Morphology Dependent Reactivity of CsOx Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH.

Cesium oxide (CsOx) nanostructures grown on Au(111) behave as active centers for the CO2 binding and hydrogenation reactions. The morphology and reactivity of these CsOx systems were investigated as a function of alkali coverage using scanning tunneling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05-0.10 ML) cesium oxide clusters (Cs2O2) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (>0.15 ML). XPS measurements reveal the presence of suboxidic (CsyO; y ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio, resulting in a stronger binding of CO2. Moreover, the O atoms in the CsyO structure undergo a rearrangement upon the adsorption of CO2 which is a reversible phenomenon. Under CO2 hydrogenation conditions, the small Cs2O2 clusters are hydroxylated, thereby preventing the adsorption of CO2. However, the hydroxylation of the higher coverages of CsyO did not prevent CO2 adsorption, and adsorbed CO2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO2 reaction with hydroxylated CsyO. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications, wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.

Study of the Dilution-Induced Deposition of Concentrated Mixtures of Polyelectrolytes and Surfactants.

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights on their behavior in concentrated formulations, less is known on their behavior under practical use conditions, e.g., under dilution and vectorization of deposits. This makes it difficult to make predictions for specific performance, as, for example, good hair manageability after a shampoo or a comfortable sensorial appreciation after a skin cleanser. This is especially important when considering the formulation of new, more eco-friendly formulations. In this work, a detailed study of the phase separation process induced by dilution is described, as well as the impact on the deposition of conditioning material on negatively charged surfaces. In order to gain a more detailed physical insight, several polyelectrolyte-surfactant pairs, formed by two different polymers and five surfactants that, although non-natural or eco-friendly, can be considered as models of classical formulations, have been studied. The results evidenced that upon dilution the behavior, and hence its deposition onto the surface, cannot be predicted in terms of the behavior of simpler pseudo-binary (mixtures of a polymer and a surfactant) or pseudo-ternary mixtures (two polymers and a surfactant). In many cases, phase separation was observed for concentrations similar to those corresponding to the components in some technological formulations, whereas the latter appeared as monophasic systems. Therefore, it may be assumed that the behavior in multicomponent formulations is the result of a complex interplay of synergistic interactions between the different components that will require revisiting when new, more eco-sustainable ingredients are considered.

Sunlight-Operated TiO2-Based Photocatalysts.

Photo-catalysis is a research field with broad applications in terms of potential technological applications related to energy production and managing, environmental protection, and chemical synthesis fields. A global goal, common to all of these fields, is to generate photo-catalytic materials able to use a renewable energy source such as the sun. As most active photocatalysts such as titanium oxides are essentially UV absorbers, they need to be upgraded in order to achieve the fruitful use of the whole solar spectrum, from UV to infrared wavelengths. A lot of different strategies have been pursued to reach this goal. Here, we selected representative examples of the most successful ones. We mainly highlighted doping and composite systems as those with higher potential in this quest. For each of these two approaches, we highlight the different possibilities explored in the literature. For doping of the main photocatalysts, we consider the use of metal and non-metals oriented to modify the band gap energy as well as to create specific localized electronic states. We also described selected cases of using up-conversion doping cations. For composite systems, we described the use of binary and ternary systems. In addition to a main photo-catalyst, these systems contain low band gap, up-conversion or plasmonic semiconductors, plasmonic and non-plasmonic metals and polymers.

Characterization of Photo-catalysts: From Traditional to Advanced Approaches.

The article provides an overview of the most relevant characterization results of heterogeneous photo-catalytic materials available in the literature. First, we present a summary of the ex situ utilization of physico-chemical characterization techniques. In the majority of current works, pre and post-reaction samples are subjected to ex situ analysis using a multitechnique approach which attempts to render information about the morphological, structural, and electronic properties of relevance to interpret photoactivity. Details of the effects on physico-chemical observables of the nanostructure and the complex chemical nature (considering mono and multiphase materials with presence of several chemical elements) of typical photo-catalysts will be analyzed. Modern studies however emphasize the use of in situ tools in order to establish activity-structure links. To this end, the first point to pay attention to is to consider carefully the interaction between light and matter at the reaction cell where the characterization is carried out. Operando and spectro-kinetic methodologies will be reviewed as they would render valuable and trusting results and thus will pave the way for the future developments in photocatalysis.