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.

Impurity Segregation and Nanoparticle Reorganization of Indium Doped MgO Cubes.

Metal oxide nanocomposites are non-equilibrium solids and promising precursors for functional materials. Annealing of such materials can provide control over impurity segregation and, depending on the level of consolidation, represents a versatile approach to engineer free surfaces, particle-particle interfaces and grain boundaries. Starting with indium-magnesium-oxide nanoparticle powders obtained via injection of an indium organic precursor into the magnesium combustion flame and subsequent particle quenching in argon, we investigated the stability of the trivalent In3+ ions in the host lattice of MgO nanoparticles by determining grain growth, morphology evolution and impurity segregation. The latter process is initiated by vacuum annealing at 873 K and can be tracked at 1173 K on a time scale of minutes. In the first instance the surface segregated indium wets the nanoparticle interfaces. After prolonged annealing indium evaporates and leaves the powder via the gas phase. Resulting MgO nanocubes are devoid of residual indium, regain their high morphological definition and show spectroscopic fingerprints (UV Diffuse Reflectance and Photoluminescence emission) that are characteristic of electronically unperturbed MgO cube corner and edge features. The results of this combined XRD, TEM, and spectroscopy study reveal the parameter window within which control over indium segregation is used to introduce a semiconducting metal oxide component into the intergranular region between insulating MgO nanograins.

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.

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.

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.

A feasible way to remove the heat during adsorptive methane storage.

Methane originating from biogas or natural gas is an attractive and environmentally friendly alternative to gasoline. Adsorption is seen as promising storage technology, but the heat released limits fast filling of these systems. Here a lab scale adsorptive methane storage tank, capable to study the temperature increase during fast filling, was realized. A variation of the filling time from 1 h to 31 s, showed a decrease of the storage capacity of 14% and temperature increase of 39.6 °C. The experimental data could be described in good accordance with a finite element simulation solving the transient mass, energy, and impulse balance. The simulation was further used to extrapolate temperature development in real sized car tanks and for different heat pipe scenarios, resulting in temperature rises of approximately 110 °C. It could be clearly shown, that with heat conductivity as solei mechanism the heat cannot be removed in acceptable time. By adding an outlet to the tank a feed flow cooling with methane as heat carrier was realized. This setup was proofed in simulation and lab scale experiments to be a promising technique for fast adsorbent cooling and can be crucial to leverage the full potential of adsorptive methane gas storage.