Charge Separation in BaTiO3 Nanocrystals: Spontaneous Polarization Versus Point Defect Chemistry.

The fate of photogenerated charges within ferroelectric metal oxides is key for photocatalytic applications. The authors study the contributions of i) tetragonal distortion, responsible for spontaneous polarization, and ii) point defects, on charge separation and recombination within BaTiO3 (BTO) nanocrystals of cubic and tetragonal structure. Electron paramagnetic resonance (EPR) in combination with O2 photoadsorption experiments show that BTO nanocrystals annealed at 600 °C have a charge separation yield enhanced by a factor > 10 compared to TiO2 anatase nanocrystals of similar geometries. This demonstrates for the first time the beneficial effect of the BTO perovskite nanocrystal lattice on charge separation. Strikingly, charge separation is considerably hindered within BTO nanoparticles annealed ≥ 600 °C, due to the formation of Ba-O divacancies that act as charge recombination centers. The opposing interplay between tetragonal distortion and annealing-induced defect formation inside the lattice highlights the importance of defect engineering within perovskite nanoparticles.

Conversion of MgO nanocrystal surfaces into ceramic interfaces: Exsolution of BaO as photoluminescent interface probes.

Ion exsolution can be instrumental to engineer intergranular regions inside ceramic microstructures. BaO admixtures that were trapped inside nanometer-sized MgO grains during gas phase synthesis undergo annealing-induced exsolution to generate photoluminescent surface and interface structures. During their segregation from the bulk into the grain interfaces, the BaO admixtures impact grain coarsening and powder densification, effects that were compared for the first time using an integrated characterization approach. For the characterization of the different stages the materials adopt between powder synthesis and compact annealing, spectroscopy measurements (UV-Vis diffuse reflectance, cathodo- and photoluminescence [PL]) were complemented by an in-depth structure characterization (density measurements, X-ray diffraction [XRD], and electron microscopy). Depending on the Ba2+ concentration, isolated impurity ions either become part of low-coordinated surface structures of the MgO grains where they give rise to a characteristic bright PL emission profile around λ = 500 nm, or they aggregate to form nanocrystalline BaO segregates at the inner pore surfaces to produce an emission feature centered at λ = 460 nm. Both types of PL emission sites exhibit O2 gas adsorption-dependent PL emission properties that are reversible with respect to its pressure. The here-reported distribution of BaO segregates between the intergranular region and the free pore surfaces inside the MgO-based compacts underlines that solid-based exsolution strategies are well suited to stabilize nanometer-sized segregates of metal oxides that otherwise would coalesce and grow in size beyond the nanoscale.

Paramagnetic electron centers in BaTiO3 nanoparticle powders.

Knowledge about the emergence and depletion of point defects in BaTiO3 (BTO) nano-structures during materials processing is key to our understanding of their later activity as components in functional dielectric devices or as photocatalysts. In this electron paramagnetic resonance (EPR) study we investigated BaTiO3 nanoparticle powders produced by flame spray pyrolysis (FSP) with powders of TiO2 anatase nanocrystals of comparable size as reference system. Paramagnetic Ti3+ ions located at regular lattice sites and with well-defined EPR signatures were measured in vacuum annealed BaTiO3 nanoparticles, which convert upon further annealing in the temperature range between 873 K and 1173 K from monocrystalline grains with an average size of d = 12 nm, BTO (873 K), to polycrystalline particles with d = 70 nm, BTO (1173 K). Whereas the starting material hosts predominantly polaron-type Ti3+ ions being surrounded by compressed O2- ion octahedra, barium-oxygen divacancy complexes, , become susceptible to electron trapping in polycrystalline and tetragonal BTO (1173 K) particles after pre-annealing at temperatures T > 873 K. The insights obtained provide a base for the detection of local distortion effects, for the identification of charge trapping sites and for the elucidation of their impact on spontaneous polarization in BaTiO3 nanoparticles as photocatalysts or dielectric components.

Isolated Cobalt Ions Embedded in Magnesium Oxide Nanostructures: Spectroscopic Properties and Redox Activity.

Atomic dispersion of dopants and control over their defect chemistry are central goals in the development of oxide nanoparticles for functional materials with dedicated electronic, optical or magnetic properties. We produced highly dispersed oxide nanocubes with atomic distribution of cobalt ions in substitutional sites of the MgO host lattice via metal organic chemical vapor synthesis. Vacuum annealing of the nanoparticle powders up to 1173 K has no effect on the shape of the individual particles and only leads to moderate particle coarsening. Such materials processing, however, gives rise to the electronic reduction of particle surfaces, which-upon O2 admission-stabilize anionic oxygen radicals that are accessible to UV/Vis diffuse reflectance and electron paramagnetic resonance (EPR) spectroscopy. Multi-reference quantum chemical calculations show that the optical bands observed mainly originate from transitions into 4 A2g (4 F), 4 T1g (4 P) states with a contribution of transitions into 2 T1g , 2 T2g (2 G) states through spin-orbit coupling and gain intensity through vibrational motion of the MgO lattice or the asymmetric ion field. Related nanostructures are a promising material system for single atomic site catalysis. At the same time, it represents an extremely valuable model system for the study of interfacial electron transfer processes that are key to nanoparticle chemistry and photochemistry at room temperature, and in heterogeneous catalysis.

Catalytic activity, water formation, and sintering: Methane activation over Co- and Fe-doped MgO nanocrystals.

Microstructure, structure, and compositional homogeneity of metal oxide nanoparticles can change dramatically during catalysis. Considering the different stabilities of cobalt and iron ions in the MgO host lattice [M. Niedermaier et al., J. Phys. Chem. C 123, 25991 (2019)], we employed MgO nanocube powders with or without transition metal admixtures for the oxidative coupling of methane (OCM) reaction to analyze characteristic differences in catalytic activity and sintering behavior. Undoped MgO nanocrystals exhibit the highest C2 selectivity and retain the nanocrystallinity of the starting material after 24 h time on stream. For the Co-Mg-O nanoparticle powder, which exhibits the highest activity and COx selectivity and where OCM-induced coarsening is strongest, we found that the Co2+ ions remain homogeneously distributed over the MgO lattice. Trivalent Fe ions migrate to the surface of Fe-Mg-O nanoparticles where they form a magnesioferrite phase (MgFe2O4) with a characteristic impact on catalytic performance: Fe-Mg-O is initially less selective than MgO despite its lower activity. An increase in C2 selectivity and a decrease in the CO2/CO ratio with time on stream are attributed to the increasing fraction of coarsened particles that become depleted in redox active Fe. Surface water is a by-product of the OCM reaction, favors mass transport across the particle surfaces, and serves as a sintering aid during catalysis. The characteristic changes in size and morphology of MgO, Co-doped, and Fe-doped MgO particles can be consistently explained by activity and C2 selectivity trends. The original morphology of the nanocubes as a starting material for the OCM reaction does not impact the catalytic activity.

From Anhydrous Zinc Oxide Nanoparticle Powders to Aqueous Colloids: Impact of Water Condensation and Organic Salt Adsorption on Free Exciton Emission.

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 hν = 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 hν = 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.

Three-Dimensional Electrochemical Axial Lithography on Si Micro- and Nanowire Arrays.

A templated electrochemical technique for patterning macroscopic arrays of single-crystalline Si micro- and nanowires with feature dimensions down to 5 nm is reported. This technique, termed three-dimensional electrochemical axial lithography (3DEAL), allows the design and parallel fabrication of hybrid silicon nanowire arrays decorated with complex metal nano-ring architectures in a flexible and modular approach. While conventional templated approaches are based on the direct replication of a template, our method can be used to perform high-resolution lithography on pre-existing nanostructures. This is made possible by the synthesis of a porous template with tunable dimensions that guides the deposition of well-defined metallic shells around the Si wires. The synthesis of a variety of ring architectures composed of different metals (Au, Ag, Fe, and Ni) with controlled sequence, height, and position along the wire is demonstrated for both straight and kinked wires. We observe a strong enhancement of the Raman signal for arrays of Si nanowires decorated with multiple gold rings due to the plasmonic hot spots created in these tailored architectures. The uniformity of the fabrication method is evidenced by a homogeneous increase in the Raman signal throughout the macroscopic sample. This demonstrates the reliability of the method for engineering plasmonic fields in three dimensions within Si wire arrays.

Thermally Activated Self-metalation of Carboxy-functionalized Porphyrin Films on MgO Nanocubes.

We investigated the adsorption of different free-base carboxyl-functionalized porphyrins, 5,10,15,20-tetrakis(4-carboxyphenyl)-21,23H-porphyrin (2H-TCPP) and 5(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-MCTPP), on MgO nanocubes combining IR, UV/Vis and photoluminescence emission spectroscopy. The thermal behavior of the films was monitored in-situ during annealing. Both porphyrins bind to the nanocubes via one and two acid groups respectively, yielding monolayer films consisting of tilted molecules. For 2H-TCPP, two acid groups remain free and give rise to a characteristic IR band. Self-assembly in a tilted adsorbate layer suppresses metalation at room temperature, in contrast to non-functionalized 2H-TPP, which adsorbs flat-lying. Upon heating, 2H-MCTPP undergoes full metalation at temperatures below 280 °C, whereas 2H-TCPP does not metalate at all. The hindered metalation reaction is attributed to the rigidity of the adsorbate film preventing complexation. Our results show that the properties of porphyrin films on oxides can be tuned in a wide range via the position and arrangement of carboxyl anchoring groups.

Anchoring of carboxyl-functionalized porphyrins on MgO, TiO2, and Co3O4 nanoparticles.

Hybrid materials consisting of functional organic molecules on metal oxide nanomaterials are key components in emerging technologies, for example in energy conversion and molecular electronics. In this work, we present the results of a comparative study of carboxyl-functionalized porphyrins on different oxide nanomaterials. Specifically, we investigated the interaction of 5(3-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-3-MCTPP) and 5(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-4-MCTPP), on MgO, TiO2, and Co3O4 nanoparticles (NPs) using isothermal and temperature-programmed diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). We show that both porphyrins bind to the NPs, yielding stable monolayer films consisting of tilted surface carboxylates. In all cases, anchoring through the carboxylic acid group suppresses self-metalation of the porphyrin unit. Upon annealing, all anchored porphyrin films undergo metalation. The position of the acid group has no major influence on the reactivity. The same is true for the nature of the metal oxide, suggesting that the observed behaviour is general for most anchored porphyrin films on oxide nanomaterials.

Thin water films and particle morphology evolution in nanocrystalline MgO.

A key question in the field of ceramics and catalysis is how and to what extent residual water in the reactive environment of a metal oxide particle powder affects particle coarsening and morphology. With X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), we investigated annealing-induced morphology changes on powders of MgO nanocubes in different gaseous H2O environments. The use of such a model system for particle powders enabled us to describe how adsorbed water that originates from short exposure to air determines the evolution of MgO grain size, morphology, and microstructure. While cubic nanoparticles with a predominant abundance of (100) surface planes retain their shape after annealing to T = 1173 K under continuous pumping with a base pressure of water p(H2O) = 10-5 mbar, higher water partial pressures promote mass transport on the surfaces and across interfaces of such particle systems. This leads to substantial growth and intergrowth of particles and simultaneously favors the formation of step edges and shallow protrusions on terraces. The mass transfer is promoted by thin films of water providing a two-dimensional solvent for Mg2+ ion hydration. In addition, we obtained direct evidence for hydroxylation-induced stabilization of (110) faces and step edges of the grain surfaces.

Bovine Serum Albumin Adsorption on TiO2 Colloids: The Effect of Particle Agglomeration and Surface Composition.

Protein adsorption at nanostructured oxides strongly depends on the synthesis conditions and sample history of the material investigated. We measured the adsorption of bovine serum albumin (BSA) to commercial Aeroxide TiO2 P25 nanoparticles in aqueous dispersions. Significant changes in the adsorption capacity were induced by mild sample washing procedures and attributed to the structural modification of adsorbed water and surface hydroxyls. Motivated by the lack of information about the sample history of commercial TiO2 nanoparticle samples, we used vapor-phase-grown TiO2 nanoparticles, a well-established model system for adsorption and photocatalysis studies, and performed on this material for the first time a systematic and quantitative BSA adsorption study. After alternating vacuum and oxygen treatment of the nanoparticle powders at elevated temperatures for surface purification, we determined size distributions covering both the size of the individualized nanoparticles and nanoparticle agglomerates using transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS) in an aqueous dispersion. Quantitative BSA adsorption measurements at different pH values and thus variable combinations of surface-charged proteins and TiO2 nanoparticles revealed a consistent picture: BSA adsorbs only at the outer agglomerate surfaces without penetrating the interior of the agglomerates. This process levels at coverages of single monolayers, which resist consecutive simple washing procedures. A detailed analysis of the protein-specific IR amide bands reveals that the adsorption-induced protein conformational change is associated with a decrease in the helical content. This study underlines that robust qualitative and quantitative statements about protein adsorption and corona formation require well-documented and controllable surface properties of the nanomaterials involved.

Enzyme adsorption-induced activity changes: a quantitative study on TiO2 model agglomerates.

BACKGROUND: Activity 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. RESULTS: Vapor 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 ß-galactosidase (ß-gal) to these dispersions leads to complete enzyme adsorption and the generation of ß-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 ß-gal/TiO2 heteroaggregates reveals an adsorption-induced decrease of the ß-sheet content and the formation of random structures leading to the deterioration of the active site. CONCLUSIONS: The 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.

Hydroxylation Induced Alignment of Metal Oxide Nanocubes.

Water vapor is ubiquitous under ambient conditions and may alter the shape of nanoparticles. How to utilize water adsorption for nanomaterial functionality and structure formation, however, is a yet unexplored field. Herein, we report the use of water vapor to induce the self-organization of MgO nanocubes into regularly staggered one-dimensional structures. This transformation evolves via an initial alignment of the MgO cubes, the formation of intermediate elongated Mg(OH)2 structures, and their reconversion into MgO cubes arranged in staggered structures. Ab initio DFT modelling identifies surface-energy changes associated with the cube surface hydration and hydroxylation to promote the uncommon staggered stacked assembly of the cubes. This first observation of metal oxide nanoparticle self-organization occurring outside a bulk solution may pave novel routes for inducing texture in ceramics and represents a great test-bed for new surface-science concepts.

Porphyrin Metalation at MgO Surfaces: A Spectroscopic and Quantum Mechanical Study on Complementary Model Systems.

We show that both single-crystalline and nanostructured MgO surfaces convert free-base tetraphenyl porphyrin (2HTPP) into magnesium tetraphenyl porphyrin (MgTPP) at room temperature. The reaction can be viewed as an ion exchange between the two aminic protons of the 2HTPP molecule with a Mg(2+) ion from the surface. The driving force for the reaction is the strong stability of the formed hydroxyl groups along the steps and at defects on the MgO surface. We have used an integrated characterization approach that includes UV/Vis diffuse reflectance measurements on nanostructured powders, X-ray photoelectron spectroscopic investigation of atomically clean MgO(100) single-crystalline thin films, and density functional theory (DFT) calculations on model systems. The DFT calculations demonstrate that MgTPP formation is strongly exothermic at the corners, edges and steps, but slightly endothermic on terrace sites. This agrees well with the UV/Vis diffuse reflectance, which upon adsorption of 2HTPP shows a decrease in the absorption band associated with corner and edge sites on MgO nanocube powders.

Changing interfaces: Photoluminescent ZnO nanoparticle powders in different aqueous environments.

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 O i 2 - in the near surface region and tracked their specific PL emission response at hvEM = 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 O2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hvEM = 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.

Size effects in MgO cube dissolution.

Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg(2+)-O(2-) surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)2 nanosheets. At a pH ≥ 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)2 nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm ≤ d ≤ 1000 nm they dissolve with a significantly smaller dissolution rate in water. On these particles water induced etching generates (110) faces which, above a certain face area, dissolve at a rate equal to that of (100) planes.1 The delayed solubility of microcrystalline MgO is attributed to surface hydroxide induced self-inhibition effects occurring at the (100) and (110) microplanes. The present work underlines the importance of morphology evolution and surface faceting of engineered nanomaterials particles during their dissolution.

Photoluminescence quenching in compressed MgO nanoparticle systems.

Efficient use of highly dispersed metal oxides for lighting, energy conversion and catalysis requires knowledge about the impact of density and microstructure of the powders on the optical nanoparticle properties. For MgO nanocube powders we present a combined photoluminescence (PL) and electron paramagnetic resonance (EPR) approach which enables for samples of different aggregation states the quantification of the fractional powder volume that becomes illuminated with UV and visible light during the PL measurements. Using O2 as a PL emission quencher and - after light induced exciton separation and oxygen adsorption - as an EPR active adsorbate we observed clear aggregation dependent trends in PL emission quenching that originate from particle-particle contacts. Upon interaction of low coordinated surface elements with the surfaces of adjacent MgO nanocubes, which occurs even at powder consolidation levels that escape sorption analysis, the radiative decay of excited surface states becomes quenched down to 15% of the original intensity. Our results underline the critical role of microstructure and the aggregation state of a nanoparticle ensemble with respect to spectroscopic properties and related adsorption induced changes.

O2 adsorption dependent photoluminescence emission from metal oxide nanoparticles.

Optical properties of metal oxide nanoparticles are subject to synthesis related defects and impurities. Using photoluminescence spectroscopy and UV diffuse reflectance in conjunction with Auger electron spectroscopic surface analysis we investigated the effect of surface composition and oxygen adsorption on the photoluminescence properties of vapor phase grown ZnO and MgO nanoparticles. On hydroxylated MgO nanoparticles as a reference system, intense photoluminescence features exclusively originate from surface excitons, the radiative deactivation of which results in collisional quenching in an O2 atmosphere. Conversely, on as-prepared ZnO nanoparticles a broad yellow emission feature centered at hνEm = 2.1 eV exhibits an O2 induced intensity increase. Attributed to oxygen interstitials as recombination centers this enhancement effect originates from adsorbate-induced band bending, which is pertinent to the photoluminescence active region of the nanoparticles. Annealing induced trends in the optical properties of the two prototypical metal oxide nanoparticle systems, ZnO and MgO, are explained by changes in the surface composition and underline that particle surface and interface changes that result from handling and processing of nanoparticles critically affect luminescence.

On the entangled growth of NaTaO3 cubes and Na2Ti3O7 wires in sodium hydroxide solution.

The entangled growth of sodium titanate Na2Ti3O7 nanowires and sodium tantalate NaTaO3 cubes was investigated with electron microscopy, X-ray diffraction, and UV diffuse reflectance spectroscopy. Depending on the composition of the Ta2O5- and TiO2-particle-based powder mixtures, which served as educts, we observed different types of hybridization effects. These include the titanium-induced contraction of the NaTaO3 perovskite-type unit cell and the generation of electronic defect states in NaTaO3 that give rise to optical subbandgap transitions and tantalum-induced limitations of the Na2Ti3O7 nanowire growth. The transformation from Ta2O5 to NaTaO3 occurs through a dissolution-recrystallization process. A systematic analysis of the impact of different titanium sources on NaTaO3 dispersion and, thus, on the properties of the entangled nanostructures revealed that a perfect intermixture of cubes and nanowires can only be achieved when titanate nanosheets emerge during transformation as reaction intermediates and shield nucleation and growth of isolated NaTaO3 cubes. The here demonstrated approach can be highly instrumental for understanding the nucleation and growth of composite and entangled nanostructures in solution and--at the same time--provides an interesting new class of photoactive composite materials.

Synthesis and aggregation of In2O3 nanoparticles: impact of process parameters on stoichiometry changes and optical properties.

Metal-organic chemical vapor synthesis provides agglomerated In2O3 nanoparticles with a low abundance of particle-particle interfaces. Via exposure to bulk water and subsequent dehydration treatment these powders can be transformed into networks of aggregated nanoparticles. Two major effects arise from the associated emergence of particle-particle interfaces: an enhanced susceptibility to annealing induced n-type doping and a significant red-shift of the optical absorption threshold by 0.2 eV. On the basis of control experiments with pure water, we further explored the impact of the environmental gas atmosphere during annealing on the integral ensemble properties. We found that residual water vapor promotes the mutual attraction of particles, facilitates their condensation, and generates particle-particle interfaces. This work may prove to be of great value for the reproducible production and formulation of percolating metal oxide nanoparticle networks with high control over particle aggregation state, on the one hand, and n-type conductivity as well as optical properties, on the other.