Facile Synthesis of Metal-Loaded Porous Carbon Thin Films via Carbonization of Surface-Mounted Metal-Organic Frameworks.

We report a facile approach to prepare metal-nanocatalyst-incorporated carbon thin films with uniform size distribution via carbonization of surface-mounted metal-organic frameworks (SURMOFs) and metal oxo-clusters loaded SURMOF. The calcinated thin films have high performance of methylene blue degradation and the reduction of nitrobenzene. This study describes a general strategy for preparing various nanoparticle-impregnated porous carbon thin films for applications in catalysis.

Epitaxial Growth of MOF Thin Film for Modifying the Dielectric Layer in Organic Field-Effect Transistors.

Metal-organic framework (MOF) thin films are important in the application of sensors and devices. However, the application of MOF thin films in organic field effect transistors (OFETs) is still a challenge to date. Here, we first use the MOF thin film prepared by a liquid-phase epitaxial (LPE) approach (also called SURMOFs) to modify the SiO2 dielectric layer in the OFETs. After the semiconductive polymer of PTB7-Th (poly[4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)benzo[1,2-b:4,5-b']dithiophene-co-3-fluorothieno[3,4-b]thiophene-2-carboxylate]) was coated on MOF/SiO2 and two electrodes on the semiconducting film were deposited sequentially, MOF-based OFETs were fabricated successfully. By controlling the LPE cycles of SURMOF HKUST-1 (also named Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate), the performance of the HKUST-1/SiO2-based OFETs showed high charge mobility and low threshold voltage. This first report on the application of MOF thin film in OFETs will offer an effective approach for designing a new kind of materials for the OFET application.

Surface-mounted MOF templated fabrication of homochiral polymer thin film for enantioselective adsorption of drugs.

A self-polymerized chiral monomer 3,4-dihydroxy-l-phenylalanine (l-DOPA) has been introduced into the pores of an achiral surface-mounted metal organic framework (SURMOF), and then the homochiral poly(l-DOPA) thin film has been successfully formed after UV light irradiation and etching of the SURMOF. Remarkably, such a poly(l-DOPA) thin film exhibited enantioselective adsorption of naproxen. This study opened a SURMOF-templated approach for preparing porous polymer thin films.

A Confined Fabrication of Perovskite Quantum Dots in Oriented MOF Thin Film.

Organic-inorganic hybrid lead organohalide perovskites are inexpensive materials for high-efficiency photovoltaic solar cells, optical properties, and superior electrical conductivity. However, the fabrication of their quantum dots (QDs) with uniform ultrasmall particles is still a challenge. Here we use oriented microporous metal-organic framework (MOF) thin film prepared by liquid phase epitaxy approach as a template for CH3NH3PbI2X (X = Cl, Br, and I) perovskite QDs fabrication. By introducing the PbI2 and CH3NH3X (MAX) precursors into MOF HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzene tricarboxylate) thin film in a stepwise approach, the resulting perovskite MAPbI2X (X = Cl, Br, and I) QDs with uniform diameters of 1.5-2 nm match the pore size of HKUST-1. Furthermore, the photoluminescent properties and stability in the moist air of the perovskite QDs loaded HKUST-1 thin film were studied. This confined fabrication strategy demonstrates that the perovskite QDs loaded MOF thin film will be insensitive to air exposure and offers a novel means of confining the uniform size of the similar perovskite QDs according to the oriented porous MOF materials.

Chiral Chemistry of Homochiral Porous Thin Film with Different Growth Orientations.

Chirality is one of the essential features in our living life and exerts a wide variety of applications in enantio-adsorption/separation. However, the mechanism between chirality and enantio-adsorption/separation is very significant in homochiral porous materials; in particular, the understanding of the relationship between crystalline orientations and chiral behavior is a challenging but important mechanism. In this work, homochiral porous crystalline metal organic framework (MOF) materials were grown on hydroxyl- and carboxyl-functionalized substrates, resulting in homochiral porous thin films with different orientations. The enantioselectivity and adsorption rates in two different oriented homochiral porous thin films were studied by using gas-phase quartz crystal microbalance (QCM) experiment of chiral probe molecules. The different mass uptake and time constant showed that the chiral behavior can be obviously influenced by the crystalline orientations on the same homochiral porous thin films. This study will not only offer a good model to understand the mechanism of chiral behavior in homochiral porous materials but also provide guidance for developing new homochiral-oriented porous thin films with high enantioselectivity or enantioseparation.

Liquid-phase epitaxial growth of a homochiral MOF thin film on poly(L-DOPA) functionalized substrate for improved enantiomer separation.

A homochiral MOF film grown on a functionalized substrate in a capillary column with high orientation and homogeneity was successfully prepared by using a layer-by-layer liquid phase epitaxial method; by introducing self-polymerized 3,4-dihydroxy-L-phenylalanine (poly(L-DOPA)) as a chiral substrate, the obtained enantiopure substrate mounted homochiral MOF thin film showed improved enantiomer separation.

Chiral Porous Metacrystals: Employing Liquid-Phase Epitaxy to Assemble Enantiopure Metal-Organic Nanoclusters into Molecular Framework Pores.

We describe the fabrication of hybrid yet well-ordered porous nanoparticle (NP) arrays with full three-dimensional periodicity by embedding nanometer-sized metal-organic clusters (MOCs) into metal-organic frameworks (MOFs). Although conventional NP@MOF encapsulation procedures failed for these fairly large (1.66 nm diameter) NPs, we achieved maximum loading efficiency (one NP per pore) by using a modified liquid phase epitaxy (LPE) layer-by-layer approach to grow and load the MOF. The preformed NPs, homochiral Ti4(OH)4(R/S-BINOL)6 clusters (Ti-MOC, BINOL = 1,1'-bi-2-naphthol), formed a regular lattice inside the pores of an achiral HKUST-1 (or Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) MOF thin film. Exposure to the different enantiomers of methyl lactate revealed that the NP@MOF metacrystal is quite efficient regarding enantiomer recognition and separation. The approach presented here is also suited for other MOF types and expected to provide a substantial stimulus for the fabrication of metacrystals, crystalline solids made from nanoparticles instead of atoms.

Liquid-Phase Epitaxy Effective Encapsulation of Lanthanide Coordination Compounds into MOF Film with Homogeneous and Tunable White-Light Emission.

As a new family of hybrid inorganic-organic materials with large porosity, metal-organic frameworks (MOFs) have received attractive attention recently on encapsulating functional guest species. Although the encapsulation of luminescent guest into bulk MOFs can tune the luminescent property, the powder composite materials are limited to the application in optical sensors and devices. In the present work, we use a modified liquid-phase epitaxial (LPE) pump method for the fabrication of lanthanide coordination compounds (LCCs)-encapsulated MOF thin film on substrate with high encapsulation efficiency. The resultant composite film reveals an oriented and homogeneous composite film, in which a white light emission by tuning the LCCs of red, blue and green emission can be obtained. This strategy may open new perspectives for developing high-encapsulation-efficiency, oriented, and homogeneous solid-state lighting composite films in the application of optical sensors and devices.