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The resurgence of interest in hydrogen-related technologies has stimulated new studies aimed at advancing lesser-developed water-splitting processes, such as solar thermochemical hydrogen production (STCH). Progress in STCH has been largely hindered by a lack of new materials able to efficiently split water at a rate comparable to ceria under identical experimental conditions. BaCe0.25Mn0.75O3 (BCM) recently demonstrated enhanced hydrogen production over ceria and has the potential to further our understanding of two-step thermochemical cycles. A significant feature of the 12R hexagonal perovskite structure of BCM is the tendency to, in part, form a 6H polytype at high temperatures and reducing environments (i.e., during the first step of the thermochemical cycle), which may serve to mitigate degradation of the complex oxide. An analogous compound, namely BaNb0.25Mn0.75O3 (BNM) with a 12R structure was synthesized and displays nearly complete conversion to the 6H structure under identical reaction conditions as BCM. The structure of the BNM-6H polytype was determined from Rietveld refinement of synchrotron powder X-ray diffraction data and is presented within the context of the previously established BCM-6H structure.

Understanding the role of oxygen vacancy–induced atomic and electronic structural changes to complex metal oxides during water-splitting processes is paramount to advancing the field of solar thermochemical hydrogen production (STCH). The formulation and confirmation of a mechanism for these types of chemical reactions necessitate a multifaceted experimental approach, featuring advanced structural characterization methods. Synchrotron X-ray techniques are essential to the rapidly advancing field of STCH in part due to properties such as high brilliance, high coherence, and variable energy that provide sensitivity, resolution, and rapid data acquisition times required for the characterization of complex metal oxides during water-splitting cycles. X-ray diffraction (XRD) is commonly used for determining the structures and phase purity of new materials synthesized by solid-state techniques and monitoring the structural integrity of oxides during water-splitting processes (e.g., oxygen vacancy–induced lattice expansion). X-ray absorption spectroscopy (XAS) is an element-specific technique and is sensitive to local atomic and electronic changes encountered around metal coordination centers during redox. While in operando measurements are desirable, the experimental conditions required for such measurements (high temperatures, controlled oxygen partial pressures, and H2O) practically necessitate in situ measurements that do not meet all operating conditions or ex situ measurements. Here, we highlight the application of synchrotron X-ray scattering and spectroscopic techniques using both in situ and ex situ measurements, emphasizing the advantages and limitations of each method as they relate to water-splitting processes. The best practices are discussed for preparing quenched states of reduction and performing synchrotron measurements, which focus on XRD and XAS at soft (e.g., oxygen K-edge, transition metal L-edges, and lanthanide M-edges) and hard (e.g., transition metal K-edges and lanthanide L-edges) X-ray energies. The X-ray absorption spectra of these complex oxides are a convolution of multiple contributions with accurate interpretation being contingent on computational methods. The state-of-the-art methods are discussed that enable peak positions and intensities to be related to material electronic and structural properties. Through careful experimental design, these studies can elucidate complex structure–property relationships as they pertain to nonstoichiometric water splitting. A survey of modern approaches for the evaluation of water-splitting materials at synchrotron sources under various experimental conditions is provided, and available software for data analysis is discussed.

Minor variations in synthesis conditions can redirect crystallization pathways through different nonequilibrium intermediates. Here, the authors present a theoretical framework to predict which polymorphs appear during MnO2 precipitation, which is validated by in situ X-ray scattering of reaction progression.

Cuprous oxide (Cu2O) is actively studied as a prototypical material for energy conversion and electronic applications. Here we reduce the growth temperature of phase pure Cu2O thin films to 300 °C by intentionally controlling solely the kinetic parameter (total chamber pressure, Ptot) at fixed thermodynamic condition (0.25 mTorr pO2). A strong non-monotonic effect of Ptot on Cu-O phase formation is found using high-throughput combinatorial-pulsed laser deposition. This discovery creates new opportunities for the growth of Cu2O devices with low thermal budget and illustrates the importance of kinetic effects for the synthesis of metastable materials with useful properties.

Transition metal oxides play important roles as contact and electrode materials, but their use as active layers in solar energy conversion requires achieving semiconducting properties akin to those of conventional semiconductors like Si or GaAs. In particular, efficient bipolar carrier transport is a challenge in these materials. Based on the prediction that a tetrahedral polymorph of MnO should have such desirable semiconducting properties, and the possibility to overcome thermodynamic solubility limits by nonequilibrium thin-film growth, we exploit both structure-property and composition-structure relationships to design and realize novel wurtzite-structure Mn_{1−x}Zn_{x}O alloys. At Zn compositions above x≈0.3, thin films of these alloys assume the tetrahedral wurtzite structure instead of the octahedral rocksalt structure of MnO, thereby enabling semiconductor properties that are unique among transition metal oxides, i.e., a band gap within the visible spectrum, a band-transport mechanism for both electron and hole carriers, electron doping, and a band lineup suitable for solar hydrogen generation. A proof of principle is provided by initial photo-electrocatalytic device measurements, corroborating, in particular, the predicted favorable hole-transport properties of these alloys.

For organic photovoltaics (OPVs) to become a truly viable technology, it is critical to correctly identify their degradation mechanism(s) and pave the way for strategies to improve device lifetime. Changes in the active organic component are often cited as the leading degradation pathway in OPVs. In this shelf life study, we monitor device performance after storage in the dark at ambient conditions to show that decay behavior is dominated by changes at the top metal electrode and/or the metal–organic interface. Cross-sectional TEM reveals extensive void formation to be the primary degradation mechanism for Ca/Al contacts. Kelvin probe measurements show the work function of Ag contacts increases over time, consistent with silver oxide formation detected by TOF-SIMS depth profiles. The evolution of the work function is found to be advantageous for Ag as a hole-extracting contact, but unsuitable for electron-extraction. The combination of Ag positive contacts (to collect holes) and ITO/ZnO negative contacts (to collect electrons) yields devices that are stable up to one year when stored in ambient conditions. [ABSTRACT FROM AUTHOR]

This article follows our previous work on the synthesis and characterization of pi-conjugated dendrimers for use in organic solar cells. Here we discuss five new thiophene-based dendrimers that were synthesized in order to study the relationship between their chemical structures and electronic properties. Three of these dendrimers incorporate acetylene spacers, included to relieve steric strain, between the thiophene arms and phenyl cores used in previous studies. Only a small effect on the electronic properties is observed upon inclusion of the acetylene spacer in the three-arm dendrimer, 3G1-2S-Ac. In contrast, a decrease in the bandgap is observed for the four-arm dendrimer, 4G1-2S-Ac, due to a reduction of interactions between the arms in the more sterically congested 1,2,4,5-arrangement around the phenyl core, resulting in delocalization of the exciton through the phenyl core. Incorporation of electron-withdrawing cyano groups on the phenyl core of the three-arm dendrimer, 3G1-2S-CN, resulted in a very large (∼0.5 eV) decrease in the bandgap, due to stabilization of the lowest unoccupied molecular orbital, and the low energy absorption band in this material is attributed to a transition with significant intramolecular charge-transfer character. The electronic properties of three- and four-arm dendrimers with electron-donating dibutylaniline moieties attached to the end of the thiophene dendron, 3G1-2S-N and 4G1-2S-N respectively, are almost identical, indicating that they are dominated by the arms, with no through-core communication allowed, even for the para-linked arms of 4G1-2S-N. However, there is a significant increase in the molar absorptivity of these materials, concomitant with significant broadening of the absorption spectrum, which is an important attribute in light-harvesting applications. [ABSTRACT FROM AUTHOR]