Tuning CuMgAl-Layered Double Hydroxide Nanostructures to Achieve CH4 and C2+ Product Selectivity in CO2 Electroreduction.

Electrochemical CO2 reduction reaction (eCO2RR) over Cu-based catalysts is a promising approach for efficiently converting CO2 into value-added chemicals and alternative fuels. However, achieving controllable product selectivity from eCO2RR remains challenging because of the difficulty in controlling the oxidation states of Cu against robust structural reconstructions during the eCO2RR. Herein, we report a novel strategy for tuning the oxidation states of Cu species and achieving eCO2RR product selectivity by adjusting the Cu content in CuMgAl-layered double hydroxide (LDH)-based catalysts. In this strategy, the highly stable Cu2+ species in low-Cu-containing LDHs facilitated the strong adsorption of *CO intermediates and further hydrogenation into CH4. Conversely, the mixed Cu0/Cu+ species in high-Cu-containing LDHs derived from the electroreduction during the eCO2RR accelerated C-C coupling reactions. This strategy to regulate Cu oxidation states using LDH nanostructures with low and high Cu molar ratios produced an excellent eCO2RR performance for CH4 and C2+ products, respectively.

Dynamic restructuring of nickel sulfides for electrocatalytic hydrogen evolution reaction.

Transition metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction in alkaline media. However, the identification of active sites and the underlying catalytic mechanism remain elusive. In this work, we employ operando X-ray absorption spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy to elucidate that NiS undergoes an in-situ phase transition to an intimately mixed phase of Ni3S2 and NiO, generating highly active synergistic dual sites at the Ni3S2/NiO interface. The interfacial Ni is the active site for water dissociation and OH* adsorption while the interfacial S acts as the active site for H* adsorption and H2 evolution. Accordingly, the in-situ formation of Ni3S2/NiO interfaces enables NiS electrocatalysts to achieve an overpotential of only 95 ± 8 mV at a current density of 10 mA cm-2. Our work highlighted that the chemistry of transition metal chalcogenides is highly dynamic, and a careful control of the working conditions may lead to the in-situ formation of catalytic species that boost their catalytic performance.

High-Performance Electrochemical and Photoelectrochemical Water Splitting at Neutral pH by Ir Nanocluster-Anchored CoFe-Layered Double Hydroxide Nanosheets.

Highly efficient electrocatalysts for the oxygen evolution reaction (OER) in neutral electrolytes are indispensable for practical electrochemical and photoelectrochemical water splitting technologies. However, there is a lack of good, neutral OER electrocatalysts because of the poor stability when H+ accumulates during the OER and slow OER kinetics at neutral pH. Herein, we report Ir species nanocluster-anchored, Co/Fe-layered double hydroxide (LDH) nanostructures in which the crystalline nature of LDH-restrained corrosion associated with H+ and the Ir species dramatically enhanced the OEC kinetics at neutral pH. The optimized OER electrocatalyst demonstrated a low overpotential of 323 mV (at 10 mA cm-2) and a record low Tafel slope of 42.8 mV dec-1. When it was integrated with an organic semiconductor-based photoanode, we obtained a photocurrent density of 15.2 mA cm-2 at 1.23 V versus reversible hydrogen in neutral electrolyte, which is the highest among all reported photoanodes to our knowledge.

Analysis of genetic diversity and population structure among cultivated potato clones from Korea and global breeding programs.

Characterizing the genetic diversity and population structure of breeding materials is essential for breeding to improve crop plants. The potato is an important non-cereal food crop worldwide, but breeding potatoes remains challenging owing to their auto-tetraploidy and highly heterozygous genome. We evaluated the genetic structure of a 110-line Korean potato germplasm using the SolCAP 8303 single nucleotide polymorphism (SNP) Infinium array and compared it with potato clones from other countries to understand the genetic landscape of cultivated potatoes. Following the tetraploid model, we conducted population structure analysis, revealing three subpopulations represented by two Korean potato groups and one separate foreign potato group within 110 lines. When analyzing 393 global potato clones, country/region-specific genetic patterns were revealed. The Korean potato clones exhibited higher heterozygosity than those from Japan, the United States, and other potato landraces. We also employed integrated extended haplotype homozygosity (iHS) and cross-population extended haplotype homozygosity (XP-EHH) to identify selection signatures spanning candidate genes associated with biotic and abiotic stress tolerance. Based on the informativeness of SNPs for dosage genotyping calls, 10 highly informative SNPs discriminating all 393 potatoes were identified. Our results could help understanding a potato breeding history that reflects regional adaptations and distinct market demands.

Homoepitaxial growth of ZnO nanostructures from bulk ZnO.

Material formation mechanisms and their selective realization must be well understood for the development of new materials for advanced technologies. Since nanomaterials demonstrate higher specific surface energies compared to their corresponding bulk materials, the homoepitaxial growth of nanomaterials on bulk materials is not thermodynamically favorable. We observed the homoepitaxial growth of nanowires with constant outer diameters on bulk materials in two different, solution-based growth systems. We also suggested potential mechanisms of the spontaneous and homoepitaxial growth of the ZnO nanostructures based on the characterization results. The first key factor for favorable growth was the crystal facet stabilization effect of capping agents during the early stages of growth. The second factor was the change in the dominant growth mode during the reaction in a closed system. The spontaneous, homoepitaxial growth of nanomaterials enables the realization of unprecedented, complex, hierarchical, single-crystalline structures required for future technologies.

High-performance and stable photoelectrochemical water splitting cell with organic-photoactive-layer-based photoanode.

Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials. We achieve a photocurrent density of 15.1 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE) with an onset potential of 0.55 V vs. RHE and a record high half-cell solar-to-hydrogen conversion efficiency of 4.33% under AM 1.5 G solar simulated light. After conducting the stability test at 1.3 V vs. RHE for 10 h, 90% of the initial photocurrent density are retained, whereas the photoactive layer without passivation lost its activity within a few minutes.

Achieving ferromagnetic insulating properties in La0.9Ba0.1MnO3 thin films through nanoengineering.

Strongly correlated manganites have a wide range of fascinating magnetic and electronic properties, one example being the coexistence of ferromagnetic and insulating properties in lightly-doped bulk. However, it is difficult to translate bulk properties to films. Here, this problem is overcome by thin film nanoengineering of the test case system, La0.9Ba0.1MnO3 (LBMO). This was achieved by using vertically aligned nanocomposite (VAN) thin films of LBMO + CeO2 in which CeO2 nanocolumns form embedded in a LBMO matrix. The CeO2 columns produce uniform tensile straining of the LBMO. Also light Ce doping of intrinsic cation vacancies in the LBMO occurs. Together, these factors strongly reduced the double exchange coupling and metallicity. Hence, while standard plain reference films showed an insulator-to-metal transition at >200 K, originating from defects and complex structural relaxation, the VAN LBMO films exhibited ferromagnetic insulating properties (while maintaining a Tc of 188 K). This is the first time that a combined strain + doping method is used in a VAN system to realise exemplary properties which cannot be realised in plain films. This work represents an important step in engineering high performance spintronic and multiferroic thin film devices.

Nanoporous Films and Nanostructure Arrays Created by Selective Dissolution of Water-Soluble Materials.

Highly porous thin films and nanostructure arrays are created by a simple process of selective dissolution of a water-soluble material, Sr3Al2O6. Heteroepitaxial nanocomposite films with self-separated phases of a target material and Sr3Al2O6 are first prepared by physical vapor deposition. NiO, ZnO, and Ni1- x Mg x O are used as the target materials. Only the Sr3Al2O6 phase in each nanocomposite film is selectively dissolved by dipping the film in water for 30 s at room temperature. This gentle and fast method minimizes damage to the remaining target materials and side reactions that can generate impurity phases. The morphologies and dimensions of the pores and nanostructures are controlled by the relative wettability of the separated phases on the growth substrates. The supercapacitor properties of the porous NiO films are enhanced compared to plain NiO films. The method can also be used to prepare porous films or nanostructure arrays of other oxides, metals, chalcogenides, and nitrides, as well as films or nanostructures with single-crystalline, polycrystalline, or amorphous nature.

Heterojunction Area-Controlled Inorganic Nanocrystal Solar Cells Fabricated Using Supra-Quantum Dots.

A supra-quantum dot (SQD) is a three-dimensional structure formed by the attachment of quantum dots. The SQDs have sizes of tens of nanometer and they maintain the characteristics of the individual quantum dots fairly well. Moreover, their sizes and elemental compositions can be tuned precisely. On the basis of their unique features, in this work, SQDs are used as constituents of the interpenetrating photoactive layers of inorganic nanocrystal p-n heterojunction solar cells to control the p-type and n-type domain sizes (i.e., p-n heterojunction areas) for optimizing the charge-carrier collection. SQD-containing p-n heterojunction solar cells exhibit improved charge transport and thereby higher power conversion efficiency (PCE) (3.03%) owing to their intermediate p-type and n-type domain sizes, which are between those of a bilayer nanorod p-n heterojunction solar cell (PCE: 1.21%) and an interpenetrating nanorod p-n heterojunction solar cell (PCE: 2.40%). This work demonstrates that the self-assembly of nanoscale materials can be utilized for tailoring the spatial distributions of charge carriers, which is beneficial for obtaining an enhanced device performance.

Design of a Vertical Composite Thin Film System with Ultralow Leakage To Yield Large Converse Magnetoelectric Effect.

Electric field control of magnetism is a critical future technology for low-power, ultrahigh density memory. However, despite intensive research efforts, no practical material systems have emerged. Interface-coupled, composite systems containing ferroelectric and ferri-/ferromagnetic elements have been widely explored, but they have a range of problems, for example, substrate clamping, large leakage, and inability to miniaturize. In this work, through careful material selection, design, and nanoengineering, a high-performance room-temperature magnetoelectric system is demonstrated. The clamping problem is overcome by using a vertically aligned nanocomposite structure in which the strain coupling is independent of the substrate. To overcome the leakage problem, three key novel advances are introduced: a low leakage ferroelectric, Na0.5Bi0.5TiO3; ferroelectric-ferrimagnetic vertical interfaces which are not conducting; and current blockage via a rectifying interface between the film and the Nb-doped SrTiO3 substrate. The new multiferroic nanocomposite (Na0.5Bi0.5TiO3-CoFe2O4) thin-film system enables, for the first time, large-scale in situ electric field control of magnetic anisotropy at room temperature in a system applicable for magnetoelectric random access memory, with a magnetoelectric coefficient of 1.25 × 10-9 s m-1.

Photoelectrochemical water splitting strongly enhanced in fast-grown ZnO nanotree and nanocluster structures.

We demonstrate selective growth of ZnO branched nanostructures: from nanorod clusters (with branches parallel to parent rods) to nanotrees (with branches perpendicular to parent rods). The growth of these structures was realized using a three-step approach: electrodeposition of nanorods (NRs), followed by the sputtering of ZnO seed layers, followed by the growth of branched arms using hydrothermal growth. The density, size and direction of the branches were tailored by tuning the deposition parameters. To our knowledge, this is the first report of control of branch direction. The photoelectrochemical (PEC) performance of the ZnO nanostructures follows the order: nanotrees (NTs) > nanorod clusters (NCs) > parent NRs. The NT structure with the best PEC performance also possesses the shortest fabrication period which had never been reported before. The photocurrent of the NT and NC photoelectrodes is 0.67 and 0.56 mA cm-2 at 1 V vs. Ag/AgCl, respectively, an enhancement of 139% and 100% when compared to the ZnO NR structures. The key reason for the improved performance is shown to be the very large surface-to-volume ratios in the branched nanostructures, which gives rise to enhanced light absorption, improved charge transfer across the nanostructure/electrolyte interfaces to the electrolyte and efficient charge transport within the material.

Self-assembled oxide films with tailored nanoscale ionic and electronic channels for controlled resistive switching.

Resistive switches are non-volatile memory cells based on nano-ionic redox processes that offer energy efficient device architectures and open pathways to neuromorphics and cognitive computing. However, channel formation typically requires an irreversible, not well controlled electroforming process, giving difficulty to independently control ionic and electronic properties. The device performance is also limited by the incomplete understanding of the underlying mechanisms. Here, we report a novel memristive model material system based on self-assembled Sm-doped CeO2 and SrTiO3 films that allow the separate tailoring of nanoscale ionic and electronic channels at high density (∼10(12) inch(-2)). We systematically show that these devices allow precise engineering of the resistance states, thus enabling large on-off ratios and high reproducibility. The tunable structure presents an ideal platform to explore ionic and electronic mechanisms and we expect a wide potential impact also on other nascent technologies, ranging from ionic gating to micro-solid oxide fuel cells and neuromorphics.

Self-Assembled Heteroepitaxial Oxide Nanocomposite for Photoelectrochemical Solar Water Oxidation.

We report on spontaneously phase ordered heteroepitaxial SrTiO3 (STO):ZnFe2O4 (ZFO) nanocomposite films that give rise to strongly enhanced photoelectrochemical solar water oxidation, consistent with enhanced photoinduced charge separation. The STO:ZFO nanocomposite yielded an enhanced photocurrent density of 0.188 mA/cm2 at 1.23 V vs a reversible hydrogen electrode, which was 7.9- and 2.6-fold higher than that of the plain STO film and ZFO film cases under 1-sun illumination, respectively. The photoelectrode also produced stable photocurrent and Faradaic efficiencies of H2 and O2 formation that were more than 90%. Incident-photon-to-current-conversion efficiency measurements, Tauc plots, Mott-Schottky plots, and electrochemical impedance spectroscopy measurements proved that the strongly enhanced photogenerated charge separation resulted from vertically aligned pseudosingle crystalline components, epitaxial heterojunctions, and a staggered band alignment of the components of the nanocomposite films. This study presents a completely new avenue for efficient solar energy conversion applications.

Development of molecular markers for genetic male sterility in Gossypium hirsutum.

Genetic male sterility (GMS) in cotton mediated by two homozygous recessive genes, ms5ms5 and ms6ms6, is expressed as non-dehiscent anthers and unviable pollen grains. Sequence analysis on ms5 and ms6 loci in Gossypium hirsutum was conducted to reveal genomic variation at these two loci between GMS and wild-type G. hirsutum inbred lines, and sequence polymorphism linked to ms5 on A12 and ms6 on D12 was revealed. A haplotype marker set that consisted of four SNPs targeting both ms5 and ms6 gene regions was developed and validated for association with GMS in cotton. Predictability of GMS phenotype by this haplotype SNP set was over 99 %. GMS haplotype marker set can serve as a high-throughput molecular breeding tool to select GMS individuals and improve hybrid production efficiency.

Aqueous-solution route to zinc telluride films for application to CO2 reduction.

As a photocathode for CO2 reduction, zinc-blende zinc telluride (ZnTe) was directly formed on a Zn/ZnO nanowire substrate by a simple dissolution-recrystallization mechanism without any surfactant. With the most negative conduction-band edge among p-type semiconductors, this new photocatalyst showed efficient and stable CO formation in photoelectrochemical CO2 reduction at -0.2--0.7 V versus RHE without a sacrificial reagent.

The barley UNICULM2 gene resides in a centromeric region and may be associated with signaling and stress responses.

Vegetative axillary meristem (AXM) activity results in the production of branches. In barley (Hordeum vulgare L.), vegetative AXM develop in the crown and give rise to modified branches, referred to as tillers. Mutations in the barley low-tillering mutant uniculm2 block vegetative AXM development and prevent tiller development. The objectives of this work were to examine gene expression in wild-type and cul2 mutant plants, fine map the CUL2 gene, and to examine synteny in the CUL2 region in barley with rice. RNA profiling experiments using two near-isogenic line pairs carrying either the cul2 mutant allele or wild-type CUL2 allele in different genetic backgrounds detected 28 unique gene transcripts exhibiting similar patterns of differential accumulation in both genetic backgrounds, indicating that we have identified key genes impacted by the CUL2 gene. Twenty-four genes had higher abundance in uniculm2 mutant tissues, and nearly half of the annotated genes likely function in stress-response or signal transduction pathways. Genetic mapping identified five co-segregating markers in 1,088 F2 individuals. These markers spanned the centromere region on chromosome 6H, and coincided with a 50-cM region on rice chromosome 2, indicating that it may be difficult to positionally clone CUL2. Taken together, the results revealed stress response and signal transduction pathways that are associated with the CUL2 gene, isolating CUL2 via positional cloning approaches that may be difficult, and the remnants of barley-rice synteny in the CUL2 region.

Strategy for synthesizing quantum dot-layered double hydroxide nanocomposites and their enhanced photoluminescence and photostability.

Layered double hydroxide-quantum dot (LDH-QD) composites are synthesized via a room temperature LDH formation reaction in the presence of QDs. InP/ZnS (core/shell) QD, a heavy metal free QD, is used as a model constituent. Interactions between QDs (with negative zeta potentials), decorated with dihydrolipoic acids, and inherently positively charged metal hydroxide layers of LDH during the LDH formations are induced to form the LDH-QD composites. The formation of the LDH-QD composites affords significantly enhanced photoluminescence quantum yields and thermal- and photostabilities compared to their QD counterparts. In addition, the fluorescence from the solid LDH-QD composite preserved the initial optical properties of the QD colloid solution without noticeable deteriorations such as red-shift or deep trap emission. Based on their advantageous optical properties, we also demonstrate the pseudo white light emitting diode, down-converted by the LDH-QD composites.

Self-assembled gold nanoparticle-mixed metal oxide nanocomposites for self-sensitized dye degradation under visible light irradiation.

Gold nanoparticle (Au NP)-mixed metal oxide (MMO) nanocomposite photocatalysts for efficient self-sensitized dye degradations under visible light were prepared by an electrostatically driven self-assembly. Dihydrolipoic acid (DHLA)-capped Au NPs (building block I) were synthesized through a room temperature reaction. Their hydrodynamic size was determined as being around 4.9 nm by dynamic light scattering measurements. MMO nanoplates with lateral dimensions of 100-250 nm (building block II) were prepared by a calcination of zinc aluminum layered double hydroxides at 750 °C for 2 h in air. In a pH 7.0 aqueous solution, the DHLA-capped Au NPs had a negative zeta potential (-22 ± 3 mV); on the other hand, the MMO nanoplates had a positive zeta potential (15 ± 2 mV). Electrostatic self-assembly was achieved by stirring an aqueous solution (pH 7.0) containing DHLA-capped Au NPs and MMO nanoplates at room temperature for 1 h. The self-assembled and sequentially calcined nanocomposites exhibited the superior self-sensitized dye degradation efficiency under visible light to that of ZnO, TiO(2) (P25), or pure MMO nanoplates. The enhanced degradation efficiency could be attributed to strong coupling interactions of ZnO and ZnAl(2)O(4) phases of the MMO and the role of Au as an electron sink and mediator for formations of reactive oxidation species and as a light concentrator.

Porous ZnO-ZnSe nanocomposites for visible light photocatalysis.

We report the synthesis of porous ZnO-ZnSe nanocomposites for use in visible light photocatalysis. Porous ZnO nanostructures were synthesized by a microwave-assisted hydrothermal reaction then converted into porous ZnO-ZnSe nanocomposites by a microwave-assisted dissolution-recrystallization process using an aqueous solution containing selenium ions. ZnO and ZnSe nanocrystallites of the nanocomposites were well-mixed (rather than forming simple core-shell (ZnO-ZnSe) structures), particularly, in the outer regions. Both ZnO and ZnSe were present at the surface and exposed to the environment. The porous ZnO-ZnSe nanocomposites showed absorption bands in the visible region as well as in the UV region. The porous ZnO-ZnSe nanocomposites had much higher activities than the porous ZnO nanostructures. Control experiments using cutoff filters revealed that the main photocatalytic activity of the synthesized nanostructures arose from photo-excitation of the semiconductor (ZnO or ZnSe) via absorption of light of an energy equal to or exceeding the band gap energy.