From Gel to Crystal: Mechanism of HfO2 and ZrO2 Nanocrystal Synthesis in Benzyl Alcohol.

Nonaqueous sol-gel syntheses have been used to make many types of metal oxide nanocrystals. According to the current paradigm, nonaqueous syntheses have slow kinetics, thus favoring the thermodynamic (crystalline) product. Here we investigate the synthesis of hafnium (and zirconium) oxide nanocrystals from the metal chloride in benzyl alcohol. We follow the transition from precursor to nanocrystal through a combination of rheology, EXAFS, NMR, TEM, and X-ray total scattering (PDF analysis). Upon dissolving the metal chloride precursor, the exchange of chloride ligands for benzylalkoxide liberates HCl. The latter catalyzes the etherification of benzyl alcohol, eliminating water. During the temperature ramp to the reaction temperature (220 °C), sufficient water is produced to turn the reaction mixture into a macroscopic gel. Rheological analysis shows a network consisting of strong interactions with temperature-dependent restructuring. After a few minutes at the reaction temperature, crystalline particles emerge from the gel, and nucleation and growth are complete after 30 min. In contrast, 4 h are required to obtain the highest isolated yield, which we attribute to the slow in situ formation of water (the extraction solvent). We used our mechanistic insights to optimize the synthesis, achieving high isolated yields with a reduced reaction time. Our results oppose the idea that nonaqueous sol-gel syntheses necessarily form crystalline products in one step, without a transient, amorphous gel state.

From Corrosion Casting to Virtual Dissection: Contrast-Enhanced Vascular Imaging using Hafnium Oxide Nanocrystals.

Vascular corrosion casting is a method used to visualize the three dimensional (3D) anatomy and branching pattern of blood vessels. A polymer resin is injected in the vascular system and, after curing, the surrounding tissue is removed. The latter often deforms or even fractures the fragile cast. Here, a method is proposed that does not require corrosion, and is based on in situ micro computed tomography (micro-CT) scans. To overcome the lack of CT contrast between the polymer cast and the animals' surrounding soft tissue, hafnium oxide nanocrystals (HfO2 NCs) are introduced as CT contrast agents into the resin. The NCs dramatically improve the overall CT contrast of the cast and allow for straightforward segmentation in the CT scans. Careful design of the NC surface chemistry ensures the colloidal stability of the NCs in the casting resin. Using only 5 m% of HfO2 NCs, high-quality cardiovascular casts of both zebrafish and mice can be automatically segmented using CT imaging software. This allows to differentiate even µ $\umu$ m-scale details without having to alter the current resin injection methods. This new method of virtual dissection by visualizing casts in situ using contrast-enhanced CT imaging greatly expands the application potential of the technique.

Fatty acid capped, metal oxo clusters as the smallest conceivable nanocrystal prototypes.

Metal oxo clusters of the type M6O4(OH)4(OOCR)12 (M = Zr or Hf) are valuable building blocks for materials science. Here, we synthesize a series of zirconium and hafnium oxo clusters with ligands that are typically used to stabilize oxide nanocrystals (fatty acids with long and/or branched chains). The fatty acid capped oxo clusters have a high solubility but do not crystallize, precluding traditional purification and single-crystal XRD analysis. We thus develop alternative purification strategies and we use X-ray total scattering and Pair Distribution Function (PDF) analysis as our main method to elucidate the structure of the cluster core. We identify the correct structure from a series of possible clusters (Zr3, Zr4, Zr6, Zr12, Zr10, and Zr26). Excellent refinements are only obtained when the ligands are part of the structure model. Further evidence for the cluster composition is provided by nuclear magnetic resonance (NMR), infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), and mass spectrometry (MS). We find that hydrogen bonded carboxylic acid is an intrinsic part of the oxo cluster. Using our analytical tools, we elucidate the conversion from a Zr6 monomer to a Zr12 dimer (and vice versa), induced by carboxylate ligand exchange. Finally, we compare the catalytic performance of Zr12-oleate clusters with oleate capped, 5.5 nm zirconium oxide nanocrystals in the esterification of oleic acid with ethanol. The oxo clusters present a five times higher reaction rate, due to their higher surface area. Since the oxo clusters are the lower limit of downscaling oxide nanocrystals, we present them as appealing catalytic materials, and as atomically precise model systems. In addition, the lessons learned regarding PDF analysis are applicable to other areas of cluster science as well, from semiconductor and metal clusters, to polyoxometalates.

Mapping out the Aqueous Surface Chemistry of Metal Oxide Nanocrystals: Carboxylate, Phosphonate, and Catecholate Ligands.

Iron oxide and hafnium oxide nanocrystals are two of the few successful examples of inorganic nanocrystals used in a clinical setting. Although crucial to their application, their aqueous surface chemistry is not fully understood. The literature contains conflicting reports regarding the optimum binding group. To alleviate these inconsistencies, we set out to systematically investigate the interaction of carboxylic acids, phosphonic acids, and catechols to metal oxide nanocrystals in polar media. Using nuclear magnetic resonance spectroscopy and dynamic light scattering, we map out the pH-dependent binding affinity of the ligands toward hafnium oxide nanocrystals (an NMR-compatible model system). Carboxylic acids easily desorb in water from the surface and only provide limited colloidal stability from pH 2 to pH 6. Phosphonic acids, on the other hand, provide colloidal stability over a broader pH range but also feature a pH-dependent desorption from the surface. They are most suited for acidic to neutral environments (pH <8). Finally, nitrocatechol derivatives provide a tightly bound ligand shell and colloidal stability at physiological and basic pH (6-10). Whereas dynamically bound ligands (carboxylates and phosphonates) do not provide colloidal stability in phosphate-buffered saline, the tightly bound nitrocatechols provide long-term stability. We thus shed light on the complex ligand binding dynamics on metal oxide nanocrystals in aqueous environments. Finally, we provide a practical colloidal stability map, guiding researchers to rationally design ligands for their desired application.