Christopher J. Oldham

Facile Conversion of Hydroxy Double Salts to Metal–Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates

Rapid room-temperature synthesis of metal-organic frameworks (MOFs) is highly desired for industrial implementation and commercialization. Here we find that a (Zn,Cu) hydroxy double salt (HDS) intermediate formed in situ from ZnO particles or thin films enables rapid growth (<1 min) of HKUST-1 (Cu3(BTC)2) at room temperature. The space-time-yield reaches >3 × 10(4) kg·m(-3)·d(-1), at least 1 order of magnitude greater than any prior report. The high anion exchange rate of (Zn,Cu) hydroxy nitrate HDS drives the ultrafast MOF formation. Similarly, we obtained Cu-BDC, ZIF-8, and IRMOF-3 structures from HDSs, demonstrating synthetic generality. Using ZnO thin films deposited via atomic layer deposition, MOF patterns are obtained on pre-patterned surfaces, and dense HKUST-1 coatings are grown onto various form factors, including polymer spheres, silicon wafers, and fibers. Breakthrough tests show that the MOF-functionalized fibers have high adsorption capacity for toxic gases. This rapid synthesis route is also promising for new MOF-based composite materials and applications.

Effect of temperature and gas velocity on growth per cycle during Al2O3 and ZnO atomic layer deposition at atmospheric pressure

The growth per cycle as a function of temperature during atomic layer deposition (ALD) of Al2O3 and ZnO at atmospheric pressure follows very closely the trend measured at typical (∼2 Torr) process pressure. However, the overall growth rate is found to be nearly 2 × larger at higher pressure and the magnitude of the growth increase can be adjusted by controlling the gas velocity near the growth surface. The growth increase at high pressure is approximately independent of process temperature at T   150 °C, especially for Al2O3. The relatively high growth/cycle measured at 760 Torr and T < 150 °C suggests that excess physisorbed water remains on the alumina or zinc oxide surface after the water purge step. Increasing the gas velocity in the growth zone reduces the growth rate, consistent with more efficient removal of excess water. To better understand the observed trends, we present analytical expressions for the boundary layer...

Ultra-Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal-organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF-nanofiber kebab structures for fast degradation of CWAs. We found TiO2 coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH2 , and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF-nanofiber textile composites capable of ultra-fast degradation of CWAs.

Conformal and highly adsorptive metal–organic framework thin films via layer-by-layer growth on ALD-coated fiber mats

Integration of metal–organic frameworks (MOFs) on textiles shows promise for enabling facile deployment and expanding MOF applications. While MOFs deposited on flat substrates can show relatively smooth surface texture, most previous reports of MOFs integrated on fibers show poor conformality with many individual crystal domains. Here we report a new low-temperature (<70 °C) method to deposit uniform and smooth MOF thin films on fiber surfaces using an energy enhanced layer-by-layer (LbL) method with an ALD Al2O3 nucleation layer. Cross-sectional TEM images show a well-defined core@shell structure of the MOF-functionalized fiber, and SEM shows a flat MOF surface texture. We analyze the thickness and mass increase data of LbL HKUST-1 MOF thin films on ALD-coated polypropylene fibers and find the growth rate to be 288–290 ng cm−2 per LbL cycle. Unlike planar LbL MOF embodiments where adsorption capacities are difficult to quantify, the large volume quantity on a typical fiber mat enables accurate surface area measurement of these unique MOF morphologies. After 40 LbL cycles the MOFs on fibers exhibit N2 adsorption BET surface areas of up to 93.6 m2 gMOF+fiber−1 (∼535 m2 gMOF−1) and breakthrough test results reveal high dynamic loadings for NH3 (1.37 molNH3 kgMOF+fiber−1) and H2S (1.49 molH2S kgMOF+fiber−1). This synthesis route is applicable to many polymer fibers, and the fiber@ALD@MOF structure is promising for gas filtration, membrane separation, catalysis, chemical sensing and other applications.

Fiber containment for improved laboratory handling and uniform nanocoating of milligram quantities of carbon nanotubes by atomic layer deposition.

The presence of nanostructured materials in the workplace is bringing attention to the importance of safe practices for nanomaterial handling. We explored novel fiber containment methods to improve the handling of carbon nanotube (CNT) powders in the laboratory while simultaneously allowing highly uniform and controlled atomic layer deposition (ALD) coatings on the nanotubes, down to less than 4 nm on some CNT materials. Moreover, the procedure yields uniform coatings on milligram quantities of nanotubes using a conventional viscous flow reactor system, circumventing the need for specialized fluidized bed or rotary ALD reactors for laboratory-scale studies. We explored both fiber bundles and fiber baskets as possible containment methods and conclude that the baskets are more suitable for coating studies. An extended precursor and reactant dose and soak periods allowed the gases to diffuse through the fiber containment, and the ALD coating thickness scaled linearly with the number of ALD cycles. The extended dose period produced thicker coatings compared to typical doses on CNT controls not encased in the fibers, suggesting some effects due to the extended reactant dose. Film growth was compared on a range of single-walled NTs, double-walled NTs, and acid-functionalized multiwalled NTs, and we found that ultrathin coatings were most readily controlled on the multiwalled NTs.

Atmospheric Pressure Atomic Layer Deposition of Al2O3 Using Trimethyl Aluminum and Ozone

High throughput spatial atomic layer deposition (ALD) often uses higher reactor pressure than typical batch processes, but the specific effects of pressure on species transport and reaction rates are not fully understood. For aluminum oxide (Al2O3) ALD, water or ozone can be used as oxygen sources, but how reaction pressure influences deposition using ozone has not previously been reported. This work describes the effect of deposition pressure, between ∼2 and 760 Torr, on ALD Al2O3 using TMA and ozone. Similar to reports for pressure dependence during TMA/water ALD, surface reaction saturation studies show self-limiting growth at low and high pressure across a reasonable temperature range. Higher pressure tends to increase the growth per cycle, especially at lower gas velocities and temperatures. However, growth saturation at high pressure requires longer O3 dose times per cycle. Results are consistent with a model of ozone decomposition kinetics versus pressure and temperature. Quartz crystal microbalance (QCM) results confirm the trends in growth rate and indicate that the surface reaction mechanisms for Al2O3 growth using ozone are similar under low and high total pressure, including expected trends in the reaction mechanism at different temperatures.

Atomic layer deposition on polymer fibers and fabrics for multifunctional and electronic textiles

Textile materials, including woven cotton, polymer knit fabrics, and synthetic nonwoven fiber mats, are being explored as low-cost, flexible, and light-weight platforms for wearable electronic sensing, communication, energy generation, and storage. The natural porosity and high surface area in textiles is also useful for new applications in environmental protection, chemical decontamination, pharmaceutical and chemical manufacturing, catalytic support, tissue regeneration, and others. These applications raise opportunities for new chemistries, chemical processes, biological coupling, and nanodevice systems that can readily combine with textile manufacturing to create new “multifunctional” fabrics. Atomic layer deposition (ALD) has a unique ability to form highly uniform and conformal thin films at low processing temperature on nonuniform high aspect ratio surfaces. Recent research shows how ALD can coat, modify, and otherwise improve polymer fibers and textiles by incorporating new materials for viable el...

Improved cut-resistance of Kevlar® using controlled interface reactions during atomic layer deposition of ultrathin (<50 Å) inorganic coatings

Conformal atomic layer deposition (ALD) of Al2O3 and TiO2 thin films on Kevlar®, poly(p-phenylene terephthalamide) (PPTA) fibers at 50 and 100 °C affects the fiber cut resistance. Systematic studies of ALD coatings between 10 to 400 A thick formed at 50 and 100 °C revealed excellent conformality, and trends in cutting performance depended on materials and process details. A 50 A/50 A TiO2/Al2O3 bilayer formed at 50 °C increased cut resistance of PPTA by 30% compared to untreated fiber materials. In situ infrared analysis shows that trimethylaluminum (TMA) Al2O3 precursor reacts sub-surface with PPTA and tends to degraded mechanical performance. The TiCl4 TiO2 precursor reacts to form a barrier that limits TMA/PPTA interactions, allowing a harder Al2O3 layer to form on top of TiO2. The thin ALD coatings do not substantially affect durability, flexibility, or weight of the PPTA, making ALD a potentially viable means to enhance the protective properties of Kevlar and other polymer fiber systems.

Multifunctional nano-accordion structures for stretchable transparent conductors

Multifunctional nano-accordion structures exhibiting a unique combination of conductivity, stretchability, and transparency are fabricated through a combination of nanolithography and atomic layer deposition. The nanostructured material demonstrated two orders-of-magnitude improvement in stretchability, repeatable electrical performance for cyclic stretching and bending, and broadband optical transmission up to 70%. The proposed experimental techniques and analytical models enable the deterministic design of nano-accordion geometry to control material stretchability. The proposed nanostructures are promising for applications in transparent flexible electronics, stretchable displays, and wearable sensors.

Temperature-dependent reaction between trimethylaluminum and poly(methyl methacrylate) during sequential vapor infiltration: experimental and ab initio analysis

Vapor-phase, metal-containing organic compounds can diffuse into polymers and modify the material composition and structure. In this work, using a sequential vapor infiltration process based on atomic layer deposition chemistry, we combine in situ Fourier transform infrared transmission and quartz crystal microbalance experiments with ab initio quantum chemical modeling analysis to evaluate and identify likely reaction mechanisms when poly(methyl methacrylate) (PMMA) thin films are exposed to trimethylaluminum (TMA) vapor. We find that TMA readily diffuses into the PMMA, where it physisorbs to ester carbonyl units (CO) to form a metastable CO⋯Al(CH3)3 adduct structure that desorbs at moderate temperatures ( 100 °C, TMA reacts with PMMA to form covalent resonant CO⋯Al–O–C bonding units, and does not form –O–C–O–Al(CH3) as previously hypothesized. This mechanistic insight will help elucidate other polymer/Lewis-acid vapor reactions and could enable new applications for sequential vapor infiltration processes.