Paolo Falcaro

Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules.

Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

Using Functional Nano- and Microparticles for the Preparation of Metal–Organic Framework Composites with Novel Properties

A critical materials challenge over the next quarter century is the sustainable use and management of the worlds natural resources, particularly the scarcest of them. Chemistrys ability to get more from less is epitomized by porous coordination polymers, also known as metal-organic frameworks (MOFs), which use a minimum amount of material to build maximum surface areas with fine control over pore size. Their large specific surface area and tunable porosity make MOFs useful for applications including small-molecule sensing, separation, catalysis, and storage and release of molecules of interest. Proof-of-concept projects have demonstrated their potential for environmental applications such as carbon separation and capture, water purification, carcinogen sequestration, byproduct separation, and resource recovery. To translate these from the laboratory into devices for actual use, however, will require synthesis of MOFs with new functionality and structure. This Account summarizes recent progress in the use of nano- and microparticles to control the function, location, and 3D structure of MOFs during MOF self-assembly, creating novel, hybrid, multifunctional, ultraporous materials as a first step towards creating MOF-based devices. The use of preformed ceramic, metallic, semiconductive, or polymeric particles allows the particle preparation process to be completely independent of the MOF synthesis, incorporating nucleating, luminescent, magnetic, catalytic, or templating particles into the MOF structure. We discuss success in combining functional nanoparticles and porous crystals for applications including molecular sieve detectors, repositionable and highly sensitive sensors, pollutant-sequestering materials, microfluidic microcarriers, drug-delivery materials, separators, and size-selective catalysts. In sections within the Account, we describe how functional particles can be used for (1) heterogeneous nucleation (seeding) of MOFs, (2) preparation of framework composites with novel properties, (3) MOF positioning on a substrate (patterning), and (4) synthesis of MOFs with novel architectures.

A new method to position and functionalize metal-organic framework crystals

With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications.

Applications of magnetic metal–organic framework composites

The high and regular porosity of metal–organic frameworks (MOFs) provides exceptional properties suitable for technological applications. The increasing interest of the scientific community is based on the exploration of these advantageous properties for industrial applications. Pure MOFs are specifically designed to offer a huge surface area; such a high specific surface area has been explored and exploited for gas storage, separation, or catalysis in a variety of chemical processes. A different and promising scientific trend aims to combine MOFs with extrinsic functionalities such as functional nanoparticles; this strategy enables the preparation of new nanocomposite materials with unprecedented properties. An interesting case is offered by the synergic combination of magnetic particles with MOF crystals. In the resulting nanocomposite material, the adaptive functional responses can be triggered by an external magnetic field. In this context, different protocols have been developed for the efficient preparation of magnetic framework composites (MFCs), a class of materials that combines magnetic nano- or micro-particles with MOFs crystals. This application paper highlights the progress on MFCs for drug delivery, environmental control, catalysis, sensing and miniaturized device fabrication.

Chemical vapour deposition of zeolitic imidazolate framework thin films

Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials.

Doping Light Emitters into Metal–Organic Frameworks

Space division with red cubes: Doping metal-organic frameworks with another metal component gives a further opportunity to tune their properties. Recent work successfully introduced europium into the inorganic nodes of frameworks. Although the doping element does not affect the framework topology, highly improved emissive performance was measured thanks to the intrinsic red emission of europium.

Patterning Techniques for Metal Organic Frameworks

The tuneable pore size and architecture, chemical properties and functionalization make metal organic frameworks (MOFs) attractive versatile stimuli-responsive materials. In this context, MOFs hold promise for industrial applications and a fervent research field is currently investigating MOF properties for device fabrication. Although the material properties have a crucial role, the ability to precisely locate the functional material is fundamental for device fabrication. In this progress report, advancements in the control of MOF positioning and precise localization of functional materials within MOF crystals are presented. Advantages and limitations of each reviewed technique are critically investigated, and several important gaps in the technological development for device fabrication are highlighted. Finally, promising patterning techniques are presented which are inspired by previous studies in organic and inorganic crystal patterning for the future of MOF lithography.

Highly Luminescent Metal–Organic Frameworks Through Quantum Dot Doping

The incorporation of highly luminescent core-shell quantum dots (QDs) within a metal-organic framework (MOF) is achieved through a one-pot method. Through appropriate surface functionalization, the QDs are solubilized within MOF-5 growth media. This permits the incorporation of the QDs within the evolving framework during the reaction. The resulting QD@MOF-5 composites are characterized using X-ray fluorescence, cross-sectional confocal microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and small-angle X-ray scattering. The synergistic combination of luminescent QDs and the controlled porosity of MOF-5 in the QD@MOF-5 composites is harnessed within a prototype molecular sensor that can discriminate on the basis of molecular size.

Humidity sensors based on mesoporous silica thin films synthesised by block copolymers

Abstract The application of mesostructured thin films to fabricate electrochemical sensors requires the control of dimension, shape and distribution of pores in the material. Silica mesoporous thin films were deposited via dip coating on silicon and alumina substrates with interdigitated electrodes. Mesostructured films were obtained by sol-gel self-assembled process using di-block, tri-block or star-block copolymers: 2-D hexagonal mesoporous phases in silica were formed. After deposition the films were calcined in air to remove the surfactant and were characterised by Fourier transform infrared spectroscopy and low angle X-ray diffraction. Current variations with relative humidity were measured using different applied d.c. voltage; I/V characteristics were performed at various relative humidity values. Moreover the dependence of response from temperature and behaviour during cyclic test in dry–wet conditions was studied. The electrical response was found to be dependent on dimension of pores and their surface. Electrical characterisation upon exposure to humidity shows that the mesoporous structure is easily accessible by external environment, and the films prepared by non-ionic surfactants exhibit good performances in comparison with commercial humidity sensors.

Combining UV Lithography and an Imprinting Technique for Patterning Metal‐Organic Frameworks

Thin metal-organic framework (MOF) films are patterned using UV lithography and an imprinting technique. A UV lithographed SU-8 film is imprinted onto a film of MOF powder forming a 2D MOF patterned film. This straightforward method can be applied to most MOF materials, is versatile, cheap, and potentially useful for commercial applications such as lab-on-a-chip type devices.