From ligands to binding motifs and beyond; the enhanced versatility of nanocrystal surfaces

Surface chemistry bridges the gap between nanocrystal synthesis and their applications. In this respect, the discovery of complex ligand binding motifs on semiconductor quantum dots and metal oxide nanocrystals opens a gateway to new areas of research. The implications are far-reaching, from catalytic model systems to the performance of solar cells

Chemical solution deposition of functional ceramic coatings using ink-jet printing

This paper discusses the development of environmentally-friendly precursor inks suited for ink-jet printing of functional ceramic coatings. We synthesized superconducting materials, SrTiO3 thin films for coated conductor applications and transparent TiO2 photocatalytic coatings. Here, we discuss all aspects of ink formulation, including the stabilization of metal ions, nanoparticle inks or combination of both. This demands the investigation and determination of the inks rheological parameters. Ceramic nanoparticles are often incorporated in our inks to decrease thermal processing temperatures (e.g., TiO2 or YSZ coatings...) or enhance the properties of the functional ceramic coating (e.g., pinning centres in superconducting coatings). These ceramic nanoparticles (ZrO2, HfO2, TiO2...) are synthesized through methods based on microwave heating from aqueous and/or organic solutions. With that, we aim at developing smart and environmentally friendly processes that require lower energy input

Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution 1H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions

Microwave-assisted YBa2Cu3O7 precursors : a fast and reliable method towards chemical precursors for superconducting films

Highly stable, pure, and anhydrous organometallic YBa2Cu3O7- (YBCO) precursor solutions were prepared by dissolving commercial YBCO powder in acetone by trifluoroacetic anhydride (TFAA) or a mixture of TFAA with propionic acid for low fluorine precursors. It is shown that compared to conventional oil bath heating reported in literature, the reaction to produce YBCO precursor occurs 72 times faster by microwave heating. More importantly, the formation of byproducts is suppressed, as shown by nuclear magnetic resonance (NMR) and mass spectrometry (MS). This approach allows a highly reproducible preparation of superconducting coatings which is of interest for low-cost manufacturing processes capable of large-scale production of the coated conductors via chemical solution deposition (CSD). This technology requires reliable and stable precursor solutions for continuous deposition. In this work, we obtained YBCO thin films on single-crystal substrates ((100)-LaAlO3) with a high critical current density (J(c)) of 3-4 MA/cm(2) in self-field at 77 K using TFA-based YBCO precursors and J(c) of 5-6 MA/cm(2) using low fluorine YBCO precursors

Fast, microwave-assisted synthesis of monodisperse HfO₂ nanoparticles

A conventional solvothermal synthesis was compared to a microwave-assisted method for the synthesis of HfO2 nanoparticles. In a microwave, the reaction could be completed in 3 h, compared to 3 days in an autoclave. In the microwave synthesis, the ensemble of particles was found to have a better size dispersion and a smaller average size (4 nm). The reaction mechanism was investigated and proof for an ether elimination process was provided. Post-synthetic modification with dopamine or dodecanoic acid permitted the suspension of the synthesized particles in both polar and apolar solvents, which is an advantage for further processing

Size tunable synthesis and surface chemistry of metastable TiO2-bronze nanocrystals

The metastable titania phase, bronze, has great potential as photocatalyst or as anode material in Li-ion batteries. Here, we report the first synthesis of colloidally stable, size-tunable TiO2-bronze (TiO2-B) nanocrystals, via a hydrothermal process. By employing definitive screening design, the experimental parameters affecting the size and agglomeration of the nanocrystals are identified. The size is mostly determined by the reaction temperature, resulting in 3-8 nm NCs in the range of 130-180 degrees C. To avoid irreversible aggregation, short reaction times are desired, and in this respect, microwave heating proved essential due to its fast heating and cooling rates. The resulting nanocrystals are deaggregated and stabilized in polar solvents using either positive or negative surface charges. In nonpolar solvents, steric stabilization is provided by long chain amines and carboxylic acids. Furthermore, we study this peculiar postsynthetic surface modification through solution H-1 NMR and elemental analysis. Surprisingly, we find ion-pairs of alkylammonium carboxylates bound to the surface, contrasting with earlier reports on carboxylic acid stabilized metal oxide nanocrystals. To rationalize this, a general framework of acid/base chemistry with metal oxide nanocrystals is constructed and discussed

Fast and tunable synthesis of ZrO2 nanocrystals : mechanistic insights into precursor dependence

In this work, ZrO2 nanocrystals (NCs) are synthesized via a solvothermal treatment in benzyl alcohol, which is an established method for the synthesis of many metal oxide nanocrystals. We found that the use of microwave heating allows for a reduction in reaction time from 2 days in the autoclave to merely 4 h in the microwave. Furthermore, we were able to tune the crystallographic phase from pure cubic to pure monoclinic zirconia by changing the reaction mechanism through the use of a different zirconium precursor. Via GC-MS measurements, we found that the release of a strong acid during synthesis controls the key mechanism behind the control over crystal phase formation. The as-synthesized ZrO2 NCs (cubic or monoclinic) are small in size (3-10 nm), yet aggregated. However, aggregate-free NCs are generated through a surface-functionalization with carboxylic acid ligands, providing stabilization in apolar solvents via steric hindrance. Solution H-1 NMR was used to study the details of this post-modification step and the surface chemistry of the resulting aggregate-free NCs. This led to the conclusion that not only a different crystal structure but also a different surface chemistry is obtained, depending on the precursor composition

Amino acid-based stabilization of oxide nanocrystals in polar media : from insight in ligand exchange to solution H-1 NMR probing of short-chained adsorbates

Ligand exchange is a crucial step between nanocrystal synthesis and nanocrystal application. Although colloidal stability and ligand exchange in nonpolar media are readily established, the exchange of native, hydrophobic ligands with polar ligands is less systematic. In this paper, we present a versatile ligand exchange strategy for the phase transfer of carboxylic acid capped HfO2 and ZrO2 nanocrystals to various polar solvents, based on small amino acids as the incoming ligand. To gain insight in the fundamental mechanism of the exchange, we study this system with a combination of FTIR, zeta potential measurements, and solution H-1 NMR techniques. The detection of surface-associated, small ligands with solution NMR proves challenging in this respect. Tightly bound amino acids are undetectable, but their existence can be proven through displacement with other ligands in titration experiments. Alternatively, we find that methyl moieties belonging to bound species can circumvent these limitations because of their more favorable relaxation properties as a result of internal mobility. As such, our results are not limited to amino acids but to any short-chained ligand and will therefore facilitate the rigorous investigation and understanding of various ligand exchange processes