Tunable green syngas generation from CO2 and H2O with sunlight as the only energy input.

The carbon-neutral synthesis of syngas from CO2 and H2O powered by solar energy holds grand promise for solving critical issues such as global warming and the energy crisis. Here we report photochemical reduction of CO2 with H2O into syngas using core/shell Au@Cr2O3 dual cocatalyst-decorated multistacked InGaN/GaN nanowires (NWs) with sunlight as the only energy input. First-principle density functional theory calculations revealed that Au and Cr2O3 are synergetic in deforming the linear CO2 molecule to a bent state with an O-C-O angle of 116.5°, thus significantly reducing the energy barrier of CO2RR compared with that over a single component of Au or Cr2O3. Hydrogen evolution reaction was promoted by the same cocatalyst simultaneously. By combining the cooperative catalytic properties of Au@Cr2O3 with the distinguished optoelectronic virtues of the multistacked InGaN NW semiconductor, the developed photocatalyst demonstrated high syngas activity of 1.08 mol/gcat/h with widely tunable H2/CO ratios between 1.6 and 9.2 under concentrated solar light illumination. Nearly stoichiometric oxygen was evolved from water splitting at a rate of 0.57 mol/gcat/h, and isotopic testing confirmed that syngas originated from CO2RR. The solar-to-syngas energy efficiency approached 0.89% during overall CO2 reduction coupled with water splitting. The work paves a way for carbon-neutral synthesis of syngas with the sole inputs of CO2, H2O, and solar light.

Photoelectron Holographic Study for Atomic Site Occupancy for Si Dopants in Si-Doped κ-Ga2O3(001).

We investigated atomic site occupancy for the Si dopant in Si-doped κ-Ga2O3(001) using photoelectron spectroscopy (PES) and photoelectron holography (PEH). From PES and PEH, we found that the Si dopant had one chemical state, and three types of inequivalent Si substitutional sites (SiGa) were formed. The ratios for the inequivalent tetrahedral, pentahedral, and octahedral SiGa sites were estimated to be 55.0%, 28.1%, and 16.9%, respectively. Higher (lower) ratios for the three inequivalent SiGa sites may come from a lower (higher) formation energy. The Tetra (Octa) SiGa site has the highest (lowest) ratio of the three SiGa sites since it has the lowest (highest) formation energy. We suggest that the tetrahedral SiGa site is due to the active dopant site, whereas the pentahedral and octahedral SiGa sites can be attributed to the inactive dopant sites for Si-doped κ-Ga2O3(001).

Atomistic Investigation of Grain Boundary Fracture in Alumina.

Grain boundary (GB) fracture is a major mechanism of material failure in polycrystalline ceramics. However, the intricate atomic arrangements of GBs have impeded our understanding of the atomistic mechanisms of these processes. In this study, we investigated the atomic-scale crack propagation behavior of an α-Al2O3 ∑13 grain boundary, using a combination of in situ transmission electron microscopy (TEM) and scanning TEM. The atomic-scale fracture path along the GB core was directly determined by the observation of the atomic structures of the fractured surfaces, which is consistent with density functional theory calculations. We found that the GB fracture can be attributed to the weaker local bonds and a smaller number of bonds along the fracture path. Our findings provide atomistic insights into the mechanisms of crack propagation along GBs, offering significant implications for GB engineering and the toughening of ceramics.

Ultrathin Ga2O3 Photodetector with Fast Response and Trajectory Tracking Capability Fabricated by Liquid Metal Oxidation.

Low-dimensional Ga2O3 demonstrates a unique ultraviolet photoresponse and could be used in various electronic and optical systems. However, the low-dimensional Ga2O3 photodetector is faced with the challenges of a complex preparation process and poor device performance. In this work, ultrathin Ga2O3 layers with ∼7 nm thickness are prepared on quartz rods by UV exposure to liquid gallium. Benefiting from low-density oxygen vacancy defects cured by UV exposure, the low-dimensional Ga2O3 photodetector exhibits a high response speed (rise: 64.7 µs; fall: 51.4 µs) and an exceptional linear dynamic range of 120 dB. Furthermore, the photodetector array based on these ultrathin Ga2O3 shows an effective trajectory tracking capability by monitoring UV source motion. This work develops a simple preparation method to construct a low-dimensional UV photodetector array with fast response and useful trajectory tracking capability, exhibiting the significance of ultrathin Ga2O3 in UV optoelectronics.

ß-Ga2O3 Air-Channel Field-Emission Nanodiode with Ultrahigh Current Density and Low Turn-On Voltage.

Field-emission nanodiodes with air-gap channels based on single ß-Ga2O3 nanowires have been investigated in this work. With a gap of ∼50 nm and an asymmetric device structure, the proposed nanodiode achieves good diode characteristics through field emission in air at room temperature. Measurement results show that the nanodiode exhibits an ultrahigh emission current density, a high enhancement factor of >2300, and a low turn-on voltage of 0.46 V. More impressively, the emission current almost keeps constant over a wide range (8 orders of magnitude) of air pressures below 1 atm. Meanwhile, the fluctuation in field-emission current is below 8.7% during long-time monitoring, which is better than the best reported field-emission device based on ß-Ga2O3 nanostructures. All of these results indicate that ß-Ga2O3 air-gapped nanodiodes are promising candidates for vacuum electronics that can also operate in air.

Nanoscale Localized Phonons at Al2O3 Grain Boundaries.

Nanoscale defects like grain boundaries (GBs) would introduce local phonon modes and affect the bulk materials' thermal, electrical, optical, and mechanical properties. It is highly desirable to correlate the phonon modes and atomic arrangements for individual defects to precisely understand the structure-property relation. Here we investigated the localized phonon modes of Al2O3 GBs by combination of the vibrational electron energy loss spectroscopy (EELS) in scanning transmission electron microscope and density functional perturbation theory (DFPT). The differences between GB and bulk obtained from the vibrational EELS show that the GB exhibited more active vibration at the energy range of <50 meV and >80 meV, and further DFPT results proved the wide distribution of bond lengths at GB are the main factor for the emergence of local phonon modes. This research provides insights into the phonon-defect relation and would be of importance in the design and application of polycrystalline materials.

Antiferromagnetic Nanoscale Bit Arrays of Magnetoelectric Cr2O3 Thin Films.

Magnetism of oxide antiferromagnets (AFMs) has been studied in single crystals and extended thin films. The properties of AFM nanostructures still remain underexplored. Here, we report on the fabrication and magnetic imaging of granular 100 nm-thick magnetoelectric Cr2O3 films patterned in circular bits with diameters ranging from 500 down to 100 nm. With the change of the lateral size, the domain structure evolves from a multidomain state for larger bits to a single domain state for the smallest bits. Based on spin-lattice simulations, we show that the physics of the domain pattern formation in granular AFM bits is primarily determined by the energy dissipation upon cooling, which results in motion and expelling of AFM domain walls of the bit. Our results provide a way toward the fabrication of single domain AFM-bit-patterned memory devices and the exploration of the interplay between AFM nanostructures and their geometric shape.

Revealing Fast Negative Capacitance in PbZr0.2Ti0.8O3 Thin Film with Acicular Ferroelastic Domains.

Negative capacitance effects with fast response times hold great potential for reducing the power consumption in high-frequency nanoelectronics. Nevertheless, the negative capacitance effect faces considerable complexity arising from the dynamic interplay among electrostatic, nucleation energies, and domain evolution. This intricate balance poses a formidable challenge to achieving fast negative capacitance. Herein, we have achieved a fast negative capacitance time of ∼16.23 ns in PbZr0.2Ti0.8O3 (PZT) thin film, and our investigation confirms the presence of acicular ferroelastic domains within the PZT thin film. Under reversal electric fields, these acicular ferroelastic domains undergo a unique flipping process, transitioning through domain expansion and contraction. This distinct domain flipping manner accelerates the nucleation and growth of ferroelectric domains, thereby facilitating the observed fast negative capacitance. The realization of fast negative capacitance holds substantial promise for reducing operational time and power consumption, offering prospects for the design of nanoelectronics with significantly lower power requirements.

Inhibition of phosphodiesterase 4 attenuates aquaporin 4 expression and astrocyte swelling following cerebral ischemia/reperfusion injury.

We have previously shown that phosphodiesterase 4 (PDE4) inhibition protects against neuronal injury in rats following middle cerebral artery occlusion/reperfusion (MCAO/R). However, the effects of PDE4 on brain edema and astrocyte swelling are unknown. In this study, we showed that inhibition of PDE4 by Roflumilast (Roflu) reduced brain edema and brain water content in rats subjected to MCAO/R. Roflu decreased the expression of aquaporin 4 (AQP4), while the levels of phosphorylated protein kinase B (Akt) and forkhead box O3a (FoxO3a) were increased. In addition, Roflu reduced cell volume and the expression of AQP4 in primary astrocytes undergoing oxygen and glucose deprivation/reoxygenation (OGD/R). Consistently, PDE4B knockdown showed similar effects as PDE4 inhibition; and PDE4B overexpression rescued the inhibitory role of PDE4B knockdown on AQP4 expression. We then found that the effects of Roflu on the expression of AQP4 and cell volume were blocked by the Akt inhibitor MK2206. Since neuroinflammation and astrocyte activation are the common events that are observed in stroke, we treated primary astrocytes with interleukin-1ß (IL-1ß). Astrocytes treated with IL-1ß showed decreased AQP4 and phosphorylated Akt and FoxO3a. Roflu significantly reduced AQP4 expression, which was accompanied by increased phosphorylation of Akt and FoxO3a. Furthermore, overexpression of FoxO3a partly reversed the effect of Roflu on AQP4 expression. Our findings suggest that PDE4 inhibition limits ischemia-induced brain edema and astrocyte swelling via the Akt/FoxO3a/AQP4 pathway. PDE4 is a promising target for the intervention of brain edema after cerebral ischemia.

Water and Cu+ Synergy in Selective CO2 Hydrogenation to Methanol over Cu-MgO-Al2O3 Catalysts.

The CO2 hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO2-neutral economy. Previous research identified isolated Cu+ species doping the oxide surface of a Cu-MgO-Al2O3-mixed oxide derived from a hydrotalcite precursor as the active site in CO2 hydrogenation, stabilizing monodentate formate species as a crucial intermediate in methanol synthesis. In this work, we present a molecular-level understanding of how surface water and hydroxyl groups play a crucial role in facilitating spontaneous CO2 activation at Cu+ sites and the formation of monodentate formate species. Computational evidence has been experimentally validated by comparing the catalytic performance of the Cu-MgO-Al2O3 catalyst with hydroxyl groups against that of its hydrophobic counterpart, where hydroxyl groups are blocked using an esterification method. Our work highlights the synergistic effect between doped Cu+ ions and adjacent hydroxyl groups, both of which serve as key parameters in regulating methanol production via CO2 hydrogenation. By elucidating the specific roles of these components, we contribute to advancing our understanding of the underlying mechanisms and provide valuable insights for optimizing methanol synthesis processes.

53BP1 regulates the self-renewal ability of neural stem/progenitor cells through modulating mitochondrial homeostasis.

The regulation of intracellular reactive oxygen species (ROS) levels is important for maintaining the self-renewal ability of neural stem/progenitor cells (NSCs). In this study, we demonstrate that 53BP1, a DNA damage response factor known to facilitate the repair of DNA double-strand breaks, supports the maintenance of NSC stemness. ReNcell VM human NSCs with depleted 53BP1 exhibited reduced self-renewal ability compared with control NSCs, as revealed by a decrease in neurosphere size and an increase in differentiation into neural or glial cells within an NSC culture. Furthermore, 53BP1 depletion elevated cellular ROS levels, accompanied by mitochondrial abnormalities. The reduced self-renewal ability and elevated ROS levels in 53BP1-deficient NSCs were restored with the treatment of a radical scavenger, N-acetyl-l-cysteine. In addition, we investigated the functional relationship in the NSC self-renewal ability between 53BP1 and ataxia-telangiectasia mutated (ATM) or forkhead box O3a (FOXO3a), factors required for mitochondrial homeostasis, and the maintenance of NSC stemness. We found that ATM inhibition or FOXO3a deficiency, in addition to 53BP1 deficiency, did not induce further NSC stemness impairment. Collectively, our findings show that 53BP1, by cooperatively functioning with ATM and FOXO3a, supports the maintenance of NSC stemness by modulating mitochondrial homeostasis.

Foliar-applied silicate potassium modulates growth, phytochemical, and physiological traits in Cichorium intybus L. under salinity stress.

One of the major problems endangering plant growth and productivity worldwide is salt stress. This study aimed to assess the effects of potassium silicate (K2O3Si) on the physical, biochemical, and morphological characteristics of chicory (Cichorium intybus L.) under various levels of salinity stress. The plants were treated with K2O3Si at concentrations of 0, 1, 2, and 3 mM and cultivated under different salt stress conditions (0, 80, 160, and 240 mM NaCl). The findings revealed that salt stress led to decreased root and shoot dry weights, Fv/Fm ratio, chlorophyll a, b, and total chlorophyll, as well as inulin contents. However, foliar exposure to K2O3Si at all salinity levels resulted in improvements in the measured traits. As salinity levels increased, there was a corresponding increase in the accumulation of sodium ions (Na+) and a sharp reduction in potassium ions (K +) in the shoot. Nonetheless, treatment with K2O3Si caused a decrease in Na + accumulation and an improvement in K+ content under all salinity levels. Carotenoid content increased under 80 mM salinity stress, but decreased with higher salinity levels. Application of K2O3Si at all levels resulted in increased carotenoid content under salinity stress conditions. The content of MDA increased significantly with increasing salinity stress, particularly at 240 mM. However, foliar spraying with K2O3Si significantly decreased MDA content at all salinity levels. Salinity stress up to 160 mM increased the total phenol, flavonoid, and anthocyanin contents, while 240 mM NaCl decreased the biosynthesis of phytochemicals. Additionally, the use of K2O3Si increased the content of total phenol, flavonoid, and anthocyanin at all salt levels. Foliar application of K2O3Si increased the tolerance of chicory plants to salinity stress by reducing MDA and increasing phenolic compounds and potassium content. These results suggest that exogenous K2O3Si can be a practical strategy to improve the growth and yield of chicory plants exposed to saline environments.

Insight into the High Mobility and Stability of In2 O3 :H Film.

Wide bandgap semiconductors, particularly In2 O3 :Sn (ITO), are widely used as transparent conductive electrodes in optoelectronic devices. Nevertheless, due to the strohave beenng scattering probability of high-concentration oxygen vacancy (VO ) defects, the mobility of ITO is always lower than 40 cm2  V-1  s-1 . Recently, hydrogen-doped In2 O3 (In2 O3 :H) films have been proven to have high mobility (>100 cm2  V-1  s-1 ), but the origin of this high mobility is still unclear. Herein, a high-resolution electron microscope and theoretical calculations are employed to investigate the atomic-scale mechanisms behind the high carrier mobility in In2 O3 :H films. It is found that VO can cause strong lattice distortion and large carrier scattering probability, resulting in low carrier mobility. Furthermore, hydrogen doping can simultaneously reduce the concentration of VO , which accounts for high carrier mobility. The thermal stability and acid-base corrosion mechanism of the In2 O3 :H film are investigated and found that hydrogen overflows from the film at high temperatures (>250 °C), while acidic or alkaline environments can cause damage to the In2 O3 grains themselves. Overall, this work provides insights into the essential reasons for high carrier mobility in In2 O3 :H and presents a new research approach to the doping and stability mechanisms of transparent conductive oxides.

Hyphae Carbon Coupled with Gel Composite Assembly for Construction of Advanced Carbon/Sulfur Cathodes for Lithium-Sulfur Batteries.

The design and fabrication of novel carbon hosts with high conductivity, accelerated electrochemical catalytic activities, and superior physical/chemical confinement on sulfur and its reaction intermediates polysulfides are essential for the construction of high-performance C/S cathodes for lithium-sulfur batteries (LSBs). In this work, a novel biofermentation coupled gel composite assembly technology is developed to prepare cross-linked carbon composite hosts consisting of conductive Rhizopus hyphae carbon fiber (RHCF) skeleton and lamellar sodium alginate carbon (SAC) uniformly implanted with polarized nanoparticles (V2O3, Ag, Co, etc.) with diameters of several nanometers. Impressively, the RHCF/SAC/V2O3 composites exhibit enhanced physical/chemical adsorption of polysulfides due to the synergistic effect between hierarchical pore structures, heteroatoms (N, P) doping, and polar V2O3 generation. Additionally, the catalytic conversion kinetics of cathodes are effectively improved by regulating the 3D carbon structure and optimizing the V2O3 catalyst. Consequently, the LSBs assembled with RHCF/SAC/V2O3-S cathode show exceptional cycle stability (capacity retention rate of 94.0% after 200 cycles at 0.1 C) and excellent rate performance (specific capacity of 578 mA h g-1 at 5 C). This work opens a new door for the fabrication of hyphae carbon composites via fermentation for electrochemical energy storage.

Phase-Dependent Phonon Heat Transport in Nanoscale Gallium Oxide Thin Films.

Different phases of Ga2O3 have been regarded as superior platforms for making new-generation high-performance electronic devices. However, understanding of thermal transport in different phases of nanoscale Ga2O3 thin-films remains challenging, owing to the lack of phonon transport models and systematic experimental investigations. Here, thermal conductivity (TC) and thermal boundary conductance (TBC) of the ( 1 ¯ 010 ) $( {\bar 1010} )$ α-, ( 2 ¯ 01 ) $( {\bar 201} )\;$ ß-, and (001) κ-Ga2O3 thin films on sapphire are investigated. At ≈80 nm, the measured TC of α (8.8 W m-1 K-1) is ≈1.8 times and ≈3.0 times larger than that of ß and κ, respectively, consistent with model based on density functional theory (DFT), whereas the model reveals a similar TC for the bulk α- and ß-Ga2O3. The observed phase- and size-dependence of TC is discussed thoroughly with phonon transport properties such as phonon mean free path and group velocity. The measured TBC at Ga2O3/sapphire interface is analyzed with diffuse mismatch model using DFT-derived full phonon dispersion relation. Phonon spectral distribution of density of states, transmission coefficients, and group velocity are studied to understand the phase-dependence of TBC. This study provides insight into the fundamental phonon transport mechanism in Ga2O3 thin films and paves the way for improved thermal management of high-power Ga2O3-based devices.

ZnO@In2O3 Core-Shell Heterojunctions Constructed With ZIF-8 and MIL-68 (In) for Improving Photogenerated Carrier Transfer Process.

The realization of fast carrier transport can effectively enhance photocatalytic performance. A core-shell structure of ZnO and In2O3 is successfully constructed by using MIL-68 (In) and ZIF-8 as a substrate, forming a heterojunction. This MOF-derived core-shell heterojunction inherits the advantages of ZIF-8, with pores facilitating carriers transfer to the surface for reactions and a large specific surface area providing more active sites. This Z-scheme heterojunction of ZnO and In2O3 can effectively separate and improve the utilization of photogenerated carriers. The well-designed interface of the core-shell structure achieves the rapid transfer of photogenerated carriers. The photocatalytic degradation capability of ZnO@ In2O3 is enhanced by the synergistic effect of Z-scheme heterojunction and core-shell structure. This work provides insight into the investigation of constructing core-shell heterojunctions.

Full Exploitation of Charge Compensation of O3-type Cathode Toward High Energy Sodium-Ion Batteries by High Entropy Strategy.

O3-type cathodes with sufficient Na content are considered as promising candidates for sodium-ion batteries (SIBs). However, these cathodes suffer from insufficient utilization of the active elements, restraining the delivered capacity. In this work, a high entropy strategy is applied to a typical O3 cathode NaLi0.1Ni0.35Mn0.55O2 (NLNM), forming a high entropy oxide NaLi0.1Ni0.15Cu0.1Mg0.1Ti0.2Mn0.35O2 (Na-HE). Results show that the active elements are fully exploited in Na-HE, with a two-electron reaction by Ni2+/4+ (further extended to Cu redox and even oxygen redox), vastly different from a one-electron reaction of Ni2+/3+ in NLNM. The full utilization of the active elements dramatically improves the output capacity of the cathode (122.6 mAh g-1 of Na-HE versus 81 mAh g-1 of NLNM). Moreover, the detrimental phase transition is well suppressed in Na-HE. The cathode exhibits high capacity retention of 88.7% after 100 cycles at 130 mA g-1, compared to only 36.4% for NLNM. These findings provide new insight for the design of new cathode materials for SIBs with high energy density and robust stability.

Defensive and Ion Conductive Surface Layer Enables High Rate and Durable O3-type NaNi1/3 Fe1/3 Mn1/3 O2 Sodium-Ion Battery Cathode.

Na-based layered transition metal oxides with an O3-type structure are considered promising cathodes for sodium-ion batteries. However, rapid capacity fading, and poor rate performance caused by serious structural changes and interfacial degradation hamper their use. In this study, a NaPO3 surface modified O3-type layered NaNi1/3 Fe1/3 Mn1/3 O2 cathode is synthesized, with improved high-voltage stability through protecting layer against acid attack, which is achieved by a solid-gas reaction between the cathode particles and gaseous P2 O5 . The NaPO3 nanolayer on the surface effectively stabilizes the crystal structure by inhibiting surface parasitic reactions and increasing the observed average voltage. Superior cyclic stability is exhibited by the surface-modified cathode (80.1% vs 63.6%) after 150 cycles at 1 C in the wide voltage range of 2.0 V-4.2 V (vs Na+ /Na). Moreover, benefiting from the inherent ionic conduction of NaPO3 , the surface-modified cathode presents excellent rate capability (103 mAh g-1  vs 60 mAh g-1 ) at 10 C. The outcome of this study demonstrates a practically relevant approach to develop high rate and durable sodium-ion battery technology.

Efficient Catalysis of Ultrathin Two-Dimensional Fe2 O3 -CoP Heterostructure Nanosheets for Polysulfide Redox Reactions.

The "shuttle effect" and slow redox reactions of Li-S batteries limit their practical application. To solve these problems, a judicious catalyst design for improved battery cycle life and rate performance is essential. Herein, this issue is addressed by modifying the Li-S battery separator using a 2D Fe2 O3 -CoP heterostructure that combines the dual functions of polar Fe2 O3 and high-conductivity CoP. The synthesized ultrathin nanostructure exposes well-dispersed active sites and shortens the ion diffusion paths. Theoretical calculations, electrochemical tests, and in situ Raman spectroscopy measurements reveal that the heterostructure facilitates the inhibition of polysulfide shuttling and enhances the electrode kinetics. A sulfur cathode constructed using the Fe2 O3 -CoP-based separator provides an astonishing capacity of 1346 mAh g-1 at 0.2 C and a high capacity retention of ≈84.5%. Even at a high sulfur loading of 5.42 mg cm-2 , it shows an area capacity of 5.90 mAh cm-2 . This study provides useful insights into the design of new catalytic materials for Li-S batteries.

Amorphous Structure Benefits in MgV2O4/V2O3 Composites for Zinc-Ion Storage: An Integration of Computational and Experimental Studies.

This study investigates the electrochemical properties of MgV2O4/V2O3 composites for Aqueous Zinc-Ion Batteries (AZIBs) using both Density Functional Theory (DFT) calculations and experimental validation. DFT analysis reveals significant electron mobility and reactivity at the MgV2O4/V2O3 interface, enhancing Zn2+ storage capabilities. This theoretical prediction is confirmed experimentally by synthesizing a novel MgV2O4/V2O3 composite that demonstrates superior electrochemical performance compared to pristine phases. Notably, the transition of the MgV2O4/V2O3 composite into an amorphous structure during electrochemical cycling is pivotal, providing enhanced diffusion pathways and increased conductivity. The composite delivers a consistent specific capacity of 330.2 mAh g-1 over 50 cycles at 0.1 A g-1 and maintains 152.7 mAh g-1 at an elevated current density of 20 A g-1 after 2000 cycles, validating the synergy between DFT insights and experimental outcomes, and underscoring the potential of amorphous structures in enhancing battery performance.