Benjamin W. Jacobs

Silver Cluster Formation, Dynamics, and Chemistry in Metal−Organic Frameworks

Synthetic methods used to produce metal nanoparticles typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal-organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with the potential for both steric and chemical stabilization. We report a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions < or =1 nm, with a significant fraction existing as Ag(3) clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible.

Metal-organic frameworks as templates for nanoscale NaAlH4.

Metal-organic frameworks (MOFs) offer an attractive alternative to traditional hard and soft templates for nanocluster synthesis because their ordered crystalline lattice provides a highly controlled and inherently understandable environment. We demonstrate that MOFs are stable hosts for metal hydrides proposed for hydrogen storage and their reactive precursors, providing platform to test recent theoretical predictions that some of these materials can be destabilized with respect to hydrogen desorption by reducing their critical dimension to the nanoscale. With the MOF HKUST-1 as template, we show that NaAlH(4) nanoclusters as small as eight formula units can be synthesized. The confinement of these clusters within the MOF pores dramatically accelerates the desorption kinetics, causing decomposition to occur at approximately 100 degrees C lower than bulk NaAlH(4). However, using simultaneous thermogravimetric modulated beam mass spectrometry, we also show that the thermal decomposition mechanism of NaAlH(4) is complex and may involve processes such as nucleation and growth in addition to the normally assumed two-step chemical decomposition reactions.

Assessing the Purity of Metal−Organic Frameworks Using Photoluminescence: MOF-5, ZnO Quantum Dots, and Framework Decomposition

Photoluminescence (PL) spectroscopy was used to characterize nanoscale ZnO impurities, amine-donor charge-transfer exciplexes, and framework decomposition in samples of MOF-5 prepared by various methods. The combined results cast doubt on previous reports describing MOF-5 as a semiconductor and demonstrate that PL as a tool for characterizing MOF purity possesses advantages such as simplicity, speed, and sensitivity over currently employed powder XRD MOF characterization methods.

Ordered metal nanostructure self-assembly using metal–organic frameworks as templates

We demonstrate that nanoporous metal–organic frameworks (MOFs) loaded with silver can serve as templates for ordered nanostructures comprising either silver nanoparticles or nanowires. Exposure to an electron beam breaks down the template, leading to rapid silver coalescence. The geometric and chemical structure of the MOF, as well as the extent of metal loading, determine whether nanoparticles or nanowires are formed and define their size and orientation. Nanowires with diameters as small as 4 nm and aspect ratios >125 can be formed, overcoming the limitations of existing templating methods. This method is relatively simple, compatible with many materials, and proceeds by a distinct template-directed growth mechanism. Since MOFs offer an unprecedented level of synthetic flexibility, combined with highly uniform porosity as a result of their crystalline structure, this approach opens a promising new route for synthesis of self-assembled, ordered nanostructures.

Nanopipes in Gallium Nitride Nanowires and Rods

Gallium nitride nanowires and rods synthesized by a catalyst-free vapor-solid growth method were analyzed with cross section high-resolution transmission electron microscopy. The cross section studies revealed hollow core screw dislocations, or nanopipes, in the nanowires and rods. The hollow cores were located at or near the center of the nanowires and rods, along the axis of a screw dislocation. The formation of the hollow cores is consistent with effect of screw dislocations with giant Burgers vector predicted by Frank.

Three-dimensional pore evolution of nanoporous metal particles for energy storage.

A well characterized and predictable aging pattern is necessary for practical energy storage applications of nanoporous particles that facilitate rapid transport of ions or redox species. Here we use STEM tomography with segmentation to show that surface diffusion and grain boundary diffusion are responsible for pore evolution at intermediate and higher temperatures, respectively. This unprecedented three dimensional understanding of pore behavior as a function of temperature suggests routes for optimizing pore stability in future energy storage materials.

Electronic and Structural Characteristics of Zinc-Blende Wurtzite Biphasic Homostructure GaN Nanowires

We report a new biphasic crystalline wurtzite/zinc-blende homostructure in gallium nitride nanowires. Cathodoluminescence was used to quantitatively measure the wurtzite and zinc-blende band gaps. High-resolution transmission electron microscopy was used to identify distinct wurtzite and zinc-blende crystalline phases within single nanowires through the use of selected area electron diffraction, electron dispersive spectroscopy, electron energy loss spectroscopy, and fast Fourier transform techniques. A mechanism for growth is identified.

Nanoporous Pd alloys with compositionally tunable hydrogen storage properties prepared by nanoparticle consolidation

Nanoporous palladium and palladium alloys are expected to have improved mass transport rates and cycle life compared to bulk materials for energy storage and other applications due to high ratios of surface area to metal volume. Preparation of such materials with high thermal stability and well-controlled metal composition, however, remains a challenge. This work describes a scalable, bottom-up technique for preparing nanoporous palladium alloys based on partial consolidation of dendrimer-encapsulated nanoparticles (DEN). Destabilization of a colloidal suspension of DEN and purification yields high surface area material (60–80 m2 g−1) with a broad pore size distribution centered between 20 and 50 nm. This approach allows for precise tuning of product composition through adjustment of the composition of the precursor DEN. Nanoporous Pd0.9Rh0.1 alloys with uniform composition or with Rh enrichment at pore walls and grain boundaries have been prepared and these structures have been confirmed with high-spatial resolution, aberration corrected quantitative STEM-EDS. Compared to bulk alloys of the same nominal composition, the nanoporous bimetallics show much faster hydrogen uptake kinetics, and store hydrogen at much lower pressure. Pore structure remains intact to temperatures above 300 °C, suggesting that these materials will have long lifetimes at the temperatures used for hydrogen storage applications.

Effect of Salt Depletion on Charging Dynamics in Nanoporous Electrodes

Electrochemical double-layer capacitors built from nanoporous electrodes can have such a high ratio of electrode surface area to pore volume that charging the capacitor can deplete the salt from the liquid volume. This can result in increased resistance, resulting in a slow, nonlinear charging rate of which quantitative understanding is limited. In some cases, this effect is masked by an external solution resistance or by the transport of salt into the pore from an external reservoir. However, in forms relevant to a compact energy storage device, the phenomenon can have an important effect on charging time and linearity, and understanding it is important for such design. We have observed salt depletion effects by using dealloyed gold, which has well-defined 10 nm pores and a chemically well-understood surface, and by minimizing the amount of external salt within range of diffusion. Good correspondence is observed with a modified de Levie model that accounts for reduced local conductivity due to salt depletion. The models assumption that the Stern layer (ions closely bound to the pore wall) makes a low contribution to conductance in the pore is validated by experimental data.

Synthesis of mesoporous palladium with tunable porosity and demonstration of its thermal stability by in situ heating and environmental transmission electron microscopy

Palladium and its alloys have high-value applications as materials for high-performance hydrogen storage, chromatographic separation of hydrogen isotopes, electrocatalysis and catalysis. These materials can be formed by chemical or electrochemical reduction in a lyotropic liquid crystalline template that constrains their growth on the nanometer scale. This approach works for a variety of metals, but Pd presents special challenges due to the autocatalytic nature of its growth, which can disrupt the template structure, resulting in disordered pores. Presented herein is a scaleable synthesis that overcomes these challenges, yielding mesoporous Pd powder having pore diameters of 7 or 13 nm. Pore size control is effected by varying the size of the molecular template, polystyrene-block-polyethylene oxide. We have used heated-stage TEM for in situ observation of the materials in vacuum and in the presence of H2 gas, demonstrating that both pore diameter and the chemical state of the surface play important roles in determining thermal stability. Improved stability compared to previously reported examples facilitates preparation of scalable quantities of regularly mesoporous Pd that retains porosity at the elevated temperatures required for applications in hydrogen charge/discharge and catalysis.