Biomass Waste Utilization as Nanocomposite Anodes through Conductive Polymers Strengthened SiO2/C from Streblus asper Leaves for Sustainable Energy Storages.

Sustainable anode materials, including natural silica and biomass-derived carbon materials, are gaining increasing attention in emerging energy storage applications. In this research, we highlighted a silica/carbon (SiO2/C) derived from Streblus asper leaf wastes using a simple method. Dried Streblus asper leaves, which have plenty of biomass in Thailand, have a unique leaf texture due to their high SiO2 content. We can convert these worthless leaves into SiO2/C nanocomposites in one step, producing eco-materials with distinctive microstructures that influence electrochemical energy storage performance. Through nanostructured design, SiO2/C is thoroughly covered by a well-connected framework of conductive hybrid polymers based on the sodium alginate-polypyrrole (SA-PPy) network, exhibiting impressive morphology and performance. In addition, an excellent electrically conductive SA-PPy network binds to the SiO2/C particle surface through crosslinker bonding, creating a flexible porous space that effectively facilitates the SiO2 large volume expansion. At a current density of 0.3 C, this synthesized SA-PPy@Nano-SiO2/C anode provides a high specific capacity of 756 mAh g-1 over 350 cycles, accounting for 99.7% of the theoretical specific capacity. At the high current of 1 C (758 mA g-1), a superior sustained cycle life of over 500 cycles was evidenced, with over 93% capacity retention. The research also highlighted the potential for this approach to be scaled up for commercial production, which could have a significant impact on the sustainability of the lithium-ion battery industry. Overall, the development of green nanocomposites along with polymers having a distinctive structure is an exciting area of research that has the potential to address some of the key challenges associated with lithium-ion batteries, such as capacity degradation and safety concerns, while also promoting sustainability and reducing environmental impact.

Microstructural and chemical features of impact melts on Ryugu particle surfaces: Records of interplanetary dust hit on asteroid Ryugu.

The Hayabusa2 spacecraft delivered samples of the carbonaceous asteroid Ryugu to Earth. Some of the sample particles show evidence of micrometeoroid impacts, which occurred on the asteroid surface. Among those, particles A0067 and A0094 have flat surfaces on which a large number of microcraters and impact melt splashes are observed. Two impact melt splashes and one microcrater were analyzed to unveil the nature of the objects that impacted the asteroid surface. The melt splashes consist mainly of Mg-Fe-rich glassy silicates and Fe-Ni sulfides. The microcrater trapped an impact melt consisting mainly of Mg-Fe-rich glassy silicate, Fe-Ni sulfides, and minor silica-rich glass. These impact melts show a single compositional trend indicating mixing of Ryugu surface materials and impactors having chondritic chemical compositions. The relict impactor in one of the melt splashes shows mineralogical similarity with anhydrous chondritic interplanetary dust particles having a probable cometary origin. The chondritic micrometeoroids probably impacted the Ryugu surface during its residence in a near-Earth orbit.

Intrinsic Visible Plasmonic Properties of Colloidal PtIn2 Intermetallic Nanoparticles.

Materials that intrinsically exhibit localized surface plasmon resonance (LSPR) in the visible region have been predominantly researched on nanoparticles (NPs) composed of coinage metals, namely Au, Ag, and Cu. Here, as a coinage metal-free intermetallic NPs, colloidal PtIn2 NPs with a C1 (CaF2 -type) crystal structure are synthesized by the liquid phase method, which evidently exhibit LSPR at wavelengths similar to face-centered cubic (fcc)-Au NPs. Computational simulations pointed out differences in the electronic structure and photo-excited electron dynamics between C1-PtIn2 and fcc-Au NPs; reduces interband transition and stronger screening with smaller number of bound d-electrons compare with fcc-Au are unique origins of the visible plasmonic nature of C1-PtIn2 NPs. These results strongly indicate that the intermetallic NPs are expected to address the development of alternative plasmonic materials by tuning their crystal structure and composition.

Insight into the Role of Conductive Polypyrrole Coated on Rice Husk-Derived Nanosilica-Reduced Graphene Oxide as the Anodes: Electrochemical Improvement in Sustainable Lithium-Ion Batteries.

Polypyrrole (PPy) is a type of conducting polymer that has garnered attention as a potential electrode material for sustainable energy storage devices. This is mostly attributed to its mechanical flexibility, ease of processing, and ecologically friendly nature. Here, a polypyrrole-coated rice husk-derived nanosilica-reduced graphene oxide nanocomposite (SiO2-rGO@PPy) as an anode material was developed by a simple composite technique followed by an in situ polymerization process. The architecture of reduced graphene oxide offers a larger electrode/electrolyte interface to promote charge-transfer reactions and provides sufficient space to buffer a large volume expansion of SiO2, maintaining the mechanical integrity of the overall electrode during the lithiation/delithiation process. Moreover, the conducting polymer coating not only improves the capacity of SiO2, but also suppresses the volume expansion and rapid capacity fading caused by serious pulverization. The present anode material shows a remarkable specific reversible capacity of 523 mAh g-1 at 100 mA g-1 current density and exhibits exceptional discharge rate capability. The cycling stability at a current density of 100 mA g-1 shows 81.6% capacity retention and high Coulombic efficiency after 250 charge-discharge cycles. The study also pointed out that this method might be able to be used on a large scale in the lithium-ion battery industry, which could have a big effect on its long-term viability. Creating sustainable nanocomposites is an exciting area of research that could help solve some of the biggest problems with lithium-ion batteries, like how easy they are to make and how big they can be used in industry. This is because they are sustainable and have less of an impact on the environment.

Development of Bronze Phase Titanium Dioxide Nanorods for Use as Fast-Charging Anode Materials in Lithium-Ion Batteries.

Bronze phase titanium dioxide (TiO2(B)) nanorods were successfully prepared via a hydrothermal method together with an ion exchange process and calcination by using anatase titanium dioxide precursors in the alkali hydrothermal system. TiO2 precursors promoted the elongation of nanorod morphology. The different hydrothermal temperatures and reaction times demonstrated that the synthesis parameters had a significant influence on phase formation and physical morphologies during the fabrication process. The effects of the synthesis conditions on the tailoring of the crystal morphology were discussed. The growth direction of the TiO2(B) nanorods was investigated by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The as-synthesized TiO2(B) nanorods obtained after calcination were used as anode materials and tested the efficiency of Li-ion batteries. This research will study the effects of particle morphologies and crystallinity of TiO2(B) derived from a modified hydrothermal method on the capacity and charging rate of the Li-ion battery. The TiO2(B) nanorods, which were synthesized by using a hydrothermal temperature of 220 °C for 12 h, presented excellent electrochemical performance with the highest Li storage capacity (348.8 mAh/g for 100 cycles at a current density of 100 mA/g) and excellent high-rate cycling capability (a specific capacity of 207.3 mAh/g for 1000 cycles at a rate of 5000 mA/g).

Efficient and Stable Carbon-Based Perovskite Solar Cells Enabled by Mixed CuPc:CuSCN Hole Transporting Layer for Indoor Applications.

Perovskite solar cells (PSCs) are an innovative technology with great potential to offer cost-effective and high-performance devices for converting light into electricity that can be used for both outdoor and indoor applications. In this study, a novel hole-transporting layer (HTL) was created by mixing copper phthalocyanine (CuPc) molecules into a copper(I) thiocyanate (CuSCN) film and was applied to carbon-based PSCs with cesium/formamidinium (Cs0.17FA0.83Pb(I0.83Br0.17)3) as a photoabsorber. At the optimum concentration, a high power conversion efficiency (PCE) of 15.01% was achieved under AM1.5G test conditions, and 32.1% PCE was acquired under low-light 1000 lux conditions. It was discovered that the mixed CuPc:CuSCN HTL helps reduce trap density and improve the perovskite/HTL interface as well as the HTL/carbon interface. Moreover, the PSCs based on the mixed CuPc:CuSCN HTL provided better stability over 1 year due to the hydrophobicity of CuPc material. In addition, thermal stability was tested at 85 °C and the devices achieved an average efficiency drop of approximately 50% of the initial PCE value after 1000 h. UV light stability was also examined, and the results revealed that the average efficiency drop of 40% of the initial value for 70 min of exposure was observed. The work presented here represents an important step toward the practical implementation of the PSC as it paves the way for the development of cost-effective, stable, yet high-performance PSCs for both outdoor and indoor applications.

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu.

Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe3+ to Fe2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (-OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss.

Different atomic contrasts in HAADF images and EELS maps of rutile TiO2.

High-angle annular dark-field (HAADF) imaging and elemental mapping at the atomic scale by scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) are widely used for material characterization, in which quantitative understanding of the contrast of the image is required. Here, we report an unexpected image contrast in the elemental mapping of rutile TiO2, where the Ti L2,3 map shows an anisotropic elliptical shape that extends along the long axis in the octahedral structure, while the atomic contrast of Ti columns in the HAADF image is almost circular. Multi-slice simulation reveals that unique electron channeling related to the rutile structure and the difference of the potentials between HAADF and EELS cause the different atomic contrasts in the two images.

Comparison of detection limits of direct-counting CMOS and CCD cameras in EELS experiments.

The noise performance and the detection limits of a direct-counting complementary metal-oxide semiconductor (CMOS) K2 camera and a charge-coupled device (CCD) camera in electron energy loss spectroscopy (EELS) experiments were evaluated. In the case of a single spectrum acquired at the shortest dwell times (2.5 ms for K2 and 1 µs for CCD), the detection limit, defined as three times the standard deviation of the spectral noise (3σ), was very low (1 e-/channel) in the counting-mode spectrum acquired with the K2 camera compared with that acquired with the CCD camera (5 e-/channel). By contrast, the spectral noise of the K2 camera changed depending on the dwell time because of the multiple read-outs related to its fixed frame rate (400 fps). The spectral noise of the K2 camera was greater than that of the CCD camera when the dwell time was longer than ∼30 ms. Thus, the CCD camera was found to still be useful when detecting a very small number of electrons using a long acquisition time. In the case of an accumulated spectrum obtained by acquiring 10,000 spectra after subtracting the ultra-high-quality dark reference signal, the detection limits per read-out were ∼0.016 and ∼0.025 e-/channel/read-out for the K2 and CCD cameras, respectively. Because both cameras have advantages and disadvantages with respect to their detection limit, speed, and dynamic range, their proper use is important.

Inter-element miscibility driven stabilization of ordered pseudo-binary alloy.

An infinite number of crystal structures in a multicomponent alloy with a specific atomic ratio can be devised, although only thermodynamically-stable phases can be formed. Here, we experimentally show the first example of a layer-structured pseudo-binary alloy, theoretically called Z3-FePd3. This Z3 structure is achieved by adding a small amount of In, which is immiscible with Fe but miscible with Pd and consists of an alternate L10 (CuAu-type)-PdFePd trilayer and Pd-In ordered alloy monolayer along the c axis. First-principles calculations strongly support that the specific inter-element miscibility of In atoms stabilizes the thermodynamically-unstable Z3-FePd3 phase without significantly changing the original density of states of the Z3-FePd3 phase. Our results demonstrate that the specific inter-element miscibility can switch stable structures and manipulate the material nature with a slight composition change.

Crystalline to amorphous transformation in solid-solution alloy nanoparticles induced by boron doping.

We synthesized a palladium-ruthenium-boron (Pd-Ru-B) solid-solution ternary alloy. Elemental mappings confirmed successful alloying of B with Pd-Ru body without changing the particle sizes, demonstrating the first discovery of this ternary alloy. Pair distribution function analysis revealed a drastic decrease in atomic correlation in Pd-Ru nanoparticles by B doping. This result gives the first example of structural transformation from crystalline to amorphous in solid-solution alloy nanoparticles induced by the doping of light elements.

Ultrafast-charging and long cycle-life anode materials of TiO2-bronze/nitrogen-doped graphene nanocomposites for high-performance lithium-ion batteries.

Emerging technologies demand a new generation of lithium-ion batteries that are high in power density, fast-charging, safe to use, and have long cycle lives. This work reports charging rates and specific capacities of TiO2(B)/N-doped graphene (TNG) composites. The TNG composites were prepared by the hydrothermal method in various reaction times (3, 6, 9, 12, and 24 h), while the N-doped graphene was synthesized using the modified Hummer's method followed by a heat-treatment process. The different morphologies of TiO2 dispersed on the N-doped graphene sheet were confirmed as anatase-nanoparticles (3, 6 h), TiO2(B)-nanotubes (9 h), and TiO2(B)-nanorods (12, 24 h) by XRD, TEM, and EELS. In electrochemical studies, the best battery performance was obtained with the nanorods TiO2(B)/N-doped graphene (TNG-24h) electrode, with a relatively high specific capacity of 500 mA h g-1 at 1C (539.5 mA g-1). In long-term cycling, excellent stability was observed. The capacity retention of 150 mA h g-1 was observed after 7000 cycles, at an ultrahigh current of 50C (27.0 A g-1). The synthesized composites have the potential for fast-charging and have high stability, showing potential as an anode material in advanced power batteries for next-generation applications.

Conversion of a Defect Pyrochlore into a Double Perovskite via High-Pressure, High-Temperature Reduction of Te6.

High-pressure, high-temperature reaction conditions can be useful to stabilize metastable polymorphs of complex transition metal oxides. We successfully prepare a new defect pyrochlore Pb2FeTeO6.5 with B-site disordered Fe and Te cations under ambient conditions. Treatment of this material under 8 GPa and 950 °C results in a reductive transformation into the B-site cation-ordered double perovskite Pb2FeTeO6. Mössbauer and EELS spectroscopy confirm the iron cations are in the +3 oxidation state in both phases indicating that this transformation proceeds via reduction of the tellurium cations under apparently oxidizing conditions. This reaction demonstrates that for a suitably chosen system, it is possible to carry out chemical reactions under pressure in unexpected ways.

Extremely low count detection for EELS spectrum imaging by reducing CCD read-out noise.

Extremely low count detection for EELS spectrum imaging is required to overcome problems with electron irradiation and widen the range of available applications. We have made a systematic statistical study of the reduction of CCD noise for EELS. We propose a calculation method to estimate the properties of noise and a procedure to reduce it. Since the dominant noise is a practically random component, it can be reduced by subtracting the population mean of the dark reference and a summation over an appropriate number of spectra, depending on the standard deviation of the noise. A gain-averaging method can further improve the signal-to-noise (SN) ratio. It is thereby demonstrated that a high-SN spectrum can be obtained even for a single-count core-loss signal. The present method would be useful for measuring low signal spectrum such as monochromated spectra and for radiation sensitive materials.

Anomalous Photoinduced Hole Transport in Type I Core/Mesoporous-Shell Nanocrystals for Efficient Photocatalytic H2 Evolution.

Controlling the carrier dynamics in a semiconductor nanoparticulate photocatalyst is the key to developing catalytic activity. Generally, type I band alignment is unsuitable for photocatalysts because the photoinduced carriers accumulate in the narrow bandgap semiconductor. To avoid the termination of reactions and/or photocorrosion of materials caused by carrier accumulation, it is common to employ type II band alignment for photoenergy conversion systems instead of type I. However, CdS/ZnS core/mesoporous-shell heterostructures show superior photocatalytic activity despite having type I band alignment that is generally unfavorable for photocatalytic reactions. Transient absorption spectroscopy and time-resolved microwave conductivity revealed efficient photoinduced hole transfer from the CdS phase to the ZnS phase. The defect-mediated hole transfer from the CdS to the ZnS phase resulted in long-lived charge separation (>2.4 ms) leading to high photocatalytic performance. This study provides insight into defect-mediated carrier transfer in nanoparticulate photocatalysts, which could be used as a guideline for the design of highly active and stable nanoparticulate photocatalysts.

Bulk Dzyaloshinskii-Moriya interaction in amorphous ferrimagnetic alloys.

Symmetry breaking is a fundamental concept that prevails in many branches of physics1-5. In magnetic materials, broken inversion symmetry induces the Dzyaloshinskii-Moriya interaction (DMI), which results in fascinating physical behaviours6-14 with the potential for application in future spintronic devices15-17. Here, we report the observation of a bulk DMI in GdFeCo amorphous ferrimagnets. The DMI is found to increase linearly with an increasing thickness of the ferrimagnetic layer, which is a clear signature of the bulk nature of DMI. We also found that the DMI is independent of the interface between the heavy metal and ferrimagnetic layer. This bulk DMI is attributed to an asymmetric distribution of the elemental content in the GdFeCo layer, with spatial inversion symmetry broken throughout the layer. We expect that our experimental identification of a bulk DMI will open up additional possibilities to exploit this interaction in a wide range of materials.

Phase segregated Cu2-x Se/Ni3Se4 bimetallic selenide nanocrystals formed through the cation exchange reaction for active water oxidation precatalysts.

Control over the composition and nanostructure of solid electrocatalysts is quite important for drastic improvement of their performance. The cation exchange reaction of nanocrystals (NCs) has been reported as the way to provide metastable crystal structures and complicated functional nanostructures that are not accessible by conventional synthetic methods. Herein we demonstrate the cation exchange-derived formation of metastable spinel Ni3Se4 NCs (sp-Ni3Se4) and phase segregated berzelianite Cu2-x Se (ber-Cu2-x Se)/sp-Ni3Se4 heterostructured NCs as active oxygen evolution reaction (OER) catalysts. A rare sp-Ni3Se4 phase was formed by cation exchange of ber-Cu2-x Se NCs with Ni2+ ions, because both phases have the face-centered cubic (fcc) Se anion sublattice. Tuning the Ni : Cu molar ratio leads to the formation of Janus-type ber-Cu2-x Se/sp-Ni3Se4 heterostructured NCs. The NCs of sp-Ni3Se4 and ber-Cu2-x Se/sp-Ni3Se4 heterostructures exhibited high catalytic activities in the OER with small overpotentials of 250 and 230 mV at 10 mA cm-2 in 0.1 M KOH, respectively. They were electrochemically oxidized during the OER to give hydroxides as the real active species. We anticipate that the cation exchange reaction could have enormous potential for the creation of novel heterostructured NCs showing superior catalytic performance.

Formation of strong L10-FePd/α-Fe nanocomposite magnets by visualizing efficient exchange coupling.

Conceptual nanocomposite magnets (NCMs) composed of exchange-coupled hard/soft magnetic phases have been expected to show excellent magnetic performance based on simultaneous high coercivity (H c) and high saturation magnetization (M s). In our previous works, however, the H c was considerably lower than its theoretical value (H a), which prevented us from improving the performance of NCMs. Here, we show that the H c of isolated particulate L10-FePd/α-Fe NCMs is dominated by their phase segregation into core/shell-like structures versus Janus-like structures. Using first-order reversal curve (FORC) analysis, we clearly distinguished a microscopically undetectable difference in the phase-segregation structure in the NCMs, finding both efficient and inefficient exchange coupling. The nanostructurally controlled NCMs dominated by core/shell-like structure with efficient exchange coupling showed the largest energy product ((BH)max = 17.5 MGOe) in the Fe-Pd system and the highest H c/H a value (26.5%) among all NCM powders.

Phase-segregated NiP x @FeP y O z core@shell nanoparticles: ready-to-use nanocatalysts for electro- and photo-catalytic water oxidation through in situ activation by structural transformation and spontaneous ligand removal.

The high overpotential of the oxygen evolution reaction is a critical issue to be overcome to realize efficient overall water splitting and enable hydrogen generation powered by sunlight. Homogeneous and stable nanoparticles (NPs) dispersed in solvents are useful as both electrocatalysts and cocatalysts of photocatalysts for the electro- and photo-catalytic oxygen evolution reaction, respectively, through their adsorption on various electrode substrates. Here, phase-segregated NiP x @FeP y O z core@shell NPs are selectively synthesized by the reaction of Fe(CO)5 with amorphous NiP x seed-NPs. The NiP x @FeP y O z NPs on conductive substrates exhibit higher electrocatalytic activity in the oxygen evolution reaction than those of other metal phosphide-based catalysts. The NiP x @FeP y O z NPs can also be used as a cocatalyst of an anodic BiVO4 photocatalyst to boost the photocatalytic water oxidation reaction. The excellent catalytic activity and high stability of the NiP x @FeP y O z NPs without any post-treatments are derived from in situ activation through both the structural transformation of NiP x @FeP y O z into mixed hydroxide species, (Ni, Fe)O x H y , and the spontaneous removal of the insulating organic ligands from NPs to form a smooth and robust (Ni, Fe)O x H y /substrate heterointerface during the oxygen evolution reaction.

Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface.

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 µs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.