Josef W. Zwanziger

A silica sol–gel design strategy for nanostructured metallic materials

Batteries, fuel cells and solar cells, among many other high-current-density devices, could benefit from the precise meso- to macroscopic structure control afforded by the silica sol-gel process. The porous materials made by silica sol-gel chemistry are typically insulators, however, which has restricted their application. Here we present a simple, yet highly versatile silica sol-gel process built around a multifunctional sol-gel precursor that is derived from the following: amino acids, hydroxy acids or peptides; a silicon alkoxide; and a metal acetate. This approach allows a wide range of biological functionalities and metals--including noble metals--to be combined into a library of sol-gel materials with a high degree of control over composition and structure. We demonstrate that the sol-gel process based on these precursors is compatible with block-copolymer self-assembly, colloidal crystal templating and the Stöber process. As a result of the exceptionally high metal content, these materials can be thermally processed to make porous nanocomposites with metallic percolation networks that have an electrical conductivity of over 1,000 S cm(-1). This improves the electrical conductivity of porous silica sol-gel nanocomposites by three orders of magnitude over existing approaches, opening applications to high-current-density devices.

Design and applications of an in situ electrochemical NMR cell

A device using a three-electrode electrochemical cell (referred to as an ECNMR cell) was successfully constructed that could be used in a standard 5mm NMR probe to acquire high-resolution NMR spectra while the working electrode was held at a constant electrical potential. The working electrode was a 20 nm thick gold film thermally coated on the outside of an inner 3mm glass tube. An underlayer consisting of (3-mercaptopropyl)trimethoxy-silane was coated on the glass surface in order to improve its adhesion to gold. Tests showed prolonged life of the gold film. Details of the design and construction of the ECNMR cell are described. The ECNMR cell could be routinely used in a multi-user service high-resolution NMR instrument under oxygen-free conditions in both aqueous and non-aqueous solvents. Different approaches were applied to suppress the noise transmitted between the potentiostat and the NMR spectrometer. These approaches were shown to be effective in reducing background noise in the NMR spectra. The electrochemical and NMR performance of the ECNMR cell is presented. The reduction of 1,4-benzoquinone in both aqueous and non-aqueous solvents was used for testing. The evolution of the in situ ECNMR spectra with time demonstrated that use of the ECNMR cell was feasible. Studies of caffeic acid and 9-chloroanthracene using this ECNMR cell were undertaken to explore its applications, such as monitoring reactions and studying their reaction mechanisms.

Residual internal stress in partially crystallized photothermorefractive glass: Evaluation by nuclear magnetic resonance spectroscopy and first principles calculations

In some circumstances, the mechanical and optical properties of multiphase brittle materials strongly depend on the level of residual micromechanical stresses that arise upon cooling due to thermal and elastic mismatch between the constituent phases. Here we study the residual internal stress in a partially crystallized oxyfluoride glass, best known as photothermorefractive (PTR) glass. This material is composed of a glass matrix with embedded nanosize sodium fluoride (NaF) crystals. Using both the Selsing model and solid-state nuclear magnetic resonance in combination with first principles calculations we found that the crystals are under a tensile stress field of approximately 610–800MPa. For this stress level the estimated critical crystal diameter for spontaneous cracking is about 2300–1900nm, which greatly exceeds the observed diameters of 7–35nm. Hence no spontaneous cracking is expected for the PTR glasses. First principles calculations indicate that the stress induced change of the refractive inde...

Powder second-harmonic generation study of (K2O)15(Nb2O5)15(TeO2)70 glass ceramic

A power second-harmonic generation (SHG) study has been carried out on (K2O)15(Nb2O5)15(TeO2)70 glass ceramic, which consists of centrosymmetric crystals embedded in a centrosymmetric glass matrix. The effective second-order nonlinear optical coefficient, χ(2), of this material at 532nm is found to be 1.3pm∕V or approximately ten times that of quartz, leading to a maximum second-harmonic intensity approximately 100 times that of quartz. This material is nonphase matchable, with a coherence length of 30μm. We conclude that the SHG in this material originates from the abrupt changes in optical susceptibility at the interfaces between the glass and crystal, together with the higher-order nonlinear response.

Stimuli-Responsive Shapeshifting Mesoporous Silica Nanoparticles

Stimuli-responsive materials have attracted great interest in catalysis, sensing, and drug delivery applications and are typically constituted by soft components. We present a one-pot synthetic method for a type of inorganic silica-based shape change material that is responsive to water vapor exposure. After the wetting treatment, the cross-sectional shape of aminated mesoporous silica nanoparticles (MSNs) with hexagonal pore lattice changed from hexagonal to six-angle-star, accompanied by the loss of periodic mesostructural order. Nitrogen sorption measurements suggested that the wetting treatment induced a shrinkage of mesopores resulting in a broad size distribution and decreased mesopore volume. Solid-state (29)Si nuclear magnetic resonance (NMR) spectroscopy of samples after wetting treatment displayed a higher degree of silica condensation, indicating that the shape change was associated with the formation of more siloxane bonds within the silica matrix. On the basis of material characterization results, a mechanism for the observed anisotropic shrinkage is suggested based on a buckling deformation induced by capillary forces in the presence of a threshold amount of water vapor available beyond a humidity of about 50%. The work presented here may open a path toward novel stimuli-responsive materials based on inorganic components.

A 43Ca and 13C NMR study of the chemical interaction between poly(ethylene-vinyl acetate) and white cement during hydration.

(43)Ca and (13)C NMR methods were used to study the chemical interaction of poly(ethylene-vinyl acetate) (PEVAc) admixture in commercial-grade white cement. From (43)Ca NMR it is shown both that PEVAc induces modest changes in the hydrated cement structure, and that hydrated commercial cement is significantly more complex than models that have been used for its structure in past work. The (13)C NMR results show that the PEVAc hydrolysis occurs early in the cement hydration acceleration period, with a rate well-fit by an exponential decay using a time constant of 6±1 days.

Multinuclear NMR study of zinc dicyanide.

Abstract The isotropic negative expansion of Zn(CN)2 has been linked to a temperature induced increase in off-axis tilting of the C–N bond direction and an increase in CN-bond length. However, the bond length could be determined only indirectly based on pair-distribution function analysis and was found to be surprisingly large. Here we study Zn(CN)2 by nuclear magnetic resonance spectroscopy and first principles calculations. By using samples enriched in 13C and 15N the dipole coupling between carbon and nitrogen is determined, and from this an upper bound on the C–N bond length of 1.19 ± 0.01 Å is derived. This quantity agrees with earlier determinations based on diffraction but is shorter than estimates based on pair distribution function analysis. The relation of this estimate to possible dynamics in the sample is discussed. Finally, 67Zn NMR is used together with first principles calculations to assess disorder in the material.

Relationships between elastic anisotropy and thermal expansion in A2Mo3O12 materials

We report calculated elastic tensors, axial Grüneisen parameters, and thermal stress distributions in Al2Mo3O12, ZrMgMo3O12, Sc2Mo3O12, and Y2Mo3O12, a series of isomorphic materials for which the coefficients of thermal expansion range from low-positive to negative. Thermal stress in polycrystalline materials arises from interactions between thermal expansion and mechanical properties, and both can be highly anisotropic. Thermal expansion anisotropy was found to be correlated with elastic anisotropy: axes with negative thermal expansion were less compliant. Calculations of axial Grüneisen parameters revealed that the thermal expansion anisotropy in these materials is in part due to the Poisson effect. Models of thermal stress due to thermal expansion anisotropy in polycrystals following cooling showed thermal stresses of sufficient magnitude to cause microcracking in all cases. The thermal expansion anisotropy was found to couple to elastic anisotropy, decreasing the bulk coefficient of thermal expansion and leading to lognormal extremes of the thermal stress distributions.

Generalized Routes to Mesostructured Silicates with High Metal Content

Abstract Nanostructured materials with high metal content are interesting for a number of applications, including catalysis as well as energy conversion and storage. Here we elaborate an approach that combines the advantages of simple silica sol-gel chemistry with the ability to tailor metal composition and structure by introducing a ligand that connects a silane with an amino acid or hydroxy acid. Reacting this ligand with a metal acetate generates a precursor for a range of metal-silica nanocomposites. Comparing this chemistry with conventional organic ligand-metal complexes that can be physically mixed into sol-gel derived silicates elucidates advantages, e.g. of going to high metal loadings. Resulting nanomaterials are characterized by a combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (NMR) to reveal structural characteristics on multiple lengths scales, i.e. from the microscopic (molecular) level (NMR) all the way to the mesoscale (SAXS) and macroscale (TEM).

125Te NMR Probes of Tellurium Oxide Crystals: Shielding-Structure Correlations

The local environments around tellurium atoms in a series of tellurium oxide crystals were probed by 125Te solid-state NMR spectroscopy. Crystals with distinct TeOn units (n from 3 to 6), including Na2TeO3, α-TeO2 and γ-TeO2, Te2O(PO4)2, K3LaTe2O9, BaZnTe2O7, and CsYTe3O8 were studied. The latter four were synthesized through a solid-state process. X-ray diffraction was used to confirm the successful syntheses. The 125Te chemical shift was found to exhibit a strong linear correlation with the Te coordination number. The 125Te chemical-shift components (δ11, δ22, and δ33) of the TeO4 units were further correlated to the O-Te-O-bond angles. With the aid of 125Te NMR, it is likely that these relations can be used to estimate the coordination states of Te atoms in unknown Te crystals and glasses.