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Reproduced from New J. Chem., 2023, 47, 231-237 with permission from the Royal Society of Chemistry., https://doi.org/10.1039/d2nj04361k, Ionic clathrate hydrates (ICHs) have been applied to thermal storage materials, which can be utilized as unusual thermal energy sources. In the present study, we developed a novel ICH including tri-n-butyl(cyclobutylmethyl)phosphonium bromide (P444(1c4)-Br) as an unprecedented guest species. The highest equilibrium temperature and the dissociation enthalpy of P444(1c4)-Br ICH were 279.5 ± 0.1 K and 202 ± 2 J g−1, respectively, at the mole fraction of 0.0255 ± 0.0008. The highest equilibrium temperature of P444(1c4)-Br ICH was slightly lower than that of the tetra-n-butylphosphonium bromide (P4444-Br) ICH. The dissociation enthalpy of P444(1c4)-Br ICH was larger than that of other ICHs with similar highest equilibrium temperatures. Cyclic hydrocarbon groups, together with normal, branched, saturated, and unsaturated hydrocarbon chains, can be one of the options for tuning the equilibrium temperature of ICHs. more...

Azuma S., Shimada J., Tsunashima K., et al. Equilibrium Phase Relations and Dissociation Enthalpies of Tri- n-butylalkenylphosphonium Bromide Semiclathrate Hydrates. Journal of Chemical and Engineering Data, 67, 6, 1415 - 1420, May 25, 2022, © 2022 American Chemical Society. https://doi.org/10.1021/acs.jced.2c00146., Semiclathrate hydrates (SCHs) have received attention as thermal storage materials because of their equilibrium temperature and relatively large dissociation enthalpy. The alkyl length of quaternary onium cations significantly affects the equilibrium temperature and dissociation enthalpy of quaternary onium salt SCHs. To investigate the effects of the double bond introduced in onium cations, in the present study, the thermodynamic stability of tri-n-butylalkenylphosphonium bromide (P444(alkenyl)-Br: alkenyl = 3-butenyl (3═1) or 4-pentenyl (4═1)) SCH was investigated. The equilibrium temperatures and the dissociation enthalpies were determined to be (277.5 ± 0.1) K and (199 ± 2) J/g for P444(3═1)-Br SCH, and (274.8 ± 0.1) K and (188 ± 2) J/g for P444(4═1)-Br SCH. The equilibrium temperatures of P444(3═1)-Br SCH and P444(4═1)-Br SCH were lower than those of the corresponding normal alkyl SCHs (P4444-Br and P4445-Br), although the equilibrium temperature of tri-n-butylallylphosphonium bromide SCH was higher than that of the P4443-Br SCH. more...

Sunlight-driven photocatalytic dinitrogen (N

Capturing and analyzing cometary coma dust lead to elucidate the origin of water and organics within the Solar System. For future sample return missions of fragile organic microparticles from a cometary nucleus, rendezvous operations will become more favorable than flyby missions because the comet rendezvous can reduce impacting velocity of cometary dust particles slow enough to capture them intact, rather than hypervelocity flyby sampling like the Stardust mission to the Comet Wild 2. At JAXA/ISAS, we are developing a core technology for sample return of microparticles ejected at as a lower velocity as an order of 0.1 m/s to 100 m/s after rendezvous with a cometary nucleus. We have devised “Vertically Aligned Carbon Nanotube (VA-CNT)” carpets as an effective capture medium for such a purpose. The VA-CNT carpets can amplify van der Waals force with impacting particles due to the large contact area and can capture intact the microparticles of sub-mm in size or smaller in the vacuum space environment while preserving its adhesive strength. In this study, we modelled capturing mechanism of microparticles on the VA-CNT carpets by the impact analysis software “LS-DYNA” to further improve its particle capture performance. The stress-strain constitutive laws for the VA-CNT carpets were derived via indentation and inputted to our simulations that were consistent with impact experiment results. The simulations reveal that the mechanical property of the VA-CNT carpets is the key for the improvement of its particle capture performance suitable for sampling the cometary dust. more...

This paper discusses the hypervelocity impacts of micrometeoroids and orbital debris (MMODs) on inverted metamorphic triple-junction (IMM3J) and perovskite solar cells, which are much thinner than conventional triple-junction (3J) solar cells. We experimentally found that IMM3J solar cells can suffer from short-circuit faults due to hypervelocity impacts of MMODs unlike conventional 3J cells, and determined the projectile diameters and velocities that could cause them using a model proposed by Burt. No short-circuit mode was identified in perovskite solar cells, but they had open-circuit faults several days after the hypervelocity impact experiment, which are possibly attributed to the decomposition of the perovskite crystal by moisture in the air due to the broken seal. more...

Jin Shimada, Moe Yamada, Atsushi Tani et al. Thermodynamic Properties of Tetra-n-butylphosphonium Dicarboxylate Semiclathrate Hydrates. Journal of Chemical & Engineering Data, 67 (1), 67-73, January 13, © 2022 American Chemical Society. https://doi.org/10.1021/acs.jced.1c00741, Semiclathrate hydrate (SCH) is one of the phase change materials suitable for cold energy storage. Thermodynamic properties of SCHs, such as an equilibrium temperature and the dissociation enthalpy, depend on the size and shape of the guest substances. In the present study, to reveal the effects of steric conformations of the guest anions on the thermodynamic properties of SCHs, tetra-n-butylphosphonium dicarboxylate (TBP-DC) SCHs, where the anion was oxalate (TBP-Oxa), malonate (TBP-Mal), succinate (TBP-Suc), glutarate (TBP-Glu), maleate (TBP-Male), or fumarate (TBP-Fum), were investigated. TBP-Oxa, -Mal, -Suc, and -Fum SCHs had similar equilibrium temperatures, whereas the equilibrium temperatures of TBP-Glu and -Male SCHs were higher. This suggests that the size and conformation of glutarate and maleate anions are appropriate for the cage structures of SCHs. Moreover, we compared the equilibrium temperatures of TBP-Suc, -Male, and -Fum SCHs because TBP-Suc, -Male, and -Fum have similar anion structures. The equilibrium temperature of TBP-Suc SCH was similar to that of TBP-Fum SCH, whereas TBP-Male SCH showed a higher equilibrium temperature. This result implies that the succinate anion is accommodated in the trans conformation, similar to the fumarate anion, in the hydrate cages. more...

The synthesis of spiropyran dyes exhibiting solvent-driven isomerization even in the dark condition is an important subject for the design of optical materials. A conventional synthesis strategy involves the conjugation of indoline moieties with electron-deficient aromatic moieties. Herein, we report that a spiropyran conjugated with a hydroxynaphthalene moiety (1) is a new member exhibiting solvent-driven isomerization, even bearing an electron-donating −OH moiety. The dye exists as a colorless spirocyclic (SP) form in nonpolar media. It, however, shows a blue color in polar media, especially in aqueous media, due to the formation of ring-opened merocyanine (MC) forms, where the isomerization terminates in 10 s even at room temperature. The spontaneous SP → MC isomerization originates from the MC forms stabilized by the highly delocalized π-electrons on the hydroxynaphthalene moiety. The solvation in polar media and the hydrogen bonding interaction with water molecules decrease the ground-state energy of the MC forms, triggering spontaneous isomerization. The dye exhibits two MC absorption bands assigned to the trans–trans–cis (TTC) and cis–trans–cis (CTC) isomers. The absorbance of the CTC band increases more significantly with an increase in the water content, and the increase exhibits a linear relationship with a hydrogen-bond donor acidity of solvents. The phenolate oxygen of the CTC form has larger hydrogen-bond acceptor basicity, resulting in stronger stabilization by the water molecule. more...

A 46-year-old man was referred to our hospital for the examination of a flat elevated lesion with an erosion-like depression, located on the greater curvature of the antrum. Endoscopic submucosal dissection was performed. Histological findings of the resected specimen demonstrated a well-differentiated tubular adenocarcinoma with a diameter of 12 mm. No atrophy was observed in the tumor-adjacent mucosa. Serum Helicobacter pylori antibody estimation and more...

The generation of hydrogen peroxide (H2O2) from water and dioxygen by sunlight-driven heterogeneous photocatalysis is a promising method for the artificial photosynthesis of a liquid solar fuel. We previously found that resorcinol-formaldehyde (RF) resin powders prepared by high-temperature hydrothermal synthesis act as highly active semiconductor photocatalysts for H2O2 generation. Herein, we report that RF resin powders doped with poly(3-hexylthiophene-2,5-diyl) (RF/P3HT) exhibit enhanced photocatalytic activities. The highly dispersed P3HT within the resin particles created charge transfer complexes with the conduction band of the resin via electron donation, facilitating efficient transfer of the photogenerated conduction band electrons through P3HT. This enhanced charge separation promoted efficient water oxidation and O2 reduction. The solar-to-chemical conversion efficiency for H2O2 generation on the RF/P3HT resin in water under simulated sunlight irradiation with atmospheric pressure of O2 was ∼1.0%, which is the highest efficiency reported for powder catalysts in artificial photosynthesis. more...

We present the science planning tool for dust instrument observations that is currently under development within the DESTINY+ project. The JAXA-led DESTINY+ mission (Demonstration and Experiment of Space Technology for Interplanetary voyage Phaethon fLyby and dUst Science), set to launch in 2024, carries two camera instruments intended to study the active asteroid 3200 Phaethon during a flyby in 2028, as well as the Destiny+ Dust Analyzer (DDA), an impact ionization time-of-flight mass spectrometer which will sample Phaethon’s dust environment. During the 4-years voyage leading up to the flyby, DDA will also study interplanetary and interstellar dust particles as its second main science objective. For this phase, the science working team is preparing tools to produce suitable high-level science operations schedules.As DESTINY+ relies on solar-electric propulsion to expand its Earth orbit and ultimately reach interplanetary space, a highly dynamic spacecraft attitude is required to achieve an optimal thrust vector and illumination of the solar panels. To maintain some pointing autonomy, DDA has a dual-axis pointing mechanism, granting a coverage of 1pi solid angle. The dynamic attitude combined with the flexibility of a pointing mechanism warrants elaborate planning to optimize coverage of directional dust fluxes, such as interstellar dust. Here we present the DDA Observation Planning Environment (DOPE), which is a graphical tool for intuitive campaign design, including visualizations such as spacecraft orientation or instrument footprint. Under the hood DOPE uses the SPICE toolkit for all geometric or time calculations, thus import of SPICE kernels for spacecraft trajectory, attitude, and clock is required. Here we describe the DDA science planning process to provide a contextual frame for the tool and demonstrate its functionality with emphasis on the geometrical capabilities. more...

Rare presolar grains originating by condensation in circumstellar atmospheres are known from meteorites [1]. These escaped processing in the solar nebula and are identified via their extremely diverse isotopic composition [1,2]. However, it is uncertain if such grains are representative for dust from the interstellar medium (ISM) [3–5], particular as [5] postulated a high fraction of interstellar grain population that formed directly in the ISM.In 1992 the Ulysses spacecraft discovered a dust flow from the Local Interstellar Cloud (LIC) [6]. During the Cassini mission at Saturn, the Cosmic Dust Analyser (CDA) could identify and analyse the chemical composition of 36 individual interstellar dust (ISD) particles [7]. These grains were distinguished from Saturn bound dust by their direction and high velocity. Their mean mass is consistent with the typical size [3-5] derived from astronomical observations. As major result, each individual ISD grain contains the major rock forming elements (Mg, Si, Fe, Ca) in roughly cosmic abundances, indicating compositional homogeneity at spatial scales as small as 100 nm. In contrast, CDA did neither detect carbon-rich grains such as graphite or SiC, nor pure metal grains (upper limit of 8% at the 2 sigma confidence level) [7].This homogeneity cannot be reconciled with isotopically and compositionally diverse populations of circumstellar dust inherited from AGB stars and supernovae found in meteorites. These grain populations consist mainly of silicates with a more diverse composition (e.g., olivine, pyroxene), however, also minor contributions (few %) of Al-oxides (e.g., corundum, hibonite), as well as carbonaceous grains (mainly silicon carbide) which contribute 20-50%, of the grains in the most primitive meteorites [2]. In contrast to circumstellar grains found in meteorites, the LIC-ISD grains detected by Cassini have a much lower variation of Mg/Si or Mg/Fe ratios [7], and appear to be a grain population homogenized by destruction, recondensation and equilibration processes in the ISM. This can be reconciled with astronomical observations of the diffuse ISM demonstrating that condensable elements of atomic mass >23 are depleted in the gas phase and hence bound in solids. Considering that the mean lifetime of ISD grains against destruction by supernova shocks is much shorter (c. 0.5 Ga) than the average residence time of ISM matter of 2.5 Ga [5], an origin of a high fraction of ISD by grain destruction followed by recondensation was suggested by [5,7]. While grain destruction most likely occurs in the hot interstellar medium, i.e., low-density cavities formed by supernova shock fronts, condensation likely occurs in the cold interstellar medium, i.e., cold molecular clouds which are also formation regions of stars and planets.The upcoming DESTINY+ mission [8] will be equipped with an improved impact ionization mass spectrometer, the DESTINY+ Dust Analyser (DDA). During the mission, hundreds of ISD particles are expected to be measured [9]), yielding high quality mass spectra with a resolution of c. 100-200 when compared to c. 20-50 of Cassini CDA [10]. This will allow much better resolution of mass peaks at 23-28 amu (Na, Mg, Al, Si) and 39-41 (K, Ca), particularly yielding improved constraints on abundances of Al and Si. This will allow, e.g., to distinguish between Mg silicates like pyroxene and olivine or Al-rich feldspar type silicates. Also, more precise values for Na and K can be expected, particularly as some of the Cassini CDA data were compromised by alkali contamination of the Rhodium target [7]. Furthermore, the higher number of ISD particle detections will allow to better quantify the ISD fraction of non-silicate particles (oxides, SiC, graphite, metal, see [1]). This will also provide constraints on dynamic forces acting on the ISD particle flux, particularly the question if high beta particles are preferentially deflected from the inner solar system by solar radiation forces. Finally, DDA measurements will also contribute to solve the problem of apparently low or “missing” organic components in CDA detected particles, which may be caused by volatilization of refractory organic material in ISD mantles upon entering the heliosphere [11].Hence, interstellar dust detections by the DESTINY+ Dust Analyser will likely improve our understanding of the chemical nature of interstellar dust, its processing and lifetime in various phases of the interstellar medium, possible processing and volatile loss upon traversing our solar system to 1 AU, flux modulations upon interaction with solar electromagnetic forces, and last but not least, a tight age constraint on the LIC dust. References:[1] E. Zinner (2014) In Meteorites and Cosmochemical Processes (ed. Davis A. M.). Elsevier, Amsterdam, pp. 181–213[2] J. Leitner, C. Vollmer, P. Hoppe, J. Zipfel (2012) Astrophysical Journal 745, 38[3] P. C. Frisch et al. (1999) Astrophysical Journal 525, 492[4] H. Kimura, I. Mann, E. K. Jessberger (2003) Astrophysical Journal 583, 314[5] S. Zhukovska, H.-P. Gail, M. Trieloff (2008) Astronomy & Astrophysics 479, 453[6] E. Grün et al. (1993) Nature 362, 428-430[7] N. Altobelli, F. Postberg, K. Fiege, M. Trieloff et al. (2016) Science 352, 312[8] H. Arai, M. Kobayashi, et al. (2018) Lun. Planet. Sci. Conf. 49, abstr. #2570[9] Krüger H., Strub P., et al. (2019) Planetary & Space Science 172, 22-42.[10] Srama R. et al. (2004) Space Science Reviews 114, 465-518. [11] H. Kimura, F. Postberg, N. Altobelli, M. Trieloff (2020) Astronomy & Astrophysics 643, A50 more...

Beyond the snow line of protoplanetary discs and inside the dense core of molecular clouds, the temperature of gas is low enough for water vapour to condense into amorphous ices on the surface of preexisting refractory dust particles. Recent numerical simulations and laboratory experiments suggest that condensation of the vapour promotes dust coagulation in such a cold region. However, in the numerical simulations, cohesion of refractory materials is often underestimated, while in the laboratory experiments, water vapour collides with surfaces at more frequent intervals compared to the real conditions. Therefore, to re-examine the role of water ice in dust coagulation, we carry out systematic investigation of available data on coagulation of water ice particles by making full use of appropriate theories in contact mechanics and tribology. We find that the majority of experimental data are reasonably well explained by lubrication theories, owing to the presence of a quasi-liquid layer (QLL). Only exceptions are the results of dynamic collisions between particles at low temperatures, which are, instead, consistent with the JKR theory, because QLLs are too thin to dissipate their kinetic energies. By considering the vacuum conditions in protoplanetary discs and molecular clouds, the formation of amorphous water ice on the surface of refractory particles does not necessarily aid their collisional growth as currently expected. While crystallisation of water ice around but outside the snow line eases coagulation of ice-coated particles, sublimation of water ice inside the snow line is deemed to facilitate coagulation of bare refractory particles., Comment: 18 pages, 14 figures, published in Monthly Notices of the Royal Astronomical Society more...

Ammonia is an indispensable chemical. Photocatalytic NH3 production via dinitrogen fixation using water by sunlight illumination under ambient conditions is a promising strategy, although previousl... more...

Clathrate hydrate as well as ice has been spotlighted as promising materials to investigate the properties of hydrogen-bonded networks formed by the water molecules. In the semiclathrate hydrate (SCH, a kind of clathrate hydrate) consisting of host water molecules and guest quaternary onium salts, the anion takes part in the hydrogen-bonded networks with the water molecules. In the present study, we measured the electrical conductivity and electrical relaxation time in the single-crystalline tetra-n-butylammonium bromide (TBAB) SCH by electrochemical impedance spectroscopy. The results clearly revealed that the conduction carrier was proton. The electrical relaxation time of proton conduction in TBAB SCH was similar to the reorientation time of the water molecules in TBAB SCH estimated by the results of nuclear magnetic resonance. more...

Phase equilibrium (temperature–composition) relations of the tetra-n-butylphosphonium trifluoroacetate (TBP-TFA) + water binary system including solid (semiclathrate hydrate, SCH)-liquid equilibria and liquid-liquid equilibria were investigated. Phase diagram of TBP-TFA SCH exhibited peritectic behavior. The maximum decomposition temperature (peritectic temperature) of TBP-TFA SCH at atmospheric pressure were 275.9 ± 0.1 K. The stoichiometric composition of TBP-TFA SCH was located at the mole fraction of 0.027 ± 0.002. The decomposition enthalpy of TBP-TFA SCH was 199 ± 2 J/g. At temperatures above the lower critical solution temperature (LCST), the liquid-liquid phase separation appeared. Interestingly, the composition at the LCST was 0.026 ± 0.002, which is very similar to the stoichiometric composition of TBP-TFA SCH. It implies that both cluster-based solution structures are similar. more...

The asteroid (3200) Phaethon is known to be the parent body of the Geminids, although meteor showers are commonly associated with the activity of periodic comets. What is most peculiar to the asteroid is its comet-like activity in the ejection of micrometer-sized dust particles at every perihelion passage, while the activity of the asteroid has never been identified outside the near-perihelion zone at $0.14~\mathrm{au}$ from the Sun. From the theoretical point of view, we argue that the activity of the asteroid is well explained by the electrostatic lofting of micrometer-sized dust particles with the aid of mobile alkali ions at high temperatures. The mass-loss rates of micrometer-sized particles from the asteroid in our model is entirely consistent with the values inferred from visible observations of Phaethon's dust tail. For millimeter-sized particles, we predict three orders of magnitudes higher mass-loss rates, which could also account for the total mass of the Geminid meteoroid stream by the electrostatic lofting mechanism., Comment: 7 pages. 2 figures, to appear in Icarus Letters more...

EQUULEUS (EQUilibriUm Lunar-Earth point 6U Spacecraft) will be the world's smallest spacecraft to explore the Earth-Moon Lagrange point. It is being jointly developed by JAXA (Japan Aerospace Exploration Agency) and the University of Tokyo, and will be launched by NASA's Space Launch System Exploration Mission-1. The spacecraft will fly to a libration orbit around the Earth-Moon L2 point (EML2) and will demonstrate low-energy trajectory-control techniques within the Sun-Earth-Moon region for the first time by a nano-class spacecraft. EQUULEUS also carries three scientific observation missions: imaging of Earth's plasmasphere by extreme ultraviolet wavelength, lunar impact flash observation on the far side of the moon, and micrometeoroid flux measurements in the cis-lunar region. While all these missions have their own scientific objectives, they will also contribute to future human activity and/or infrastructure development in the cis-lunar region. Most parts of the spacecraft system use commercial off-the-shelf components, or are designed based on the experiences of various past space missions, with the exception of the newly developed water resistojet propulsion system. EQUULEUS uses X-band frequency for deep space telecommunication. Japanese deep space antennas (64-m and 34-m) will be nominally used for spacecraft operation, and support from the deep space network of JPL (Jet Propulsion Laboratory) is also being planned, especially for the initial phase of operation. The spacecraft will fly to EML2 in less than one year, and will remain there for scientific observations until shortly before the depletion of the onboard propellant, when the spacecraft will leave the orbit for space-debris compliance. more...

Photocatalytic splitting of aqueous NH3 into H2 and N2 on semiconductor powders is an important reaction toward on-site production of H2 from NH3, a promising hydrogen carrier for sustainable energ... more...

Ternary polymer blends of polyamide 6 (PA6), polycarbonate (PC), and phenol novolac (PN) were prepared by a melt mixing process. PN catalyzes the exchange reaction between PA6 and PC and promotes the generation of a copolymer, which improves the compatibility. Herein, the catalytic effect of PN was experimentally supported by an increase in torque during melt mixing and mass signals from copolymer fragments detected by mass spectroscopy. The characteristic behavior of the exchange reaction changed significantly with increasing PN amount. The promotion of in situ copolymer generation led to the formation of ternary blends, which show homogeneous morphologies and superior mechanical properties, such as high stiffness and good elongation, compared with those of the binary blends without PN. Using excess PN causes some drawbacks like brittleness due to the decomposition of the PC component. A loading amount of 1–3 wt % PN was suitable for achieving a ternary blend with improved properties. more...

Ternary polymer blends comprising miscible and immiscible components are examined to improve the mechanical properties of polyamide 6 (PA6) under humid and high-temperature conditions. Miscible polymers increase the glass transition temperature (Tg), owing to their strong inter-molecular interactions, while phase-separated immiscible polymers reinforce the physical properties of PA6 as filler materials. Ternary blends exhibit these combined miscible and immiscible component contributions. Thus, in this study, ternary blends comprising PA6, polyethylene terephthalate (PET, immiscible component), and phenol novolac (PN, miscible component) are prepared by melt mixing. The PA6 stiffness in the water-absorbed state is reinforced by PET. Moreover, the proposed PA6/PET/PN ternary blends exhibit higher Tg values and lower water absorption rates than those of the PA6/PET binary blend, owing to the PN contribution. The PET and PN contributions are achieved independently and can be controlled via the composition ratios of the component polymers. Multifaceted property tailoring is thus demonstrated. more...

The dual spacecraft mission BepiColombo is the first joint mission between the European Space Agency (ESA) and the Japanese Aerospace Exploration Agency (JAXA) to explore the planet Mercury. BepiColombo was launched from Kourou (French Guiana) on October 20th, 2018, in its packed configuration including two spacecraft, a transfer module, and a sunshield. BepiColombo cruise trajectory is a long journey into the inner heliosphere, and it includes one flyby of the Earth (in April 2020), two of Venus (in October 2020 and August 2021), and six of Mercury (starting from 2021), before orbit insertion in December 2025. A big part of the mission instruments will be fully operational during the mission cruise phase, allowing unprecedented investigation of the different environments that will encounter during the 7-years long cruise. The present paper reviews all the planetary flybys and some interesting cruise configurations. Additional scientific research that will emerge in the coming years is also discussed, including the instruments that can contribute. Open Access funding provided by Istituto Nazionale di Astrofisica within the CRUI-CARE Agreement. Peerreview more...

An in-situ cosmic-dust instrument called the Mercury Dust Monitor (MDM) had been developed as a part of the science payload for the Mio (Mercury Magnetospheric Orbiter, MMO) stage of the joint European Space Agency (ESA)–JAXA Mercury-exploration mission. The BepiColombo spacecraft was successfully launched by an Ariane 5 rocket on October 20, 2018, and commissioning tests of the science payload were successfully completed in near-earth orbit before injection into a long journey to Mercury. MDM has a sensor consisting of four plates of piezoelectric lead zirconate titanate (PZT), which converts the mechanical stress (or strain) induced by dust-particle impacts into electrical signals. After the commencement of scientific operations, MDM will measure the impact momentum at which dust particles in orbit around the Sun collide with the sensor and record the arrival direction. This paper provides basic information concerning the MDM instrument and its predicted scientific operation as a future reference for scientific articles concerning the MDM’s observational data. more...

The photocatalytic generation of hydrogen peroxide from water and dioxygen (H2O + 1/2O2 → H2O2, ΔG° = +117 kJ mol–1) under sunlight is a promising strategy for the artificial photosynthesis of a liquid fuel. We had previously found that resorcinol–formaldehyde (RF) resin powders prepared by the base-catalysed high-temperature hydrothermal method act as semiconductor photocatalysts for H2O2 generation. Herein, we report that RF resins prepared by the acid-catalysed high-temperature hydrothermal method (~523 K) using common acids at pH < 4 exhibit enhanced photocatalytic activity. The base- and acid-catalysed methods both produce methylene- and methine-bridged resins consisting of π-conjugated and π-stacked benzenoid–quinoid donor–acceptor resorcinol units. The acidic conditions result in the resins with a lower bandgap (1.7 eV) and higher conductivity because the lower-degree of crosslinking creates a strongly π-stacked architecture. The irradiation of the RF-acid resins with simulated sunlight in water with atmospheric-pressure O2 generates H2O2 at a solar-to-chemical conversion efficiency of 0.7%, which is the highest efficiency ever reported for powder catalysts used in artificial photosynthesis. Low-bandgap polymers hold great potential for photocatalytic generation of hydrogen peroxide, but increasing catalytic activity remains challenging. Here, a solar-to-chemical conversion efficiency of 0.7 % is reached for a resorcinol-formaldehyde resin powder prepared via acid-catalyzed high-temperature hydrothermal synthesis. more...

The Destiny+ mission (Demonstration and Experiment of Space Technology for Interplanetary voyage Phaethon fLyby and dUst Science) has been selected as part of its M-class Space Science Program by the Japanese space agency JAXA/ISAS and is set to launch in 2023/2024. The mission target is the active asteroid (3200) Phaethon with a projected flyby in early 2028. The scientific payload consists of two cameras (the Telescopic Camera for Phaethon, TCAP, and the Multi-band Camera for Phaethon, MCAP), and the Destiny+ Dust Analyzer (DDA). DDA is the technological successor to the Cosmic Dust Analyzer (CDA) aboard Cassini-Huygens, which prominently investigated the dust environment of the Saturnian system. The DDA sensor is designed as a combination of impact ionization time-of-flight mass spectrometer and trajectory sensor, which will allow for the analysis of sub-micron and micron sized dust particles with respect to their composition (mass resolution m/Δm ≈ 100-150), mass, electrical charge, velocity (about 10% accuracy), and impact direction (about 10° accuracy). Besides attempting to sample the impact-generated dust cloud around Phaethon during the flyby, DDA will be actively observing the interplanetary & interstellar dust environment over the roughly four years spanning cruise phase from the Earth-Moon system through interplanetary space. After launch into a GTO-like orbit, Destiny+ will first employ its solar-electric propulsion system to spiral up to the lunar orbit within about 18 months, followed by a series of lunar swingbys and interim coasting phases in distant cislunar space, accumulating momentum to leave the Earth-Moon system at high excess velocity. The subsequent roughly 2-year interplanetary transfer to intercept Phaethon will be characterized by moderate orbital eccentricity of up to 0.1 and largely unpowered coasting phases. During these four years, the DDA sensor will benefit from a maximum pointing coverage range enabled by its dual-axis pointing mechanism and spacecraft attitude flexibility (during times of unpowered flight). This will allow for exhaustive mapping and analysis of the different interplanetary dust populations, as well as interstellar dust encountered in the region between 0.9-1.1 AU. Here, we give a progress report on the science planning efforts for the 4-year transfer phase. We present a tentative observation timeline that assigns scientific campaigns to different phases of the mission, taking into account results of various dust models, as well as operational and technical constraints. more...

Electrospinning is a widely used production method for nanoscale fine polymer fiber fabrics. An ultrafine fiber made of polymers such as polyvinylpyrrolidone (PVP) polyacrylic acid (PAA) has immense potential for applications in air filters, batteries, and biosensors. However, producing fabrics with long uniformly distributed ultrafine fibers of a mean diameter below ~ 200 nm is still a challenge, because such elongated-ultrafine fibers tend to break into beads before they reach the collector. Here, we exploits the thixotropy of the solution given by the addition of 2,2,6,6-tetramethylpiperidin-1-oxyl-oxidized cellulose nanofibers to recover the solution viscosity for stabilizing the electrostatically elongated nanofibers, whereby the solution is smooth in the syringe needle owing to the shear force but regain its original viscosity after being freed from electrostatic force. Using this method, we successfully fabricated a non-woven ultrafine-long nanofiber made of PVP and PAA with a mean diameter as low as ~ 90 nm with a negligible number of beads. more...

Au nanoparticles loaded on semiconductor TiO2 absorb visible light due to their surface plasmon resonance (SPR) and inject the photogenerated hot electrons (ehot-) into the conduction band of TiO2. The separated charges promote oxidation and reduction reactions. The step that determines the rate of the plasmonic photocatalysis on the Au/TiO2 system is the ehot- injection through the Schottky barrier created at the Au-TiO2 interface. In the present work, niobium (Nb5+) oxide species were doped at the Au-TiO2 interface by loading Nb5+ onto the TiO2 surface followed by deposition of Au particles (2 wt % of TiO2). Visible light irradiation of the Au/Nb5+/TiO2 catalysts promotes aerobic oxidation of alcohols with much higher efficiency than that of undoped Au/TiO2. Lewis acidity of the Nb5+ species located at the interface cancels the negative charges of Au and creates a barrier with a narrower depletion layer, promoting tunneling ehot- injection. Efficiency of the ehot- injection depends on the amount of Nb5+ doped. Loading small amounts of Nb5+ (∼0.1 wt % of TiO2) creates mononuclear NbO4 species and shows large activity enhancement. In contrast, loading larger amounts of Nb5+ creates aggregated polynuclear Nb2O5 species. They decrease the electron density of Au particles and weaken their SPR absorption. This suppresses the ehot- generation on the Au particles and decreases the activity of plasmonic photocatalysis. more...