Precursor- and waste-free synthesis of spark-ablated nanoparticles with enhanced photocatalytic activity and stability towards airborne organic pollutant degradation.

Photocatalyst synthesis typically involves multiple steps, expensive precursors, and solvents. In contrast, spark ablation offers a simple process of electrical discharges in a gap between two electrodes made from a desirable material. This enables a precursor- and waste-free generation of pure metal oxide nanoparticles or mixtures of various compositions. This study presents a two-step method for the production of photocatalytic filters with deposited airborne MnOx, TiO2, and ZnO nanoparticles using spark ablation and calcination processes. The resulting MnOx and TiO2 filters demonstrated almost twice the activity with outstanding performance stability, as compared to sol-gel MnO2 and commercial TiO2. The introduced method is not only simple, precursor- and waste-free, and leads to superior performance for the case studied, but it also has future potential due to its versatility. It can easily produce mixed and doped materials with further improved properties, making it an interesting avenue for future research.

Cataluminescence in Er-Substituted Perovskites.

Thermophotovoltaic devices have promising applications for energy conversion. However, current conversion efficiency of chemical energy to light is very low, limited by the competing process of heat dissipation released as black body radiation. From a fundamental point of view, the direct conversion of chemical energy into light without this detour is possible. This so called cataluminescence from methanol combustion over Er-substituted SrTiO3 with high efficiency is demonstrated. The catalytically active quaternary perovskites Er0.15 La0.15 Sr0.55 Ti0.95 Cu0.05 O3 - δ exsolute and reabsorb metallic Cu particles onto the surface in reducing and oxidizing conditions, respectively. Thus, it is able to manipulate the surface structure and investigate its influence on the catalytic as well as luminescent properties. The fuel to air ratio around the stoichiometry point changes the conditions from reducing to oxidizing and thereby alters the surface properties. This is evidenced by post mortem X-ray diffraction and X-ray photoemission as well as operando optical spectroscopy. Cataluminescence takes place under oxidizing conditions (lean fuel to air mixture) on the Er-perovskite oxide with a strong selective near infrared emission, while reducing conditions stimulate formation of plasmonic Cu-nanoparticles, which emit black body radiation.

Hydrogen in methanol catalysts by neutron imaging.

Although of pivotal importance in heterogeneous hydrogenation reactions, the amount of hydrogen on catalysts during reactions is seldom known. We demonstrate the use of neutron imaging to follow and quantify hydrogen containing species in Cu/ZnO catalysts operando during methanol synthesis. The steady-state measurements reveal that the amount of hydrogen containing intermediates is related to the reaction yields of CO and methanol, as expected from simple considerations of the likely reaction mechanism. The time-resolved measurements indicate that these intermediates, despite indispensable within the course of the reaction, slow down the overall reaction steps. Hydrogen-deuterium exchange experiments indicate that hydrogen reduction of Cu/ZnO nano-composites modifies the catalyst in such a way that at operating temperatures, hydrogen is dynamically absorbed in the ZnO-nanoparticles. This explains the extraordinary good catalysis of copper if supported on ZnO by its ability to act as a hydrogen reservoir supplying hydrogen to the surface covered by CO2, intermediates, and products during catalysis.

Carboxylate Functional Groups Mediate Interaction with Silver Nanoparticles in Biofilm Matrix.

Biofilms causing medical conditions or interfering with technical applications can prove undesirably resistant to silver nanoparticle (AgNP)-based antimicrobial treatment, whereas beneficial biofilms may be adversely affected by the released silver nanoparticles. Isolated biofilm matrices can induce reduction of silver ions and stabilization of the formed nanosilver, thus altering the exposure conditions. We thus study the reduction of silver nitrate solution in model experiments under chemically defined conditions as well as in stream biofilms. Formed silver nanoparticles are characterized by state-of-the art methods. We find that isolated biopolymer fractions of biofilm organic matrix are capable of reducing ionic Ag, whereas other isolated fractions are not, meaning that biopolymer fractions contain both reducing agent and nucleation seed sites. In all of the investigated systems, we find that silver nanoparticle-biopolymer interface is dominated by carboxylate functional groups. This suggests that the mechanism of nanoparticle formation is of general nature. Moreover, we find that glucose concentration within the biofilm organic matrix correlates strongly with the nanoparticle formation rate. We propose a simple mechanistic explanation based on earlier literature and the experimental findings. The observed generality of the extracellular polymeric substance/AgNP system could be used to improve the understanding of impact of Ag+ on aqueous ecosystems, and consequently, to develop biofilm-specific medicines and bio-inspired water decontaminants.

Hydrogen reduction of molybdenum oxide at room temperature.

The color changes in chemo- and photochromic MoO3 used in sensors and in organic photovoltaic (OPV) cells can be traced back to intercalated hydrogen atoms stemming either from gaseous hydrogen dissociated at catalytic surfaces or from photocatalytically split water. In applications, the reversibility of the process is of utmost importance, and deterioration of the layer functionality due to side reactions is a critical challenge. Using the membrane approach for high-pressure XPS, we are able to follow the hydrogen reduction of MoO3 thin films using atomic hydrogen in a water free environment. Hydrogen intercalates into MoO3 forming HxMoO3, which slowly decomposes into MoO2 +1/2 H2O as evidenced by the fast reduction of Mo6+ into Mo5+ states and slow but simultaneous formation of Mo4+ states. We measure the decrease in oxygen/metal ratio in the thin film explaining the limited reversibility of hydrogen sensors based on transition metal oxides. The results also enlighten the recent debate on the mechanism of the high temperature hydrogen reduction of bulk molybdenum oxide. The specific mechanism is a result of the balance between the reduction by hydrogen and water formation, desorption of water as well as nucleation and growth of new phases.