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.

Food web structure for high carbon retention in marine plankton communities.

Total annual net primary productions in marine and terrestrial ecosystems are similar. However, a large portion of the newly produced marine phytoplankton biomass is converted to carbon dioxide because of predation. Which food web structure retains high carbon biomass in the plankton community in the global ocean? In 6954 individual samples or locations containing phytoplankton, unicellular protozooplankton, and multicellular metazooplankton in the global ocean, phytoplankton-dominated bottom-heavy pyramids held higher carbon biomass than protozooplankton-dominated middle-heavy diamonds or metazooplankton-dominated top-heavy inverted pyramids. Bottom-heavy pyramids predominated, but the high predation impact by protozooplankton on phytoplankton or the vertical migration of metazooplankton temporarily changed bottom-heavy pyramids to middle-heavy diamonds or top-heavy inverted pyramids but returned to bottom-heavy pyramids shortly. This finding has profound implications for carbon retention by plankton communities in the global ocean.

Seasonal change and subniche dynamics of three Alexandrium species in the Korea Strait.

Some members of the dinoflagellate genus Alexandrium produce toxins responsible for paralytic shellfish poisoning, which causes environmental impacts and large economic losses worldwide. The Outlying Mean Index (OMI) and the Within Outlying Mean Index (WitOMI) were used to examine the ecological niches of three Alexandrium species identifying factors affecting their population dynamics in the Korea Strait (KS). Species niches were divided into seasonal subniches based on species' temporal and spatial patterns, with A. catenella being highest in the spring, A. pacificum in the summer, and A. affine in the autumn. These shifts in abundance are likely due to changes in their habitat preferences and resource availability, as well as the effects of biological constraints. A subniche-based approach, which considers the interactions between the environment and the biological characteristics of a species, was useful in understanding the factors shaping the population dynamics of the individual species. Additionally, a species distribution model was used to predict the phenology and biogeography of the three Alexandrium species in the KS and their thermal niches on a larger scale. The model predicted that, in the KS, A. catenella exists on the warm side of the thermal niche, while A. pacificum and A. affine exist on the cold side, indicating that these species may respond differently to increases in water temperature. However, the predicted phenology was incongruent with the abundance of the species as measured by droplet digital PCR. Overall, the WitOMI analysis and species distribution model can provide valuable insights into how population dynamics are influenced by the integrated interplay of biotic and abiotic processes.

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.

The value of ecosystem services in global marine kelp forests.

While marine kelp forests have provided valuable ecosystem services for millennia, the global ecological and economic value of those services is largely unresolved. Kelp forests are diminishing in many regions worldwide, and efforts to manage these ecosystems are hindered without accurate estimates of the value of the services that kelp forests provide to human societies. Here, we present a global estimate of the ecological and economic potential of three key ecosystem services - fisheries production, nutrient cycling, and carbon removal provided by six major forest forming kelp genera (Ecklonia, Laminaria, Lessonia, Macrocystis, Nereocystis, and Saccharina). Each of these genera creates a potential value of between $64,400 and $147,100/hectare each year. Collectively, they generate between $465 and $562 billion/year worldwide, with an average of $500 billion. These values are primarily driven by fisheries production (mean $29,900, 904 Kg/Ha/year) and nitrogen removal ($73,800, 657 Kg N/Ha/year), though kelp forests are also estimated to sequester 4.91 megatons of carbon from the atmosphere/year highlighting their potential as blue carbon systems for climate change mitigation. These findings highlight the ecological and economic value of kelp forests to society and will facilitate better informed marine management and conservation decisions.

Force uniformity control for large-area roll-to-roll process.

Demand for high throughput manufacturing has recently increased in various fields, such as electronics, photonics, optical devices, and energy. Moreover, flexible electronic devices are indispensable in applications such as touch screens, transparent conductive electrodes, transparent film heaters, organic photovoltaics, organic light-emitting diodes, and battery. For these applications, a large-area roll-to-roll (R2R) process is a promising method for producing with high throughput. However, bending deformation of rollers is unavoidable in a large-scale R2R system, which produces non-uniformity in force distribution during processing and reduces the sample quality. In this study, we propose a new R2R imprinting module to mitigate the deformation by using an additional backup roller to achieve uniform force distribution. From numerical simulations, we found that there exists an optimal imprinting force for each backup roller length to obtain the best uniformity. Experimental results using a large-area pressure sensor verified the effectiveness of the proposed method. Finally, the R2R nanoimprint lithography process showed that the proposed method produces patterns of 100 nm width with uniform residual layer thickness, which are distributed across the substrate of 1.2 m width.

Feeding diverse prey as an excellent strategy of mixotrophic dinoflagellates for global dominance.

Microalgae fuel food webs and biogeochemical cycles of key elements in the ocean. What determines microalgal dominance in the ocean is a long-standing question. Red tide distribution data (spanning 1990 to 2019) show that mixotrophic dinoflagellates, capable of photosynthesis and predation together, were responsible for ~40% of the species forming red tides globally. Counterintuitively, the species with low or moderate growth rates but diverse prey including diatoms caused red tides globally. The ability of these dinoflagellates to trade off growth for prey diversity is another genetic factor critical to formation of red tides across diverse ocean conditions. This finding has profound implications for explaining the global dominance of particular microalgae, their key eco-evolutionary strategy, and prediction of harmful red tide outbreaks.

Quantification of the paralytic shellfish poisoning dinoflagellate Alexandrium species using a digital PCR.

A ubiquitous dinoflagellate, Alexandrium, produces paralytic shellfish toxin (PST), and its outbreaks have negative impacts on aquaculture, fisheries, human health, and the marine ecosystem. To minimize such damages, a routine monitoring program of toxic species must be implemented with a suitable analytical technique for their identification and quantification. However, the taxonomic identification and cell quantification of Alexandrium species based on their external morphology under a light microscope, or by using conventional molecular approaches have limited sensitivity and reproducibility. To address these challenges, we have developed an advanced protocol using droplet-digital PCR (ddPCR) for the discrimination and enumeration of three co-occurring Alexandrium species (A. affine, A. catenella, and A. pacificum) in environmental samples. Copies of species-specific internal transcribed spacer (ITS) per cell, which were calculated from environmental samples spiked with various numbers of culture cells, were used to estimate the abundance of species in the field samples. There were no significant differences in ITS copies estimated by the digital PCR assay between environmental samples from different localities, spiked artificially with a consistent number of cells from Alexandrium cultures. This sensitive assay was applied to determine the abundance and vertical distribution of those populations in the southern coastal waters of Korea. In spring, A. catenella was the dominant species, followed by the non-toxic A. affine in summers. A novel digital PCR assay can also be used to monitor other harmful marine protists that require high sample throughput and low detection limit with high accuracy and precision.

Effects of warming and eutrophication on coastal phytoplankton production.

Phytoplankton production in coastal waters influences seafood production and human health and can lead to harmful algal blooms. Water temperature and eutrophication are critical factors affecting phytoplankton production, although the combined effects of warming and nutrient changes on phytoplankton production in coastal waters are not well understood. To address this, phytoplankton production changes in natural waters were investigated using samples collected over eight months, and under 64 different initial conditions, established by combining four different water temperatures (i.e., ambient T, +2, +4, and + 6 °C), and two different nutrient conditions (i.e., non-enriched and enriched). Under the non-enriched conditions, the effect of warming on phytoplankton production was significantly positive in some months, significantly negative in others, or had no effect. However, under enriched conditions, warming affected phytoplankton production positively in all months except one, when the salinity was as low as 6.5. These results suggest that nutrient conditions can alter the effects of warming on phytoplankton production. Of several parameters, the ratio of initial nitrate concentration to chlorophyll a concentration [NCCA, µM (µg L-1)-1] was one of the most critical factors determining the directionality of the warming effects. In laboratory experiments, when NCCA in the ambient or nutrient-enriched waters was ≥1.2, warming increased or did not change phytoplankton production with one exception; however, when NCCA was <1.2, warming did not change or decreased production. In the time series data obtained from the coastal waters of four target countries, when NCCA was 1.5 or more, warming increased phytoplankton production, whereas when NCCA was lower than 1.5, warming lowered phytoplankton production, Thus, it is suggested that NCCA could be used as an index for predicting future phytoplankton production changes in coastal waters.

Sodium-Containing Spinel Zinc Ferrite as a Catalyst Precursor for the Selective Synthesis of Liquid Hydrocarbon Fuels.

A microwave-assisted hydrothermal synthesis produces ZnFe2 O4 containing Na residue as a precursor to a CO2 hydrogenation catalyst that displays high CO2 conversion and high selectivity to liquid hydrocarbon products in the gasoline and diesel range with high olefin-to-paraffin ratios. Compared to reference catalysts derived from Fe2 O3 and a ZnO-Fe2 O3 physical mixture, the ZnFe2 O4 -derived catalyst contains well-dispersed iron particles with Zn serving as a structural promoter. A profound effect of the residual Na as an electronic promoter is also observed, which improves the selectivity for C5+ hydrocarbons and olefins. The ZnFe2 O4 -derived catalyst exhibits excellent performance in the CO2 Fischer-Tropsch reaction as it forms the active Hägg iron carbide (χ-Fe5 C2 ) phase readily through the in situ carburization of iron.

A highly active and stable palladium catalyst on a g-C3N4 support for direct formic acid synthesis under neutral conditions.

Graphitic carbon nitride (g-C3N4) is applied as a support of the Pd catalyst for direct HCOOH synthesis by CO2 hydrogenation under neutral conditions. The high CO2 affinity of g-C3N4 is responsible for the enhanced catalytic activity and stability relative to the inert support such as a carbon nanotube.

Continuous Patterning of Copper Nanowire-Based Transparent Conducting Electrodes for Use in Flexible Electronic Applications.

Simple, low-cost and scalable patterning methods for Cu nanowire (NW)-based flexible transparent conducting electrodes (FTCEs) are essential for the widespread use of Cu NW FTCEs in numerous flexible optoelectronic devices, wearable devices, and electronic skins. In this paper, continuous patterning for Cu NW FTCEs via a combination of selective intense pulsed light (IPL) and roll-to-roll (R2R) wiping process was explored. The development of continuous R2R patterning could be achieved because there was significant difference in adhesion properties between NWs and substrates depending on whether Cu NW coated area was irradiated by IPL or not. Using a custom-built, R2R-based wiping apparatus, it was confirmed that nonirradiated NWs could be clearly removed out without any damage on irradiated NWs strongly adhered to the substrate, resulting in continuous production of low-cost Cu NW FTCE patterns. In addition, the variations in microscale pattern size by varying IPL process parameters/the mask aperture sizes were investigated, and possible factors affecting on developed pattern size were meticulously examined. Finally, the successful implementation of the patterned Cu NW FTCEs into a phosphorescent organic light-emitting diode (PhOLED) and a flexible transparent conductive heater (TCH) were demonstrated, verifying the applicability of the patterned FTCEs. It is believed that our study is the key step toward realizing the practical use of NW FTCEs in various flexible electronic devices.

The effect of starvation on plastid number and photosynthetic performance in the kleptoplastidic dinoflagellate Amylax triacantha.

The dinoflagellate Amylax triacantha is known to retain plastids of cryptophyte origin by engulfing the mixotrophic ciliate Mesodinium rubrum, itself a consumer of cryptophytes. However, there is no information on the fate of the prey's organelles and the photosynthetic performance of the newly retained plastids in A. triacantha. In this study, we conducted a starvation experiment to observe the intracellular organization of the prey's organelles and temporal changes in the photosynthetic efficiency of acquired plastids in A. triacantha. The ultrastructural observations revealed that while the chloroplast-mitochondria complexes and nucleus of cryptophyte were retained by A. triacantha, other ciliate organelles were digested in food vacuoles. Acquired plastids were retained in A. triacantha for about 1 mo and showed photosynthetic activities for about 18 d when measured by a pulse-amplitude modulation fluorometer.

Improved method for minimizing sulfur loss in analysis of particulate organic sulfur.

The global sulfur cycle depends primarily on the metabolism of marine microorganisms, which release sulfur gas into the atmosphere and thus affect the redistribution of sulfur globally as well as the earth's climate system. To better quantify sulfur release from the ocean, analysis of the production and distribution of organic sulfur in the ocean is necessary. This report describes a wet-based method for accurate analysis of particulate organic sulfur (POS) in the marine environment. The proposed method overcomes the considerable loss of sulfur (up to 80%) that occurs during analysis using conventional methods involving drying. Use of the wet-based POS extraction procedure in conjunction with a sensitive sulfur analyzer enabled accurate measurements of cellular POS. Data obtained using this method will enable accurate assessment of how rapidly sulfur can transfer among pools. Such information will improve understanding of the role of POS in the oceanic sulfur cycle.

Electrical and optical properties of Y-doped indium zinc oxide films grown by RF magnetron sputtering.

Y2O3-doped IZO (YIZO) films was investigated in order to control the carrier concentration of semiconducting IZO layer. Stoichiometric thin YIZO films were deposited on glass substrates by RF magnetron sputtering method using indium zinc oxide (IZO) including 50 wt.% ZnO and Y2O3 targets. During the deposition of YIZO films, the working pressure was fixed at 0.17 Pa and the deposition temperature was kept at room temperature while the oxygen partial pressure (P(O2)) was changed to find the optimal film condition. In order to check the PO2 effect on structural, electrical and optical properties of the grown YIZO layer on glass, X-ray diffraction (XRD) was employed to analyze the structure of YIZO films and the electrical properties were characterized by Hall measurements using the Van der Pauw geometry at room temperature. From the measured XRD patterns, exhibiting crystalline peak of the YIZO film deposited under PO2 condition is revealed while amorphous phase structure is only observed from the YIZO film deposited under pure Ar gas condition. As the O2 contents in gas increase, the resistivity of YIZO film also drastically increases, whereas the carrier concentration of the YIZO films sharply decreases with mobility.

Characteristics of Al-doped ZnO films grown by atomic layer deposition for silicon nanowire photovoltaic device.

We report the structural, electrical, and optical characteristics of Al-doped ZnO (ZnO:Al) films deposited on glass by atomic layer deposition (ALD) with various Al2O3 film contents for use as transparent electrodes. Unlike films fabricated by a sputtering method, the diffraction peak position of the films deposited by ALD progressively moved to a higher angle with increasing Al2O3 film content. This indicates that Zn sites were effectively replaced by Al, due to layer-by-layer growth mechanism of ALD process which is based on alternate self-limiting surface chemical reactions. By adjusting the Al2O3 film content, a ZnO:Al film with low electrical resistivity (9.84 x 10(-4) Omega cm) was obtained at an Al2O3 film content of 3.17%, where the Al concentration, carrier mobility, optical transmittance, and bandgap energy were 2.8 wt%, 11.20 cm2 V(-1) s(-1), 94.23%, and 3.6 eV, respectively. Moreover, the estimated figure of merit value of our best sample was 8.2 m7Omega(-1). These results suggest that ZnO:Al films deposited by ALD could be useful for electronic devices in which especially require 3-dimensional conformal deposition of the transparent electrode and surface passivation.

Thin transparent W-doped indium-zinc oxide (WIZO) layer on glass.

Annealing effect on structural and electrical properties of W-doped IZO (WIZO) films for thin film transistors (TFT) was studied under different process conditions. Thin WIZO films were deposited on glass substrates by RF magnetron co-sputtering technique using indium zinc oxide (10 wt.% ZnO-doped In2O3) and WO3 targets in room temperature. The post annealing temperature was executed from 200 degrees C to 500 degrees C under various O2/Ar ratios. We could not find any big difference from the surface observation of as grown films while it was found that the carrier density and sheet resistance of WIZO films were controlled by O2/Ar ratio and post annealing temperature. Furthermore, the crystallinity of WIZO film was changed as annealing temperature increased, resulting in amorphous structure at the annealing temperature of 200 degrees C, while clear In2O3 peak was observed for the annealed over 300 degrees C. The transmittance of as-grown films over 89% in visible range was obtained. As an active channel layer for TFT, it was found that the variation of resistivity, carrier density and mobility concentration of WIZO film decreased by annealing process.

Enhanced production of oceanic dimethylsulfide resulting from CO2-induced grazing activity in a high CO2 world.

Oceanic dimethylsulfide (DMS) released to the atmosphere affects the Earth's radiation budget through the production and growth of cloud condensation nuclei over the oceans. However, it is not yet known whether this negative climate feedback mechanism will intensify or weaken in oceans characterized by high CO(2) levels and warm temperatures. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a perturbation experiment in a coastal environment. Two sets of CO(2) and temperature conditions (a pCO(2) of ∼900 ppmv at ambient temperature conditions, and a pCO(2) of ∼900 ppmv at a temperature ∼3 °C warmer than ambient) significantly stimulated the grazing rate and the growth rate of heterotrophic dinoflagellates (ubiquitous marine microzooplankton). The increased grazing rate resulted in considerable DMS production. Our results indicate that increased grazing-induced DMS production may occur in high CO(2) oceans in the future.

Feeding by the newly described mixotrophic dinoflagellate Paragymnodinium shiwhaense: feeding mechanism, prey species, and effect of prey concentration.

To investigate the feeding by the newly described mixotrophic dinoflagellate Paragymnodinium shiwhaense (GenBank accession number=AM408889), we explored the feeding process and the kinds of prey species that P. shiwhaense is able to feed on using several different types of microscopes, including a transmission electron microscope and high-resolution video-microscopy. In addition, we measured the growth and ingestion rates of P. shiwhaense on its optimal algal prey Amphidinium carterae as a function of prey concentration. We also measured these parameters for edible prey at a single concentration at which the growth and ingestion rates of P. shiwhaense on A. carterae were saturated. Paragymnodinium shiwhaense feed on algal prey using a peduncle after anchoring the prey by a tow filament. Among the algal prey offered, P. shiwhaense ingested small algal species that had equivalent spherical diameters (ESDs) < or =11 microm (e.g. the prymnesiophyte Isochrysis galbana, the cryptophytes Teleaulax sp. and Rhodomonas salina, the raphidophyte Heterosigma akashiwo, and the dinoflagellates Heterocapsa rotundata and A. carterae). However, it did not feed on larger algal species that had ESDs > or =12 microm (e.g. the dinoflagellates Prorocentrum minimum, Heterocapsa triquetra, Scrippsiella trochoidea, Alexandrium tamarense, Prorocentrum micans, Gymnodinium catenatum, Akashiwo sanguinea, and Lingulodinium polyedrum) or the small diatom Skeletonema costatum. The specific growth rates for P. shiwhaense feeding upon A. carterae increased rapidly with increasing mean prey concentration before saturating at concentrations of ca. 350 ng C/ml (5,000 cells/ml). The maximum specific growth rate (i.e. mixotrophic growth) of P. shiwhaense on A. carterae was 1.097/d at 20 degrees C under a 14:10 h light-dark cycle of 20 microE/m(2)/s, while its growth rate (i.e. phototrophic growth) under the same light conditions without added prey was -0.224/d. The maximum ingestion and clearance rates of P. shiwhaense on A. carterae were 0.38 ng C/grazer/d (5.4 cells/grazer/d) and 0.7 microl/grazer/h, respectively. The calculated grazing coefficients for P. shiwhaense on co-occurring Amphidinium spp. was up to 0.07/h (i.e. 6.7% of the population of Amphidinium spp. was removed by P. shiwhaense populations in 1 h). The results of the present study suggest that P. shiwhaense can have a considerable grazing impact on algal populations.