Combined Effect of Underlayer and Deposition Solution to Optimize the Alignment of Hematite Photoanodes.

This study investigates the optimization of hematite (α-Fe2O3) photoanodes for enhanced photoelectrochemical (PEC) performance and reproducibility, which are crucial for photocatalytic applications. Despite hematite's potential, hindered by inherent limitations, significant improvements were realized by introducing a titanium dioxide (TiO2) underlayer and ethanol-modified deposition. The influence of the deposition methods was understood by potential-dependent photoelectrochemical impedance spectroscopy analysis. The introduction of the TiO2 underlayer effectively increased the density of states, preferable for the electron transport in the bulk hematite, and the ethanol deposition on a TiO2 underlayer led to a stable surface state formation (S1 state) for the photoexcited hole transfer. This analysis illuminated the intricate interplay between electron transport in the bulk and photogenerated hole transfer at the solution interface, thereby facilitating smoother charge transfer. These findings underscore the viability of surface engineering and meticulous process optimization in addressing critical challenges in photocatalyst development.

Illumination-Induced Solute Uptake in Liquid Crystal Droplets: The Role of 5CB Excimers.

This study investigates the phenomenon of solute uptake into liquid crystal (LC) droplets, illuminated under UV light, focusing on the role of 4-cyano-4'-pentylbiphenyl (5CB) excimer formation in this process. Our experiments reveal that upon UV irradiation solute molecules, including surfactants and dyes, are actively drawn into the LC phase, forming distinctive assemblies within the droplets. Contrary to previous assumptions that the uptake was driven by the direct photoreactivity of the solutes, we found that the 5CB excimer state plays a critical role for this phenomenon. This state, identifiable through its photoluminescence yet invisible to conventional UV/vis absorption spectroscopy, correlates strongly with the molecular assembly process inside of the droplets. Notably, this mechanism operates across a broad spectrum of solute molecules, from simple surfactants like sodium dodecyl sulfate (SDS) to complex dyes, demonstrating the generality of the excimer-induced solute uptake. The excimer's role is pivotal, facilitating solute incorporation without reliance on their inherent light-absorbing properties. This insight not only advances our understanding of LC behavior under light irradiation but also opens new avenues for designing light-responsive materials.

A robust methodology for PEC performance analysis of photoanodes using machine learning and analytical data.

Machine learning (ML) is increasingly applied across various fields, including chemistry, for molecular design and optimizing reaction parameters. Yet, applying ML to experimental data is challenging due to the limited number of synthesized samples, which restricts its broader application in device development. In energy harvesting, photoanodes are crucial for solar-driven water splitting, generating hydrogen and oxygen. We explored electrodes like hematite and bismuth vanadate for photocatalytic uses, noting varied photoelectrochemical performances despite similar preparations. To understand this variability, we applied a data-driven ML approach, predicting photocurrent values and identifying key performance influencers even with limited experimental data in the research development of inorganic devices. We have utilized multiple machine learning algorithms to predict the target value in the calculation process, where the contributions of the dominant descriptors were unknown. We introduced a novel methodology, incorporating clustering to manage multicollinearity from correlated analytical data and Shapley analysis for clear interpretation of contributions to performance prediction. This method was validated on hematite and bismuth vanadate, showing superior predictability and factor identification, and then extended to tungsten oxide and bismuth vanadate heterojunction photoanodes. Despite their complexity, our approach achieved determination coefficients (R2) with a prediction accuracy over 0.85, successfully pinpointing performance-determining factors, demonstrating the robustness of the new scheme in advancing photodevice research.

Pattern-illumination time-resolved phase microscopy and its applications for photocatalytic and photovoltaic materials.

Pattern-illumination time-resolved phase microscopy (PI-PM) is a technique used to study the microscopic charge carrier dynamics in photocatalytic and photovoltaic materials. The method involves illuminating a sample with a pump light pattern, which generates charge carriers and they decay subsequently due to trapping, recombination, and transfer processes. The distribution of photo-excited charge carriers is observed through refractive index changes using phase-contrast imaging. In the PI-PM method, the sensitivity of the refractive index change is enhanced by adjusting the focus position, the method takes advantage of photo-excited charge carriers to observe non-radiative processes, such as charge diffusion, trapping in defect/surface states, and interfacial charge transfer of photocatalytic and photovoltaic reactions. The quality of the image sequence is recovered using various informatics calculations. Categorizing and mapping different types of charge carriers based on their response profiles using clustering analysis provides spatial information on charge carrier types and the identification of local sites for efficient and inefficient photo-induced reactions, providing valuable information for the design and optimization of photocatalytic materials such as the cocatalyst effect.

Cocatalyst activity mapping for photocatalytic materials revealed by the pattern-illumination time-resolved phase microscopy.

Photocatalytic water-splitting represents a promising avenue for clean hydrogen production, necessitating an in-depth understanding of the photocatalytic reaction mechanism. The majority of the photocatalytic materials need cocatalysts to enhance the photo-oxidation or reduction reactions. However, the working mechanism, such as collecting charge carriers or reducing the reaction barrier, is not clear because they disperse inhomogeneously on a surface, and it is difficult to follow the local charge carrier behavior. This study employs the pattern-illumination time-resolved phase microscopy (PI-PM) method to unravel the spatial charge carrier behavior in photocatalytic systems, utilizing time-resolved microscopic image (refractive index change) sequences and their clustering analyses. This approach is robust for studying the change in local charge carrier behavior. We studied two major cocatalyst effects on photocatalysts: TiO2 with/without Pt and hematite with/without CoPi. The PI-PM method, supported by charge type clustering and the effects of scavengers, allowed for the analysis of local activity influenced by cocatalysts. This approach revealed that the introduction of cocatalysts alters the local distribution of charge carrier behavior and significantly impacts their decay rates. In TiO2 systems, the presence of Pt cocatalysts led to a local electron site on the micron scale, extending the lifetime to a few tens of microseconds from a few microseconds. Similarly, in hematite films with CoPi, we observed a notable accumulation of holes at cocatalyst sites, emphasizing the role of cocatalysts in enhancing photocatalytic efficiency. The study's findings highlight the complexity of charge carrier dynamics in photocatalytic processes and the significant influence of cocatalysts.

Simultaneous Structural and Electronic Engineering on Bi- and Rh-co-doped SrTiO3 for Promoting Photocatalytic Water Splitting.

Activating metal ion-doped oxides as visible-light-responsive photocatalysts requires intricate structural and electronic engineering, a task with inherent challenges. In this study, we employed a solid (template)-molten (dopants) reaction to synthesize Bi- and Rh-codoped SrTiO3 (SrTiO3:Bi,Rh) particles. Our investigation reveals that SrTiO3:Bi,Rh manifests as single-crystalline particles in a core (undoped)/shell (doped) structure. Furthermore, it exhibits a well-stabilized Rh3+ energy state for visible-light response without introducing undesirable trapping states. This precisely engineered structure and electronic configuration promoted the generation of high-concentration and long-lived free electrons, as well as facilitated their transfer to cocatalysts for H2 evolution. Impressively, SrTiO3:Bi,Rh achieved an exceptional apparent quantum yield (AQY) of 18.9% at 420 nm, setting a new benchmark among Rh-doped-based SrTiO3 materials. Furthermore, when integrated into an all-solid-state Z-scheme system with Mo-doped BiVO4 and reduced graphene oxide, SrTiO3:Bi,Rh enabled water splitting with an AQY of 7.1% at 420 nm. This work underscores the significance of simultaneous structural and electronic engineering and introduces the solid-molten reaction as a viable approach for this purpose.

Formation of topological defects at liquid/liquid crystal interfaces in micro-wells controlled by surfactants and light.

Topological defects, the fundamental entities arising from symmetry-breaking, have captivated the attention of physicists, mathematicians, and materials scientists for decades. Here we propose and demonstrate a novel method for robust control of topological defects in a liquid crystal (LC), an ideal testbed for the investigation of topological defects. A liquid layer is introduced on the LC in microwells in a microfluidic device. The liquid/LC interface facilitates the control of the LC alignment thereby introducing different molecules in the liquid/LC phase. A topological defect is robustly formed in a microwell when the liquid/LC interface and the microwell surface impose planar and homeotropic alignment, respectively. We also demonstrate the formation/disappearance of topological defects by light illumination, realized by dissolving photo-responsive molecules in the LC. Our platform that facilitates the control of LC topological defects by the introduction of different molecules and external stimuli could have potential for sensor applications.

Prediction of the photoelectrochemical performance of hematite electrodes using analytical data.

Machine learning (ML) has been extensively utilized in various fields of chemistry, such as molecular design and optimization of the fabrication parameters of the material. However, there is still a difficulty in applying ML for devices/materials fabricated in a lab because plenty of data for accurate calculation are difficult to obtain due to the limited number of samples. As a promising energy-harvesting material, we have studied hematite electrodes for photocatalytic water splitting. Herein, we have examined the critical factors affecting the photoelectrochemical (PEC) performance by applying ML for a limited number of fabricated electrodes to reveal the origin of poor reproducibility of the performance. To find the dominant factors affecting the PEC performance, the feature values were directly extracted from analytical data such as X-ray diffraction, Raman, UV/vis and photoelectrochemical impedance spectroscopy (PEIS) measurements. The dominant factors for the performance were identified from the prediction analysis of the performance by ML. Two types of descriptors were examined; all the analytical data were included and those without the PEIS data, which had a high correlation with the photocurrent. The determination coefficients (R2) of the prediction accuracy were >0.8 in both cases and the dominant features were identified for the improvement of PEC performance without any prior knowledge.

Local charge carrier dynamics of a particulate Ga-doped La5Ti2Cu0.9Ag0.1O7S5 photocatalyst and the impact of Rh cocatalysts.

Visible-light responsive photocatalytic materials are expected to be deployed for practical use in photocatalytic water splitting. One of the promising materials as a p-type semiconductor, oxysulfides, was investigated in terms of the local charge carrier behavior for each particle by using a home-built time-resolved microscopic technique in combination with clustering analysis. We could differentiate electron and hole trapping to the surface states and the following recombination on a micron-scale from the nanosecond to microsecond order. The map of the charge carrier type revealed that charge trapping sites for electrons and holes were spatially separated within each particle/aggregate. Furthermore, the effect of the rhodium cocatalyst was recognized as a new electron pathway, trapping to the rhodium site and the following recombination, which was delayed compared with the original electron recombination process. The Rh effect was discussed based on the phenomenological simulation, revealing a possible reason for the decay was due to the anisotropic diffusion of charge carriers in oxysulfides or the interfacial energy barrier at the interface.

Polyploid QTL-seq towards rapid development of tightly linked DNA markers for potato and sweetpotato breeding through whole-genome resequencing.

Potato (Solanum tuberosum L.) and sweetpotato (Ipomoea batatas L.), which are nutritionally and commercially important tuberous crops, possess a perplexing heredity because of their autopolyploid genomes. To reduce cross-breeding efforts for selecting superior cultivars from progenies with innumerable combinations of traits, DNA markers tightly linked to agronomical traits are required. To develop DNA markers, we developed a method for quantitative trait loci (QTL) mapping using whole-genome next-generation sequencing (NGS) in autopolyploid crops. To apply the NGS-based bulked segregant method, QTL-seq was modified. (1) Single parent-specific simplex (unique for one homologous chromosome) single-nucleotide polymorphisms (SNPs), which present a simple segregation ratio in the progenies, were exploited by filtering SNPs by SNP index (allele frequency). (2) Clusters of SNPs, which were inherited unevenly between bulked progenies with opposite phenotypes, especially those with an SNP index of 0 for the bulk that did not display the phenotypes of interest, were explored. These modifications allowed for separate tracking of alleles located on each of the multiple homologous chromosomes. By applying this method, clusters of SNPs linked to the potato cyst nematode resistance H1 gene and storage root anthocyanin (AN) content were identified in tetraploid potato and hexaploid sweetpotato, respectively, and completely linked DNA markers were developed at the site of the presented SNPs. Thus, polyploid QTL-seq is a versatile method that is free from specialized manipulation for sequencing and construction of elaborate linkage maps and facilitates rapid development of tightly linked DNA markers in autopolyploid crops, such as potato and sweetpotato.

Multivariate curve resolution combined with estimation by cosine similarity mapping of analytical data.

We developed a multivariate curve resolution (MCR) calculation combined with the mapping of cosine similarity (cos-s) for estimating multiple mixture spectra of chemicals. The cos-s map was obtained by calculating the similarities of the variation of the signal intensities at each scanning parameter, such as the wavelength. The cos-s map was utilized for the initial estimation of the spectra of pure chemicals and also for the restriction of the iterative least-squares calculation of the MCR. These calculations were performed without arbitrary parameters by introducing soft clustering to the cos-s map. The chemically meaningful initial estimation could prevent the convergence at an incorrect local minimum, which frequently happens for the wrong initial estimation of spectra far away from the real answer. Herein, we demonstrated the robustness of this calculation method by applying it for UV/Vis spectra and XRD patterns of multiple unknown chemical mixtures, whose shapes were totally different (broad overlapped peaks and multiple complicated peaks). Pure spectra/patterns were recovered as >84% consistency with the reference spectra, and <6% accuracy of the concentration ratios was demonstrated.

Photo-excited charge carrier imaging by time-resolved pattern illumination phase microscopy.

A nanosecond time-resolved imaging technique has been developed for the observation of the photo-excited charge carrier dynamics in photo-devices such as photocatalysts and solar cells. An arbitrary spatial pattern of pump pulse light excites the charge carriers, which are observed by phase-contrast imaging. This patterned excitation is preferable for various statistical image reconstruction techniques based on robust principal component analysis and the least absolute shrinkage and selection operator, which helped the enhancement of the signal-to-noise ratio and the removal of unwanted image components. By using data assimilation with the charge decay model, the lifetime and diffusion coefficients were mapped for the photo-excited electrons in a nano-particulate titanium oxide film and other photo-device materials.

Optical motion control of liquid crystalline droplets by host-guest molecular interaction.

Photo-induced motion is demonstrated for a photo-responsive dye-doped liquid crystal (LC) droplet in a surfactant solution. The LC droplets started rolling on a substrate during UV irradiation and moved either toward or away from the UV light, depending on the functional groups of the guest dyes. The mechanism is explained by the Marangoni flow caused by the photo-isomerization-induced adsorption and desorption of the dye molecules to and from the LC/solution interfaces.

An initial estimation method using cosine similarity for multivariate curve resolution: application to NMR spectra of chemical mixtures.

Multivariate curve resolution (MCR) has been widely utilized to reveal the constituents of chemicals from multiple spectral data of chemical mixtures. In the MCR calculation, the singular value decomposition (SVD) has been utilized to obtain the initial estimation of the spectra for pure chemicals and they are adjusted to obtain the best fit using the alternating least squares (ALS) algorithm. However, wrong initial estimation by SVD frequently leads to convergence at an incorrect local minimum of the least square error. To overcome this problem, we have developed a robust calculation technique, which utilizes a new initial estimation using cosine similarity, and the following optimization was performed by MCR. The calculation was applied for 1H-NMR mixture spectra of 4 different chemicals, and this methodology could recover the spectra of pure chemicals (>85% consistency) and the concentration profile for each mixture within an accuracy of <10%.

Optically induced motion of liquid crystalline droplets.

The controlled motion of a liquid crystalline active droplet was demonstrated in a surfactant solution and by irradiation with UV light. The droplet could be induced to roll on a glass substrate toward the UV light source. This was explained by the Marangoni flow induced by the UV-induced desorption of surfactants.

Photoexcited charge carrier dynamics of interconnected TiO2 nanoparticles: evidence of enhancement of charge separation at anatase-rutile particle interfaces.

The charge carrier kinetics of hydrothermally treated TiO2 nanoparticles, consisting of interconnected anatase and rutile crystallographic forms, was investigated using a heterodyne transient grating technique to obtain direct evidence of the enhancement of charge separation efficiency. We found that surface recombination arising from trapped electrons was retarded, compared with that of P25 TiO2 nanoparticles, with the aid of an increase of particle interfaces. This means that the charge separation efficiency of hydrothermally treated TiO2 nanoparticles is higher than that of P25 TiO2 nanoparticles, to which the enhanced photocatalytic performance of the hydrothermally treated TiO2 nanoparticles could be attributed.

Ligand-dependent exciton dynamics and photovoltaic properties of PbS quantum dot heterojunction solar cells.

The surface chemistry of colloidal quantum dots (QDs) plays an important role in determining the photoelectric properties of QD films and the corresponding quantum dot heterojunction solar cells (QDHSCs). To investigate the effects of the ligand structure on the photovoltaic performance and exciton dynamics of QDHSCs, PbS QDHSCs were fabricated by the solid state ligand exchange method with mercaptoalkanoic acid as the cross-linking ligand. Temperature-dependent photoluminescence and ultrafast transient absorption spectra show that the electronic coupling and charge transfer rate within QD ensembles were monotonically enhanced as the ligand length decreased. However, in practical QDHSCs, the second shortest ligand 3-mercaptopropionic acid (MPA) showed higher power conversion efficiency than the shortest ligand thioglycolic acid (TGA). This could be attributed to the difference in their surface trap states, supported by thermally stimulated current measurements. Moreover, compared with the non-conjugated ligand MPA, the conjugated ligand 4-mercaptobenzoic acid (MBA) introduces less trap states and has a similar charge transfer rate in QD ensembles, but has poor photovoltaic properties. This unexpected result could be contributed by the QD-ligand orbital mixing, leading to the charge transfer from QDs to ligands instead of charge transfer between adjacent QDs. This work highlights the significant effects of ligand structures on the photovoltaic properties and exciton dynamics of QDHSCs, which would shed light on the further development of QD-based photoelectric devices.

Recent progress in sweetpotato breeding and cultivars for diverse applications in Japan.

Sweetpotato (Ipomoea batatas (L.) Lam.) is an outcrossing hexaploid that is cultivated in the tropics and warm-temperate regions of the world. Sweetpotato has played an important role as a famine-relief crop during its long history and has recently been reevaluated as a health-promoting food. In Japan, sweetpotato is used for a wide range of applications, such as table use, processed foods, and alcohol and starch production, and two groups at National Agriculture Research Organization (NARO) undertake the breeding of cultivars for these applications. Sweetpotato breeders utilize breeding processes such as grafting for flower induction and the identification of incompatibility groups before crossing to conquer problems peculiar to sweetpotato. For table use, new cultivars with high sugar content were released recently and have become popular among Japanese consumers. New cultivars with high anthocyanin or ß-carotene content were released for processed foods and use as colorants. As raw materials, new cultivars with high alcohol yield were released for the production of shochu spirits. In addition, new cultivars with high starch yield and a cultivar containing starch with excellent cold-storage ability were released for starch production. This review deals with recent progress in sweetpotato breeding and cultivars for diverse applications in Japan.

Distinction of electron pathways at titanium oxide/liquid interfaces in photocatalytic processes and co-catalyst effects.

Photocatalytic reactions include several different steps and routes for photoexcited carriers, and each dynamic is closely related to the reaction efficiency. Although commonly used time-resolved techniques can reveal the kinetics of photoexcited carriers, the reaction pathways are difficult to distinguish due to decay kinetics extending over many temporal orders and various contributions from the carriers and species involved. Herein, we report the distinction of the electron dynamics in the photocatalytic processes of titanium oxide through the combination of the transient grating method and maximum entropy analysis for the estimation of time constants. We were able to confirm three different carrier responses corresponding to an intrinsic recombination, an interfacial transfer or the decay of surface-trapped electrons, and the decay of polarons. Based on the responses, it appears that both gold and platinum work as good electron acceptors, but that only platinum shortened the lifetime of the polaron state due to the acceleration in the adsorption/desorption exchange of ions, which explains the shorter cycles of the photocatalytic reactions for platinum.

The cause for the low efficiency of dye sensitized solar cells with a combination of ruthenium dyes and cobalt redox.

It has been a concern that the cobalt redox cannot give a good performance for the dye-sensitized solar cells when it is used with ruthenium dyes. The electron dynamics measurements clarified the electron loss processes, and clarified the cause. The result indicated the direct interaction between the ruthenium dyes with the cobalt redox, and it reduced the charge injection from the triplet state of the dyes to the titanium oxide, and also it increased the electron recombination process with the cobalt redox species. Both the problems of injection and recombination were solved by using the ruthenium dye with alkyl chains keeping a distance between the dye and the cobalt redox.