordination with bipyridine units in the framework. Zr-MOF-bpy-PtCl2 has been employed for a hydrogen production reaction from water containing a sacrificial electron donor under visible-light irradiation (λ > 420 nm). Zr-MOF-bpy-PtCl2 realizes steady hydrogen production, and the amount of evolved hydrogen reaches 8.3 μmol after the 9 h reaction period, while Zr-MOF-bpy exhibits no photocatalytic activity under the same conditions. It has also been found that the activity of Zr-MOF-bpy-PtCl2 is superior to that of the corresponding homogeneous complex analogue (bpy)PtCl2.

Construction of Pt complex within Zr-based MOF and its application for hydrogen production under visible-light irradiation

Disclosed is an electrode catalyst for fuel cells, which uses a polynuclear complex, wherein a ligand having 5-15 coordinating atoms in a molecule is coordinated to 2-4 transition metal atoms, or a mononuclear metal complex, which contains an organic compound having two or more phenol rings and three or more aromatic heterocyclic rings as a ligand.

Masatoshi Iwata

Papers

Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework

Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst

Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation

Construction of Pt complex within Zr-based MOF and its application for hydrogen production under visible-light irradiation

Electrode catalyst for fuel cell