Characterizing photocatalysts for water splitting: from atoms to bulk and from slow to ultrafast processes

Research on light-driven catalysis has gained tremendous importance due to the ever-increasing power consumption and the threatening situation of global warming related to burning fossil fuels. Significant efforts have been dedicated to artificial photosynthesis mimicking nature to split H2O into H2 and O2 by solar energy. Novel semiconductor und molecular photocatalysts focusing on one-step excitation processes via single component photocatalysts or via two-step excitation processes mimicking the Z-scheme of natural photosynthesis are currently developed. Analytical and physicochemical methods, which provide information at different time and length scales, are used to gain fundamental understanding of all processes leading to catalytic activity, i.e., light absorption, charge separation, transfer of charges to the reaction centres and catalytic turnover, but also understanding degradation processes of the photocatalytic active material. Especially, molecular photocatalysts still suffer from limited long-Term stability due to the formation of reactive intermediates, which may lead to degradation. Although there is an overwhelming number of research articles and reviews focussing on various materials for photocatalytic water splitting, to date only few reviews have been published providing a comprehensive overview on methods for characterizing such materials. This review will highlight spectroscopic, spectroelectrochemical, and electrochemical approaches in respect to their potential in studying processes in semiconductor and (supra)molecular photocatalysts. Special emphasis will be on spectroscopic methods to investigate light-induced processes in intermediates of sequential electron transfer chains. Further, microscopic characterization methods, which are predominantly used for semiconducting and hybrid photocatalytic materials will be reviewed as surface area, structure, facets, defects, and bulk properties such as crystallinity and crystal size are key parameters for charge separation, transfer processes and suppression of charge recombination. Recent developments in scanning probe microscopy will also be highlighted as such techniques are highly suited for studying photocatalytic active material. © The Royal Society of Chemistry

Optimization of total vaporization solid-phase microextraction (TV-SPME) for the determination of lipid profiles of Phormia regina, a forensically important blow fly species

A new method has been developed for the determination of fatty acids, sterols, and other lipids which naturally occur within pupae of the blow fly Phormia regina. The method relies upon liquid extraction in non-polar solvent, followed by derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) w/ 1% trimethylchlorsilane (TMCS) carried out inside the sample vial. The analysis is facilitated by total vaporization solid-phase microextraction (TV-SPME), with gas chromatography-mass spectrometry (GC-MS) serving as the instrumentation for analysis. The TV-SPME delivery technique is approximately a factor of five more sensitive than traditional liquid injection, which may alleviate the need for rotary evaporation, reconstitution, collection of high performance liquid chromatography fractions, and many of the other pre-concentration steps that are commonplace in the current literature. Furthermore, the ability to derivatize the liquid extract in a single easy step while increasing sensitivity represents an improvement over current derivatization methods. The most common lipids identified in fly pupae were various saturated and unsaturated fatty acids ranging from lauric acid (12:0) to arachinoic acid (20:4), as well as cholesterol. The concentrations of myristic acid (14:0), palmitelaidic acid (16:2), and palmitoleic acid (16:1) were the most reliable indicators of the age of the pupae

Factors Affecting Species Identifications of Blow Fly Pupae Based upon Chemical Profiles and Multivariate Statistics

Alternative methods for the identification of species of blow fly pupae have been developed over the years that consist of the analyses of chemical profiles. However, the effect of biotic and abiotic factors that could influence the predictive manner for the tests have not been evaluated. The lipids of blowfly pupae (Cochliomyia macellaria, Lucilia cuprina, Lucilia sericata, and Phormia regina) were extracted in pentane, derivatized, and analyzed by total-vaporization solid phase microextraction gas chromatography-mass spectrometry (TV-SPME GC-MS). Peak areas for 26 compounds were analyzed. Here we evaluated one biotic factor (colonization) on four species of blow flies to determine how well a model produced from lipid profiles of colonized flies predicted the species of flies of offspring of wild-caught flies and found very good species identification following 10 generations of inbreeding. When we evaluated four abiotic factors in our fly rearing protocols (temperature, humidity, pupation substrate, and diet), we found that the ability to assign the chemical profile to the correct species was greatly reduced

Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Sodium-ion batteries are among the most promising alternatives to lithium-ion batteries. Hard carbon (HC) electrodes have been recognized as suitable active anode material for mono-valent ion batteries. Here, we present a simple and cost-effective spray-coating process to prepare HC composite electrodes on copper current collectors with different binder (sodium carboxymethyl cellulose, CMC) content and different HC particle sizes. The spray-coated electrodes were evaluated and tested in 1 M sodium perchlorate (NaClO$_4$) in propylene carbonate (PC) in dependence of the CMC content with and without fluoroethylene carbonate (FEC) as additive, and the performance was also compared to doctor bladed HC electrodes. Spray-coated anodes in Na half-cells revealed improved capacity during the first cycles compared with doctor bladed anodes with similar thicknesses. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) studies were performed, which revealed a significant increase of inorganic fluoro-compounds in the formed solid electrolyte interphase (SEI) when FEC was present as additive. In addition, first single electrode microcalorimetry studies on spray-coated thin HC composite electrodes yielded an entropy of the sodiation process of 80 J mol$^{−1}$ K$^{−1}$ at high state of charge (SoC), comparable to that of bulk Na deposition

Modification of Al Surface via Acidic Treatment and its Impact on Plating and Stripping

Amorphous Al$_2$O$_3$ film that naturally exists on any Al substrate is a critical bottleneck for the cyclic performance of metallic Al in rechargeable Al batteries. The so-called electron/ion insulator Al oxide slows down the anode\u27s activation and hinders Al plating/stripping. The Al$_2$O$_3$ film induces different surface properties (roughness and microstructure) on the metal. Al foils present two optically different sides (shiny and non-shiny), but their surface properties and influence on plating and stripping have not been studied so far. Compared to the shiny side, the non-shiny one has a higher (~28 %) surface roughness, and its greater concentration of active sites (for Al plating and stripping) yields higher current densities. Immersion pretreatments in Ionic-Liquid/AlCl$_3$-based electrolyte with various durations modify the surface properties of each side, forming an electrode-electrolyte interphase layer rich in Al, Cl, and N. The created interphase layer provides more tunneling paths for better Al diffusion upon plating and stripping. After 500 cycles, dendritic Al deposition, generated active sites, and the continuous removal of the Al metal and oxide cause accelerated local corrosion and electrode pulverization. We highlight the mechanical surface properties of cycled Al foil, considering the role of immersion pretreatment and the differences between the two sides

Simultaneous pit generation and visualization of pit topography using combined atomic force-scanning electrochemical microscopy

Combined atomic force microscopy – scanning electrochemical microscopy (AFM-SECM) is for the first time used to generate single corrosion pits on passivating iron surfaces in the micrometer range. The AFM-SECM probe locally generates nitric acid during the oxidation of nitrite ions with the release of protons at selected sites on the surface of the otherwise passive metal. High confinement of passive film breakdown is achieved from the combination of a small probe size and the inhibiting properties of non-reacted nitrite ions on the surrounding passivated surface. Simultaneous visualization of pit nucleation and propagation can be obtained in the same solution without changing the probe by AFM

In situ investigation of copper corrosion in acidic chloride solution using atomic force - scanning electrochemical microscopy

The anodic dissolution of pure copper surfaces in acidic chloride solution has been monitored in-situ using combined atomic force – scanning electrochemical microscopy (AFM-SECM). Here, the initial studies performed on model copper-modified substrates have been extended to the investigation of bulk copper samples used in industrial settings. The local release of Cu2+ ions was monitored through electrochemical reduction and deposition of the metal ions on the conductive frame of the AFM-SECM probe. Simultaneous monitoring of the topographical changes due to the corrosion process allowed the distinction and correlation of local passivation and pitting phenomena. The extent of the attack was estimated by anodic stripping of the copper metal deposited at the probe

In situ monitoring of pit nucleation and growth at iron passive oxide layer using combined atomic force and scanning electrochemical microscopy

Generation of single corrosion pits and in situ monitoring of pit growth on iron exposed to 0.5 M NaCl solution was achieved using combined atomic force - scanning electrochemical microscopy (AFM-SECM). Pits as small as 2.7 μm in diameter were formed at arbitrary locations on the substrate by local generation of highly concentrated nitric acid in the vicinity of the AFM-SECM probe. Addition of nitrite ions to the environment, which act as corrosion inhibitors for iron, ensures passivation of the metal, and hinders metal corrosion despite exposure to the chloride-containing media. Localized acidification was achieved by oxidizing nitrite ions at the probe. Acidification in combination with the high chloride content in the solution leads to a local rapid attack at the surface and pit generation below the AFM-SECM probe. Besides improved spatial resolution and precise control of the pit nucleation site, combined AFM-SECM allows simultaneous imaging of the generated pits by the AFM tip

Surface Physicochemical Properties At The Micro And Nano Length Scales: Role On Bacterial Adhesion And Xylella Fastidiosa Biofilm Development.

The phytopathogen Xylella fastidiosa grows as a biofilm causing vascular occlusion and consequently nutrient and water stress in different plant hosts by adhesion on xylem vessel surfaces composed of cellulose, hemicellulose, pectin and proteins. Understanding the factors which influence bacterial adhesion and biofilm development is a key issue in identifying mechanisms for preventing biofilm formation in infected plants. In this study, we show that X. fastidiosa biofilm development and architecture correlate well with physicochemical surface properties after interaction with the culture medium. Different biotic and abiotic substrates such as silicon (Si) and derivatized cellulose films were studied. Both biofilms and substrates were characterized at the micro- and nanoscale, which corresponds to the actual bacterial cell and membrane/ protein length scales, respectively. Our experimental results clearly indicate that the presence of surfaces with different chemical composition affect X. fastidiosa behavior from the point of view of gene expression and adhesion functionality. Bacterial adhesion is facilitated on more hydrophilic surfaces with higher surface potentials; XadA1 adhesin reveals different strengths of interaction on these surfaces. Nonetheless, despite different architectural biofilm geometries and rates of development, the colonization process occurs on all investigated surfaces. Our results univocally support the hypothesis that different adhesion mechanisms are active along the biofilm life cycle representing an adaptation mechanism for variations on the specific xylem vessel composition, which the bacterium encounters within the infected plant.8e7524