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 world's natural resources, particularly the scarcest of them. Chemistry's 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.

Simultaneous microfabrication and tuning of the permselective properties in microporous polymers using X-ray lithography.

Microchannels are fabricated using a photosensitive polymer to which microporosity is tuned with different X-ray doses. Using hard X-ray irradiation, the micropattern is positioned with various geometries in a multi-level, three-dimensional structure, while controlling the pore size and transport properties of small molecules. This highly reliable fabrication process has potential for use in microfluidic devices with enhanced transport properties through microchannels.

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.

Engineering the refractive index of three-dimensional photonic crystals through multilayer deposition of CdS films.

Woodpile photonic crystals are amongst the preferred candidates for the next generation of photonics components. However, the photocurable resists used to produce them still lack the optical properties (high-n, non-linearity) suitable for photonics applications. A chemical bath deposition protocol has been adapted to deposit high-n/non-linear chalcogenide CdS on the surface of Ormocer woodpiles. The deposition parameters have been adjusted to obtain heterogeneous growth of CdS layers on the Ormocer surface. The layers shift the photonic band-gap and increase its amplitude by more than 15%. Software simulation confirmed that the woodpile effective refractive index underwent an excess of 30% increase.

Three-dimensional hybrid photonic crystals merged with localized plasmon resonances.

Localized plasmon resonances are proposed in a new concept of 3D photonic crystals stacked by hybrid rods made of dielectric-cores and metallic-nanoshells. The resonant plasmon coupling of inner and outer surfaces of the metallic-nanoshells forms the localized plasmon resonances which can be flexibly tuned by mediating the dielectric cores. At the resonance wavelengths, the strong electromagnetic wave-plasmon interaction leads to the enhancement in the structural absorption by more than 20 times. The tunability of the enhanced absorption is demonstrated in experiments.

Patterning of sol-gel hybrid organic-inorganic film doped with luminescent semiconductor quantum dots.

Two different sol-gel hybrid organic-inorganic films doped with luminescent CdS or PbS quantum dots (QDs) have been successfully synthesized and patterned using nanolithographic techniques. The feasibility of applying X-ray lithography and RIE to pattern hybrid materials doped with highly luminescent nanoparticles has been demonstrated for GPTMS-GeO2 (G-GeO2) and MPTMS-ZrO2 (M-ZrO2) hybrids obtained form 3-glycidoxypropyltrymethoxysilane (GPTMS), methacryloxy-propil-trimethoxysilane (MPTMS), germanium ethoxide and zirconium propoxide. Semiconductor doped film have been obtained by mixing ZrO2-SiO2 or GeO2-SiO2 sol-gel hybrid organic-inorganic matrix solution with CdS or PbS colloidal doping solution to obtain up to 20% molar concentration of QDs inside the films. Patterns consisting of pillars with different aspect ratio have been obtained by X-ray lithography and reactive ion etching (RIE). Structural and optical characterization of films before and after the lithographic process pointed out that both matrices and QDs retain their original properties without been affected by X-rays irradiation and RIE in the conditions here described.

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.

Rapid detection of hendra virus using magnetic particles and quantum dots.

A proof-of-concept for the development of a fast and portable Hendra virus biosensor is presented. Hendra virus, a deadly emerging pathogen in Australia, can be co-localized, concentrated and revealed using simultaneously magnetic and luminescent functional particles. This method should be applicable for the early detection of any other virus by targeting the specific virus with the corresponding antibody.

Chemical tailoring of hybrid sol-gel thick coatings as hosting matrix for functional patterned microstructures.

A phenyl-based hybrid organic - inorganic coating has been synthesized and processed by hard X-ray lithography. The overall lithography process is performed in a two-step process only (X-rays exposure and chemical etching). The patterns present high aspect ratio, sharp edges, and high homogeneity. The coating has been doped with a variety of polycyclic aromatic hydrocarbon functional molecules, such as anthracene, pentacene, and fullerene. For the first time, hard X-rays have been combined with thick hybrid functional coatings, using the sol-gel thick film directly as resist. A new technique based on a new material combined with hard X-rays is now available to fabricate optical devices. The effect due to the high-energy photon exposure has been investigated using FT-IR and Raman spectroscopy, laser scanner, optical profilometer, and confocal and electron microscope. High-quality thick hybrid fullerene-doped microstructures have been fabricated.

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.