We transformed vapor phase grown ZnO nanoparticle powders into aqueous ZnO nanoparticle dispersions and studied the impact of associated microstructure and interface property changes on their spectroscopic properties. With photoluminescence (PL) spectroscopy, we probed oxygen interstitials in the near surface region and tracked their specific PL emission response at hv EM = 2.1 eV during the controlled conversion of the solid-vacuum into the solid-liquid interface. While oxygen adsorption via the gas phase does affect the intensity of the PL emission bands, the O 2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hv EM = 3.2 eV gains relative intensity with regard to the PL emission features in the visible light region. Searching for potential PL indicators that are specific to early stages of particle dissolution, we addressed for aqueous ZnO nanoparticle dispersions the effect of formic acid adsorption. In the absence of related spectroscopic features, we were able to consistently track ZnO nanoparticle dissolution and the concomitant formation of sol- vated Zinc formate species by means of PL and FT-IR spectroscopy, dynamic light scattering, and zeta potential measurements. For a more consistent and robust assessment of nanoparticle properties in different continuous phases, we discuss characterization challenges and potential pitfalls that arise upon replacing the solid-gas with the solid-liquid interface.

Nanotechnology is a fast growing field and already a multi-billion dollar market with numerous consumer products.

BackgroundActivity retention upon enzyme adsorption on inorganic nanostructures depends on different system parameters such as structure and composition of the support, composition of the medium as well as enzyme loading. Qualitative and quantitative characterization work, which aims at an elucidation of the microscopic details governing enzymatic activity, requires well-defined model systems.ResultsVapor phase-grown and thermally processed anatase TiO2 nanoparticle powders were transformed into aqueous particle dispersions and characterized by dynamic light scattering and laser Doppler electrophoresis. Addition of β-galactosidase (β-gal) to these dispersions leads to complete enzyme adsorption and the generation of β-gal/TiO2 heteroaggregates. For low enzyme loadings (~4% of the theoretical monolayer coverage) we observed a dramatic activity loss in enzymatic activity by a factor of 60–100 in comparison to that of the free enzyme in solution. Parallel ATR-IR-spectroscopic characterization of β-gal/TiO2 heteroaggregates reveals an adsorption-induced decrease of the β-sheet content and the formation of random structures leading to the deterioration of the active site.ConclusionsThe study underlines that robust qualitative and quantitative statements about enzyme adsorption and activity retention require the use of model systems such as anatase TiO2 nanoparticle agglomerates featuring well-defined structural and compositional properties.Electronic supplementary materialThe online version of this article (doi:10.1186/s12951-017-0283-4) contains supplementary material, which is available to authorized users.

Variations in the composition and structure of ZnO nanoparticle interfaces have a key influence on the materials’ optoelectronic properties and are responsible for high number of discrepant results reported for ZnO-based nanomaterials. Here, we conduct a systematic study of the room-temperature photoluminescence of anhydrous ZnO nanocrystals, as synthesized in the gas phase and processed in water-free atmosphere, and of their colloidal derivatives in aqueous dispersions with varying amounts of organic salt admixtures. A free exciton band at hv = 3.3 eV is essentially absent in the anhydrous ZnO nanocrystal powders measured in vacuum or in oxygen atmosphere. Surface hydration of the nanoparticles during colloid formation leads to the emergence of the free exciton band at hv = 3.3 eV and induces a small but significant release in lattice strain as detected by X-ray diffraction. Most importantly, admixture of acetate or citrate ions to the aqueous colloidal dispersions not only allows for the control of the ζ-potential but also affects the intensity of the free exciton emission in a correlated manner. The buildup of negative charge at the solid—liquid interface, as produced by citrate adsorption, increases the free exciton emission. This effect is attributed to the suppression of electron trapping in the near-surface region, which counteracts nonradiative exciton recombination. Using well-defined ZnO nanoparticles as model systems for interface chemistry studies, our findings highlight water-induced key effects that depend on the composition of the aqueous solution shell around the semiconducting metal oxide nanoparticles.

Adsorption of organic molecules at ZnO nanoparticle surfaces enables the transfer of energy or charge across resulting organic–inorganic interfaces and, consequently, determines the optoelectronic performance of ZnO‐based hybrids. We investigated adsorption‐induced changes with photoluminescence (PL) and electron paramagnetic resonance (EPR) spectroscopy on aqueous colloidal ZnO dispersions. Citrate and acetate ion adsorption increases or decreases radiative exciton annihilation at hν=3.3 eV and at room temperature, respectively. Searching for a correspondence between PL emission and the yield of trapped charge carriers originating from exciton separation (using photon energies of hν=4.6 eV and fluxes of ṄPh=1014 cm−2 s−1 for excitation), we found that there is a negligible fraction of paramagnetic products that originates from exciton separation. Upon polychromatic excitation with significantly higher photon fluxes (ṄPh=1016 cm−2 s−1), ZnO‐specific shallow defects trap unpaired electrons in citrate‐ and acetate‐functionalized samples. The adsorption‐dependent PL intensity changes and the excitation parameter dependent yield of separated charges (EPR) in colloidal ZnO nanoparticles underline that the distribution over the different exciton annihilation channels sensitively depends on interface composition and the intensity of the photoexcitation light.

The rare-earth fluoride borate LaB 2 O 4 F was synthesized under high-pressure/high-temperature conditions of 1.1 GPa and 1300 • C in a Walker-type multianvil apparatus from lanthanum oxide, lanthanum fluoride, and boron oxide. The single-crystal structure determination revealed that LaB 2 O 4 F is isotypic to CeB 2 O 4 F. The compound crystallizes in the orthorhombic space group Pbca (no. 61) with eight formula units and the lattice parameters a = 8.2493(9), b = 12.6464(6), c = 7.3301(5)Å, V = 764.7(2)Å 3 , R 1 = 0.0354, and wR 2 = 0.0474 (all data). The structure exhibits a 9+1 coordinated lanthanum cation, one threefold coordinated fluoride ion and a chain of corner-sharing [BO 3 ] 3− groups. In addition to the IR-and Raman-spectroscopic investigations, DFT calculations were performed to support the assignment of the vibrational bands.

High-Pressure Synthesis and Characterization of the Rare-Earth Fluoride BorateLaB2O4F. -LaB2O4F is prepared from stoichiometric mixtures of La2O3, B2O3, and LaF3 under high-pressure/high-temperature conditions (BN crucibles in multianvil press, 1300°C, 1.1 GPa). The compound is isotypic with CeB2O4F and crystallizes in the orthorhombic space group Pbca with Z = 8 (single crystal XRD). The structure exhibits a 9+1 coordinated La 3+ cation, one threefold coordinated Fion and a chain of corner-sharing [BO3] groups. In addition to the IR-and Raman-spectroscopic investigations, DFT calculations are performed to support the assignment of the vibrational bands. -(HINTEREGGER, E.; KOCSIS, K.; HOFER, T. S.; HEYMANN, G.; PERFLER, L.; HUPPERTZ*, H.; Z. Naturforsch., B: Chem. Sci. 68b (2013) 9, 951-959, http://dx.doi.org/10.5560/ZNB.2013-3177 ; Inst. Allg. Anorg. Theor. Chem., Leopold-Franzens-Univ., A-6020 Innsbruck, Austria; Eng.) -J. Schramke 48-008

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