Regulation of the d-band center of metal-organic frameworks for energy-saving hydrogen generation coupled with selective glycerol oxidation.

The hybrid electrolyzer coupled glycerol oxidation (GOR) with hydrogen evolution reaction (HER) is fascinating to simultaneously generate H2 and high value-added chemicals with low energy input, yet facing a challenge. Herein, Cu-based metal-organic frameworks (Cu-MOFs) are reported as model catalysts for both HER and GOR through doping of atomically dispersed precious and nonprecious metals. Remarkably, the HER activity of Ru-doped Cu-MOF outperformed a Pt/C catalyst, with its Faradaic efficiency for formate formation at 90% at a low potential of 1.40 V. Furthermore, the hybrid electrolyzer only needed 1.36 V to achieve 10 mA cm-2, 340 mV lower than that for splitting pure water. Theoretical calculations demonstrated that electronic interactions between the host and guest (doped) metals shifted downward the d-band centers (εd) of MOFs. This consequently lowered water adsorption and dissociation energy barriers and optimized hydrogen adsorption energy, leading to significantly enhanced HER activities. Meanwhile, the downshift of εd centers reduced energy barriers for rate-limiting step and the formation energy of OH*, synergistically enhancing the activity of MOFs for GOR. These findings offered an effective means for simultaneous productions of hydrogen fuel and high value-added chemicals using one hybrid electrolyzer with low energy input.

Nitrogen and Sulfur Co-Doped Carbon-Coated Ni3S2/MoO2 Nanowires as Bifunctional Catalysts for Alkaline Seawater Electrolysis.

Bifunctional catalysts have inherent advantages in simplifying electrolysis devices and reducing electrolysis costs. Developing efficient and stable bifunctional catalysts is of great significance for industrial hydrogen production. Herein, a bifunctional catalyst, composed of nitrogen and sulfur co-doped carbon-coated trinickel disulfide (Ni3S2)/molybdenum dioxide (MoO2) nanowires (NiMoS@NSC NWs), is developed for seawater electrolysis. The designed NiMoS@NSC exhibited high activity in alkaline electrolyte with only 52 and 191 mV overpotential to attain 10 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Significantly, the electrolyzer (NiMoS@NSC||NiMoS@NSC) based on this bifunctional catalyst drove 100 mA cm-2 at only 1.71 V along with a robust stability over 100 h in alkaline seawater, which is superior to a platinum/nickel-iron layered double hydroxide couple (Pt||NiFe LDH). Theoretical calculations indicated that interfacial interactions between Ni3S2 and MoO2 rearranged the charge at interfaces and endowed Mo sites at the interfaces with Pt-like HER activity, while Ni sites on Ni3S2 surfaces at non-interfaces are the active centers for OER. Meanwhile, theoretical calculations and experimental results also demonstrated that interfacial interactions improved the electrical conductivity, boosting reaction kinetics for both HER and OER. This study presented a novel insight into the design of high-performance bifunctional electrocatalysts for seawater splitting.

The nematode effector Mj-NEROSs interacts with Rieske's iron-sulfur protein influencing plastid ROS production to suppress plant immunity.

Root-knot nematodes (RKN; Meloidogyne species) are plant pathogens that introduce several effectors in their hosts to facilitate infection. The actual targets and functioning mechanism of these effectors largely remain unexplored. This study illuminates the role and interplay of the Meloidogyne javanica nematode effector ROS suppressor (Mj-NEROSs) within the host plant environment. Mj-NEROSs suppresses INF1-induced cell death as well as flg22-induced callose deposition and reactive oxygen species (ROS) production. A transcriptome analysis highlighted the downregulation of ROS-related genes upon Mj-NEROSs expression. NEROSs interacts with the plant Rieske's iron-sulfur protein (ISP) as shown by yeast-two-hybrid and bimolecular fluorescence complementation. Secreted from the subventral pharyngeal glands into giant cells, Mj-NEROSs localizes in the plastids where it interacts with ISP, subsequently altering electron transport rates and ROS production. Moreover, our results demonstrate that isp Arabidopsis thaliana mutants exhibit increased susceptibility to M. javanica, indicating ISP importance for plant immunity. The interaction of a nematode effector with a plastid protein highlights the possible role of root plastids in plant defense, prompting many questions on the details of this process.

Carbon superstructure-supported half-metallic V2O3 nanospheres for high-efficiency photorechargeable zinc ion batteries.

Photorechargeable zinc ion batteries (PZIBs), which can directly harvest and store solar energy, are promising technologies for the development of a renewable energy society. However, the incompatibility requirement between narrow band gap and wide coverage has raised severe challenges for high-efficiency dual-functional photocathodes. Herein, half-metallic vanadium (III) oxide (V2O3) was first reported as a dual-functional photocathode for PZIBs. Theoretical and experimental results revealed its unique photoelectrical and zinc ion storage properties for capturing and storing solar energy. To this end, a synergistic protective etching strategy was developed to construct carbon superstructure-supported V2O3 nanospheres (V2O3@CSs). The half-metallic characteristics of V2O3, combined with the three-dimensional superstructure assembled by ultrathin carbon nanosheets, established rapid charge transfer networks and robust framework for efficient and stable solar-energy storage. Consequently, the V2O3@CSs photocathode delivered record zinc ion storage properties, including a photo-assisted discharge capacities of 463 mAh∙g-1 at 2.0 A∙g-1 and long-term cycling stability over 3000 cycles. Notably, the PZIBs assembled using V2O3@CSs photocathodes could be photorecharged without an external circuit, exhibiting a high photo conversion efficiency (0.354%) and photorecharge voltage (1.0 V). This study offered a promising direction for the direct capture and storage of solar energy.

Stress Dissipation Driven by Multi-Interface Built-In Electric Fields and Desert-Rose-Like Structure for Ultrafast and Superior Long-Term Sodium Ion Storage.

The kinetics and durability of conversion-based anodes greatly depend on the intrinsic stress regulating ability of the electrode materials, which has been significantly neglected. Herein, a stress dissipation strategy driven by multi-interface built-in electric fields (BEFs) and architected structure, is innovatively proposed to design ultrafast and long-term sodium ion storage anodes. Binary Mo/Fe sulfide heterostructured nanorods with multi-interface BEFs and staggered cantilever configuration are fabricated to prove our concept. Multi-physics simulations and experimental results confirm that the inner stress in multiple directions can be dissipated by the multi-interface BEFs at the micro-scale, and by the staggered cantilever structure at the macro-scale, respectively. As a result, our designed heterostructured nanorods anode exhibits superb rate capability (332.8 mAh g-1 at 10.0 A g-1 ) and durable cyclic stability over 900 cycles at 5.0 A g-1 , outperforming other metal chalcogenides. This proposed stress dissipation strategy offers a new insight for developing stable structures for conversion-based anodes.

Volatile Perovskite Precursor Ink Enables Window Printing of Phase-Pure FAPbI3 Perovskite Solar Cells and Modules in Ambient Atmosphere.

Despite the great success of perovskite photovoltaics in terms of device efficiency and stability using laboratory-scale spin-coating methods, the demand for high-throughput and cost-effective solutions remains unresolved and rarely reported because of the complicated nature of perovskite crystallization. In this work, we propose a stable precursor ink design strategy to control the solvent volatilization and perovskite crystallization to enable the wide speed window printing (0.3 to 18.0 m/min) of phase-pure FAPbI3 perovskite solar cells (pero-SCs) in ambient atmosphere. The FAPbI3 perovskite precursor ink uses volatile acetonitrile (ACN) as the main solvent with DMF and DMSO as coordination additives is beneficial to improve the ink stability, inhibit the coffee rings, and the complicated intermediate FAPbI3 phases, delivering high-quality pin-hole free and phase-pure FAPbI3 perovskite films with large-scale uniformity. Ultimately, small-area FAPbI3 pero-SCs (0.062 cm2 ) and large-area modules (15.64 cm2 ) achieved remarkable efficiencies of 24.32 % and 21.90 %, respectively, whereas the PCE of the devices can be maintained at 23.76 % when the printing speed increases to 18.0 m/min. Specifically, the unencapsulated device exhibits superior operational stability with T90 >1350 h. This work represents a step towards the scalable, cost-effective manufacturing of perovskite photovoltaics with both high performance and high throughput.

Migration from Lysosome to Nucleus: Monitoring Lysosomal Alkalization-Related Biological Processes with an Aminofluorene-Based Probe.

Aberrant lysosomal alkalization is associated with various biological processes, such as oxidative stress, cell apoptosis, ferroptosis, etc. Herein, we developed a novel aminofluorene-based fluorescence probe named FAN to monitor the lysosomal alkalization-related biological processes by its migration from lysosome to nucleus. FAN possessed NIR emission, large Stokes shift, high pH stability, and high photostability, making it suitable for real-time and long-term bioimaging. As a lysosomotropic molecule, FAN can accumulate in lysosomes first and then migrate to the nucleus by right of its binding capability to DNA after lysosomal alkalization. In this manner, FAN was successfully used to monitor these physiological processes which triggered lysosomal alkalization in living cells, including oxidative stress, cell apoptosis, and ferroptosis. More importantly, at higher concentrations, FAN could also serve as a stable nucleus dye for the fluorescence imaging of the nucleus in living cells and tissues. This novel multifunctional fluorescence probe shows great promise for application in lysosomal alkalization-related visual research and nucleus imaging.

Regulation of Impedance Matching and Dielectric Loss Properties of N-Doped Carbon Hollow Nanospheres Modified With Atomically Dispersed Cobalt Sites for Microwave Energy Attenuation.

The rational design of lightweight, broad-band, and high-performance microwave absorbers is urgently required for addressing electromagnetic pollution issue. Metal single atoms (M-SAs) absorbers receive considerable interest in the field of microwave absorption due to the unique electronic structures of M-SAs. However, the simultaneous engineering of the morphology and electronic structure of M-SAs based absorbers remains challenging. Herein, a template-assisted method is utilized to fabricate isolated Co-SAs on N-doped hollow carbon spheres (NHCS@Co-SAs) for high-performance microwave absorption. The combination of atomically dispersed Co sites and hollow supports endows NHCS@Co-SAs with excellent microwave absorption properties. Typically, at an ultralow filler content of 8 wt%, the minimum reflection loss and effective absorption bandwidth of the NHCS@Co-SAs are up to -44.96 dB and 5.25 GHz, respectively, while the absorbing thickness is only 2 mm. Theoretical calculations and experimental results indicate that the impedance matching characteristic and dielectric loss of the NHCSs can be tuned via the introduction of M-SAs, which are responsible for the excellent microwave absorption properties of NHCS@Co-SAs. This work provides an atomic-level insight into the relationship between the electronic states of absorbers and their microwave absorption properties for developing advanced microwave absorbers.

NiO/Ni Heterojunction on N-Doped Hollow Carbon Sphere with Balanced Dielectric Loss for Efficient Microwave Absorption.

Hollow carbon spheres are potential candidates for lightweight microwave absorbers. However, the skin effect of pure carbon-based materials frequently induces a terrible impedance mismatching issue. Herein, small-sized NiO/Ni particles with heterojunctions on the N-doped hollow carbon spheres (NHCS@NiO/Ni) are constructed using SiO2 as a sacrificing template. The fabricated NHCS@NiO/Ni displayed excellent microwave absorbability with a minimum reflection loss of -44.04 dB with the matching thickness of 2 mm and a wider efficient absorption bandwidth of 4.38 GHz with the thickness of 1.7 mm, superior to most previously reported hollow absorbers. Experimental results demonstrated that the excellent microwave absorption property of the NHCS@NiO/Ni are attributed to balanced dielectric loss and optimized impedance matching characteristic due to the presence of NiO/Ni heterojunctions. Theoretical calculations suggested that the redistribution of charge at the interfaces and formation of dipoles induced by N dopants and defects are responsible for the enhanced conduction and polarization losses of NHCS@NiO/Ni. The simulations for the surface current and power loss densities reveal that the NHCS@NiO/Ni has- applicable attenuation ability toward microwave under the practical application scenario. This work paves an efficient way for the reasonable design of small-sized particles with well-defined heterojunctions on hollow nanostructures for high-efficiency microwave absorption.

Precise determination of energy transfer upconversion coefficient for the erbium and ytterbium codoped laser crystals.

Energy transfer upconversion (ETU) coefficient plays a crucial role in investigating complex laser systems as it greatly influences both the laser output behavior and heat generation. For some quasi-three-energy-level lasers based on Er3+ doped, Ho3+ doped and codoped gain media, the available theoretical studies relied on some unreasonable approximations due to the lack of spectroscopic data, notably the ETU coefficient. We put forward what we believe is a novel approach to overcome the difficulties caused by wavelength jump occurred in aforementioned laser systems. Based on net gain cross-section analysis and rate equations modelling, the functional relationship between the ETU coefficient, the laser power and pump power at the jumping wavelength are established. ETU coefficients and their temperature dependences of Er,Yb:YAB crystals with different crystal doped concentrations are experimentally determined for the first time. The results reveal that the ETU process in Er,Yb:YAB laser system is 5∼35 times stronger than that in Er3+ and Yb3+ codoped phosphate glass. The determination of these spectroscopic data paves the way for precise modelling of laser system based on Er,Yb:YAB or similar gain media.

56-fs diode-pumped SESAM mode-locked Yb:YAl3(BO3)4 laser.

We report on the first sub-60 fs pulse generated from a diode-pumped SESAM mode-locked Yb-laser based on a non-centrosymmetric Yb:YAl3(BO3)4 crystal as a gain medium. In the continuous-wave regime, pumping with a spatially single-mode, fiber-coupled 976 nm InGaAs laser diode, the Yb:YAl3(BO3)4 laser generated 391 mW at 1041.7 nm with a slope efficiency as high as 65.1%, and a wavelength tuning across 59 nm (1019 to 1078 nm) was achieved. By implementing a commercial SESAM to initiate and sustain the soliton type mode-locking, and using only a 1 mm-thick laser crystal, the Yb:YAl3(BO3)4 laser delivered pulses as short as 56 fs at a central wavelength of 1044.6 nm with an average output power of 76 mW at a pulse repetition rate of ∼67.55 MHz. To the best of our knowledge, this result represents the shortest pulses ever achieved from Yb:YAB crystal.

Lignan intake and risk of cardiovascular disease and type 2 diabetes: a meta-analysis of prospective cohort studies.

We conducted a meta-analysis of 12 prospective cohort studies to further illuminate the associations of lignan intake with risk of cardiovascular disease (CVD) and type 2 diabetes mellitus (T2DM). Compared with the lowest intake, the highest intake of lignans was correlated with a decreased incidence of CVD (relative risk [RR]: 0.85, 95% confidence interval [CI]: 0.80-0.90) and T2DM (RR: 0.82, 95% CI: 0.68-0.99). The benefits of lignan intake in CVD prevention were consistent across subgroups. In dose-response analysis, the RR for every 500-µg/d increment in lignan intake was 0.83 (95% CI: 0.74-0.92) for CVD and 0.96 (95% CI: 0.95-0.98) for T2DM. Moreover, a curvilinear dose-response pattern was observed for both CVD (p for nonlinearity < 0.001) and T2DM (p for nonlinearity < 0.001) in relation to lignan intake. These results indicated that higher lignan intake may be associated, in a dose-dependent manner, with a lower risk of CVD and T2DM.

Dual-Functional Z-Scheme TiO2 @MoS2 @NC Multi-Heterostructures for Photo-Driving Ultrafast Sodium Ion Storage.

Exploiting dual-functional photoelectrodes to harvest and store solar energy is a challenging but efficient way for achieving renewable energy utilization. Herein, multi-heterostructures consisting of N-doped carbon coated MoS2 nanosheets supported by tubular TiO2 with photoelectric conversion and electronic transfer interfaces are designed. When a photo sodium ion battery (photo-SIB) is assembled based on the heterostructures, its capacity increases to 399.3 mAh g-1 with a high photo-conversion efficiency of 0.71 % switching from dark to visible light at 2.0 A g-1 . Remarkably, the photo-SIB can be recharged by light only, with a striking capacity of 231.4 mAh g-1 . Experimental and theoretical results suggest that the proposed multi-heterostructures can enhance charge transfer kinetics, maintain structural stability, and facilitate the separation of photo-excited carriers. This work presents a new strategy to design dual-functional photoelectrodes for efficient use of solar energy.

Continuous-wave and passively Q-switched pulsed 1.5†µm Er:Yb:Ba3Gd(PO4)3 lasers.

An eye-safe 1567 nm continuous-wave laser with a maximum output power of 50 mW and a slope efficiency of 21.1% was demonstrated in an Er:Yb:Ba3Gd(PO4)3 crystal. By using a Co2+:MgAl2O4 crystal with an initial transmission of 95% as a saturable absorber, a stable passively Q-switched pulsed laser was also realized in the crystal. The effects of the output coupler transmission and cavity length on pulsed performance were investigated. At an absorbed pump power of 350 mW, a 1541 nm Er:Yb:Ba3Gd(PO4)3 pulsed laser with a repetition frequency of 0.86 kHz, duration of 38 ns, energy of 21.2 µJ, and peak output power of 0.56 kW was obtained.

Soliton mode-locked Yb:Ca3Gd2(BO3)4 laser.

We report on a soliton mode-locked Yb:Ca3Gd2(BO3)4 laser at ∼1.06 µm stabilized by a semiconductor saturable absorber mirror. Pumping with a single-transverse mode, fiber-coupled laser diode at 976 nm, the Yb:Ca3Gd2(BO3)4 laser delivers soliton pulses as short as 39 fs at a central wavelength of 1059.2 nm with an average output power of 70 mW and a pulse repetition rate of ∼67.3 MHz.

Lightweight, Fire-Retardant, and Anti-Compressed Honeycombed-Like Carbon Aerogels for Thermal Management and High-Efficiency Electromagnetic Absorbing Properties.

Ordered porous carbon materials (PCMs) have potential applications in various fields due to their low mass densities and porous features. However, it yet remains extremely challenging to construct PCMs with multifunctionalization for electromagnetic wave absorption. Herein, the honeycombed-like carbon aerogels with embedded Co@C nanoparticles are fabricated by a directionally freeze-casting and carbonization method. The optimized aerogel possesses low density (0.017 g cm-3 ), fire-retardant, robust mechanical performance (compression moduli reach 1411 and 420 kPa in the longitudinal and transverse directions at 80% strain, respectively), and high thermal management (high thermal insulation capability and high-efficiency electrothermal conversion ability). Notably, the optimized aerogel exhibits the excellent electromagnetic wave absorption properties with broad effective absorption bandwidth (13.12-17.14 GHz) and strong absorption (-45.02 dB) at a thickness of only 1.5 mm. Density functional theory calculations and the experimental results demonstrate that the excellent electromagnetic wave absorption properties stem from the synergetic effects among high electrical conductivity, numerous interfaces and dipoles and unique ordered porous structure. Meanwhile, the computer simulation technology (CST) simulation confirms that the multifunctional aerogel can attenuate more electromagnetic energy in a practical environment. This work paves the way for rational design and fabrication of the next-generation electromagnetic wave absorbing materials.

Continuous-wave and SESAM mode-locked operation of the Yb:Bi4Si3O12 laser.

We demonstrate a comprehensive characterization of the diode-pumped Yb:Bi4Si3O12 laser operating in the continuous-wave and soliton mode-locked regimes. Pumping with a 650 mW, single-transverse mode, fiber-coupled laser diode, a maximum continuous-wave output power amounted to 213 mW with a slope efficiency up to 57.6%. A broadband wavelength tuning range of more than 70 nm was achieved in CW regime with a fused silica prism. Applying a SESAM as mode locker, nearly transform-limited pulses as short as 113 fs were generated for a maximum average power of 53 mW and a pulse repetition rate of ∼106 MHz. To the best of our knowledge, this is the first report on passively mode-locked operation with the Yb:Bi4Si3O12 crystal.

25.4†kW, 1.9†ns passively Q-switched 1522†nm Er:Yb:LuAl3(BO3)4 pulse microlaser at 100†Hz.

Passively Q-switched Er:Yb:LuAl3(BO3)4 pulse microlasers were investigated at a low repetition frequency of 10-200 Hz. End-pumped by a 975.6 nm quasi-continuous-wave laser diode with pump pulse width of 0.5 ms and period of 10 ms, a stable 1522 nm pulse microlaser with single pulse energy of 48.3 µJ, duration of 1.9 ns, repetition frequency of 100 Hz, peak output power of 25.4 kW and beam quality factor less than 1.2 was realized at a pump beam waist diameter of 260 µm. This eye-safe passively Q-switched pulse microlaser with high peak output power and narrow duration can be used in the portable laser rangefinder.

The growth of a large GdPO4 crystal guided by theoretical simulation and the study of its phonon properties.

It has remained a big challenge to grow large crystals of compounds at very anisotropic crystal growth rates. GdPO4 is such an example, which usually grows into a needle-like shape. This work solved this problem by using Li+ ions, predicted by first-principles calculations, to adjust the crystal morphology of GdPO4. Based on the calculated surface energies and the polar properties of the surfaces, we identified two crystal planes, i.e. (-102) and (-111), which can be used to adjust the morphology of the GdPO4 crystal by using extrinsic cations in the flux system. With a predicted Li containing flux system, Li2O-MoO3-B2O3, a large crystal with a record size, 10.0 × 9.0 × 18.2 mm3, was grown by using the top-seeded solution growth (TSSG) method. Based on the grown large crystal and the polarized Raman measurements, four new Raman bands missing in early studies and other bands were unambiguously assigned. By introducing a new formula, the phonon-phonon interactions were shown to be weak in the temperature range from 83 to 803 K. Our study indicates that the crystal of GdPO4 can be used as a promising laser host material working under relatively high temperature conditions.

Ferromagnetism and optical properties of SnS2 doped with two impurities: first-principles calculations.

Based on the first principles of the GGA method, the magnetic and optical properties of intrinsic SnS2; Fe, Cr mono-doped SnS2; and (Fe, Cr) co-doped SnS2 are studied. The results show that the ground states of Fe, Cr mono-doped SnS2 are spin polarized, and the magnetic moments caused are 1.99 µB and 3.00 µB, respectively. The magnetic moment of Fe mono-doped SnS2 is mainly produced by Fe:3d orbitals, and the magnetic moment of Cr mono-doped SnS2 is mainly produced by Cr:3d and Sn:4d orbitals. We calculate that in the (Fe, Cr) co-doped SnS2 system, Fe, Cr and the adjacent S atoms form a strong hybrid, that is, the closest S atom between Fe and Cr atoms mediates the spin polarization and ferromagnetic (FM) coupling. This promotes the formation of a Fe:3d-S:3p-Cr:3d coupling chain, so that (Fe, Cr) co-doped SnS2 obtains FM stability. In addition, with the introduction of Fe and Cr atoms, the absorption coefficient is the largest in the long-wavelength infrared region of 0.23-1.63 eV. This shows that Fe and Cr doping can make up for the lack of absorption of intrinsic materials in the infrared region. In summary, Fe, Cr doped SnS2 dilute magnetic semiconductors may be a good candidate in the field of spintronic devices.