Ge-Doped Hematite with FeCoNi-Bi as Cocatalyst for High-Performing Photoelectrochemical Water Splitting.

Hematite is a promising photoanode material for photoelectrochemical water-splitting technology. However, the low current density associated with the low conductivity, low charge carrier mobility, and poor oxygen evolution catalytic activity is a challenging issue for the material. In this study, the challenge is addressed by introducing Germanium (Ge) doping, coupled with the use of FeCoNi-Bi as a co-catalyst. Ge doping not only increases the conductivity and charge carrier concentration of the hematite photoanode, but also induces nanopores, thereby expanding its electrochemical reactive surface area to facilitate the oxygen evolution reaction. In the meantime, the FeCoNi-Bi cocatalyst electrodeposited onto the surface of Ge-doped hematite, improves the oxygen evolution reaction performance. As a result, the obtained photoanode achieves a photocurrent density of 2.31 mA cm-2 at 1.23 VRHE, which is three times higher than that of hematite (0.72 mA cm-2). Moreover, a new analytical method is introduced to scrutinize both the positive and negative effects of Ge doping and FeCoNi-Bi cocatalyst on the photoanode performance by decoupling the photoelectrochemical process steps. Overall, this study not only enhances the performance of hematite photoanodes but also guides their rational design and systematic assessment.

Pressure-Induced Defects and Reduced Size Endow TiO2 with High Capacity over 20 000 Cycles and Excellent Fast-Charging Performance in Sodium Ion Batteries.

Anatase TiO2 as sodium-ion-battery anode has attracted increased attention because of its low volume change and good safety. However, low capacity and poor rate performance caused by low electrical conductivity and slow ion diffusion greatly impede its practical applications. Here, a bi-solvent enhanced pressure strategy that induces defects (oxygen vacancies) into TiO2 via N doping and reduces its size by using mutual-solvent ethanol and dopant dimethylformamide as pressure-increased reagent of tetrabutyl orthotitanate tetramer is proposed to fabricate N-doped TiO2 /C nanocomposites. The induced defects can increase ion storage sites, improve electrical conductivity, and decrease bandgap and ion diffuse energy barrier of TiO2 . The size reduction increases contact interfaces between TiO2 and C and shortens ion diffuse distance, thus increasing extra ion storage sites and boosting ion diffusion rate of TiO2 . The N-doped TiO2 possesses highly stable crystal structure with a slightly increase of 0.86% in crystal lattice spacing and 3.2% in particle size after fully sodiation. Consequently, as a sodium-ion battery anode, the nanocomposite delivers high capacity and superior rate capability along with ultralong cycling life. This work proposes a novel pressure-induced synthesis strategy that provides unique guidance for designing TiO2 -based anode materials with high capacity and excellent fast-charging capability.

Echinatin mitigates sevoflurane-induced neurotoxicity through regulation of ferroptosis and iron homeostasis.

Surgery and anesthesia are vital medical interventions, but concerns over their potential cognitive side effects, particularly with the use of inhalational anesthetics like sevoflurane, have surfaced. This study delves into the neuroprotective potential of Echinatin against sevoflurane-induced neurotoxicity and the underlying mechanisms. Echinatin, a natural compound, has exhibited anti-inflammatory, antioxidant, and anticancer properties. Sevoflurane, while a popular anesthetic, is associated with perioperative neurocognitive disorders (PND) and neurotoxicity. Our investigation began with cellular models, where Echinatin demonstrated a significant reduction in sevoflurane-induced apoptosis. Mechanistically, we identified ferroptosis, a novel form of programmed cell death characterized by iron accumulation and lipid peroxidation, as a key player in sevoflurane-induced neuronal injury. Echinatin notably suppressed ferroptosis in sevoflurane-exposed cells, suggesting a pivotal role in neuroprotection. Expanding our research to a murine model, we observed perturbations in iron homeostasis, inflammatory cytokines, and antioxidants due to sevoflurane exposure. Echinatin treatment effectively restored iron balance, mitigated inflammation, and preserved antioxidant levels in vivo. Behavioral assessments using the Morris water maze further confirmed Echinatin's neuroprotective potential, as it ameliorated sevoflurane-induced spatial learning and memory impairments. In conclusion, our study unveils Echinatin as a promising candidate for mitigating sevoflurane-induced neurotoxicity. Through the regulation of ferroptosis, iron homeostasis, and inflammation, Echinatin demonstrates significant neuroprotection both in vitro and in vivo. These findings illuminate the potential for Echinatin to enhance the safety of surgical procedures involving sevoflurane anesthesia, minimizing the risk of cognitive deficits and neurotoxicity.

Engineering the d-Orbital Energy of Metal-Organic Frameworks-Based Solid-State Electrolytes for Lithium-Metal Batteries.

Having an orbital-level understanding of the relationship between the electronic state of a central metal in metal-organic frameworks (MOFs) as solid-state electrolytes (SSEs) and Li+ ion conductivity is crucial yet challenging for lithium-metal batteries (LMBs). In this study, we report the synthesis of functionalized UiO-66 as a model system to investigate the relationship between the d-band energy of Zr 3d orbitals and Li+ ion conductivity. Specifically, the NO2 group in electron-withdrawing NO2-decorated UiO-66 (NO2-UiO-66) can capture electron from ZrO8 sites, resulting the increased energy in 3dz2 and 3dxz/yz orbitals of Zr atom. The high-energy 3dz2 and 3dxz/yz orbitals of Zr in NO2-UiO-66 hybridize with the 2pz and 2px/y orbitals of O in ClO4-, leading to decreased antibonding orbital energy and resulting in a strong adsorption, ultimately immobilizing the anions and enhancing ion conductivities. Establishing the correlation between the d-orbital energy and Li+ ion conductivity may create a descriptor for designing efficient SSEs for LMBs.

Dead-zone-compensated design as general method of flow field optimization for redox flow batteries.

One essential element of redox flow batteries (RFBs) is the flow field. Certain dead zones that cause local overpotentials and side effects are present in all conventional designs. To lessen the detrimental effects, a dead-zone-compensated design of flow field optimization is proposed. The proposed architecture allows for the detection of dead zones and their compensation on existing flow fields. Higher reactant concentrations and uniformity factors can be revealed in the 3D multiphysical simulation. The experiments also demonstrate that at an energy efficiency (EE) of 80%, the maximum current density of the novel flow field is 205 mA cm-2, which is much higher than the values for the previous ones (165 mA cm-2) and typical serpentine flow field (153 mA cm-2). Extensions of the design have successfully increased system EE (2.7 to 4.3%) for a variety of flow patterns. As a result, the proposed design is demonstrated to be a general method to support the functionality and application of RFBs.

3D hierarchical graphene matrices enable stable Zn anodes for aqueous Zn batteries.

Metallic zinc anodes of aqueous zinc ion batteries suffer from severe dendrite and side reaction issues, resulting in poor cycling stability, especially at high rates and capacities. Herein, we develop two three-dimensional hierarchical graphene matrices consisting of nitrogen-doped graphene nanofibers clusters anchored on vertical graphene arrays of modified multichannel carbon. The graphene matrix with radial direction carbon channels possesses high surface area and porosity, which effectively minimizes the surface local current density, manipulates the Zn2+ ions concentration gradient, and homogenizes the electric field distribution to regulate Zn deposition. As a result, the engineered matrices achieve a superior coulombic efficiency of 99.67% over 3000 cycles at 120 mA cm-2, the symmetric cells with the composite zinc anode demonstrates 2600 h dendrite-free cycles at 80 mA cm-2 and 80 mAh cm-2. The as-designed full cell exhibits an inspiring capacity of 16.91 mAh cm-2. The Zn capacitor matched with activated carbon shows a superior long-term cycle performance of 20000 cycles at 40 mA cm-2. This strategy of constructing a 3D hierarchical structure for Zn anodes may open up a new avenue for metal anodes operating under high rates and capacities.

An artificial interfacial layer with biomimetic ionic channels towards highly stable Li metal anodes.

Lithium (Li) metal with low electrochemical potential and high theoretical capacity is a promising anode material for next-generation batteries. However, the low reversibility and safety problems caused by the notorious dendrite growth significantly impede the development of high-energy-density lithium metal batteries (LMBs). Here, to enable a dendrite-free and highly reversible Li metal anode (LMA), we develop a cytomembrane-inspired artificial layer (CAL) with biomimetic ionic channels using a scalable spread coating method. The negatively charged CAL with uniform intraparticle and interparticle ionic channels facilitates the Li-ion transport and redistributes the Li-ion flux, contributing to stable and homogeneous Li stripping and plating. Furthermore, a robust underneath transition layer with abundant lithiophilic inorganic components is in-situ formed through the transformation of CAL during cycling, which promotes Li-ion diffusion and suppresses the continuous side reactions with the electrolyte. Additionally, the resulting cytomembrane-inspired artificial Janus layer (CAJL) displays an ultrahigh Young's modulus (≥10.7 GPa) to inhibit the dendrite growth. Consequently, the CAJL-protected LMA (Li@CAJL) is stably cycled with a high areal capacity of 10 mAh cm-2 at a high current density of 10 mA cm-2. More importantly, the effective CAJL modification realizes the stable operation of a practical 429.2 Wh kg-1 lithium-sulfur (Li-S) pouch cell using a low electrolyte/sulfur (E/S) ratio of 3 µL mg-1. The facile yet effective protection strategy of LMAs can promote the practical application of LMBs.

Boosting the performance and durability of heterogeneous electrodes for solid oxide electrochemical cells utilizing a data-driven powder-to-power framework.

Solid oxide electrochemical cells (SOCs) hold potential as a critical component in the future landscape of renewable energy storage and conversion systems. However, the commercialization of SOCs still requires further breakthroughs in new material development and engineering designs to achieve high performance and durability. In this study, a data-driven powder-to-power framework has been presented, fully digitizing the morphology evolution of heterogeneous electrodes from fabrication to long-term operation. This framework enables accurate performance prediction over the full life cycle. The intrinsic correlation between microstructural parameters and electrode durability is elucidated through parameter analysis. Rational control of the ion-conducting phase volume fraction can effectively suppress Ni coarsening and mitigate the excessive ohmic loss caused by Ni migration. The initial and degraded electrode performances are attributed to the interplay of multiple parameters. A practical optimization strategy to enhance the initial performance and durability of the electrode is proposed through the construction of the surrogate model and the application of the optimization algorithm. The optimal electrode parameters are determined to accommodate various maximum operation time requirements. By implementing the data-driven powder-to-power framework, it is possible to reduce the degradation rate of Ni-based electrodes from 2.132% to 0.703% kh-1 with a required maximum operation time of over 50,000 h.

An Electrolyte with Elevated Average Valence for Suppressing the Capacity Decay of Vanadium Redox Flow Batteries.

Nafion series membranes are widely used in vanadium redox flow batteries (VRFBs). However, the poor ion selectivity of the membranes to vanadium ions, especially for V2+, results in a rapid capacity decay during cycling. Although tremendous efforts have been made to improve the membrane's ion selectivity, increasing the ion selectivity without sacrificing the proton conductivity is still a challenging issue. In this work, instead of focusing on enhancing the membranes' ion selectivity, we develop an efficient valence regulation strategy to suppress the capacity decay caused by the crossover of V2+ in VRFBs. Despite the discharge capacity of the VRFB with the elevated average valence electrolytes (V3.68+) being slightly lower than that with commercial electrolytes (V3.50+) in the first 35 cycles, the accumulated discharge capacity in 400 cycles is improved by 52.33%. Moreover, this method is efficient, is easy to scale up, and provides deep insights into the capacity decay mechanism of VRFBs.

Enhancing Voltage Reversal Tolerance of Proton Exchange Membrane Fuel Cells by Tuning the Microstructure of IrOx Catalysts.

Voltage reversal of proton exchange membrane fuel cells caused by hydrogen deficiency seriously deteriorates the anodes and lowers their performance and lifetime. A commonly used method is to add oxygen evolution reaction catalysts (e.g., IrO2) to the anode to extend the water electrolysis plateau against harmful carbon corrosion. Herein, strongly connected IrOx nanoparticles (SC-IrOx) are prepared by removing the low surface area carbon carrier of the as-synthesized Ir/C catalyst. The reversal-tolerant anode with SC-IrOx owns an anti-reversal time of 9.32 h, which is 3.2 and 4.4 times that of the reversal-tolerant anode with commercial IrOx and weakly connected IrOx, respectively. Further transmission electron microscope characterizations reveal that SC-IrOx can construct a stable electron and proton transport pathway in the anode catalyst layer, which can delay the isolation of oxygen evolution reaction catalyst from the electron and proton conducting network, thus extending the water electrolysis plateau. Herein, our findings suggest that tuning the microstructures of IrOx catalysts is indeed an effective and promising approach to extend the water electrolysis plateau and alleviate the performance degradation of proton exchange membrane fuel cells during the voltage reversal process.

Echinatin mitigates sevoflurane-induced hippocampal neurotoxicity and cognitive deficits through mitigation of iron overload and oxidative stress.

CONTEXT: Sevoflurane (Sev) is a commonly used surgical anaesthetic; it has neurotoxic effects on the brain. Echinatin (Ech) is reported to have anti-inflammatory and antioxidant activity. OBJECTIVE: This research confirms the effect of Ech on Sev-induced neurotoxicity and cognitive deficits. MATERIALS AND METHODS: Primary rat hippocampal neurons were treated with 4.1% Sev for 6 h in the presence of Ech (5, 10, and 20 µM) or vehicle, followed by a further 42 h of culture. Male Sprague-Dawley aged rats were divided into 6 groups (n = 6): control, Sev, Sev + Ech (20 mg/kg;), Sev + Ech (40 mg/kg), and Sev + Ech (80 mg/kg). Rats were intraperitoneally injected with Ech or vehicle 1 h before Sev exposure (2% Sev for 5 h). RESULTS: We found that Ech (5, 10, and 20 µM) elevated cell viability (1.29-, 1.51-, 1.68-fold) but mitigated apoptosis (23.87% vs. 16.48%, 12.72%, 9.02%), oxidative stress, and ferroptosis in hippocampal neurons with Sev treatment. Ech activated the Nrf2 expression in Sev-induced in vitro and in vivo models of anaesthetic neurotoxicity. Ech also weakened neurotoxicity in hippocampal neurons with Sev treatment by increasing Nrf2 expression level. Moreover, Ech alleviated hippocampus neurons apoptosis (19.38% vs. 16.05%, 11.71%, 8.88%), oxidative stress, and ferroptosis in rats with Sev treatment. Ech improved Sev-induced cognitive deficits in rats. CONCLUSIONS: Ech alleviates Sev-induced neurotoxicity and cognitive deficits by mitigation of ferroptosis and oxidative stress. Ech may be developed as a new promising therapeutic drug for treatment of cerebral nerve injury caused by surgical anaesthesia.

Boosting the reaction kinetics in aprotic lithium-carbon dioxide batteries with unconventional phase metal nanomaterials.

Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO2) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO2 batteries with unconventional phase 4H/face-centered cubic (fcc) iridium (Ir) nanostructures grown on gold template. Significantly, 4H/fcc Ir exhibits superior electrochemical performance over fcc Ir in facilitating the round-trip reaction kinetics of Li+-mediated CO2 reduction and evolution, achieving a low charge plateau below 3.61 V and high energy efficiency of 83.8%. Ex situ/in situ studies and theoretical calculations reveal that the boosted reaction kinetics arises from the highly reversible generation of amorphous/low-crystalline discharge products on 4H/fcc Ir via the Ir-O coupling. The demonstration of flexible Li-CO2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

Sponge-Like Microfiber Electrodes for High-Performance Redox Flow Batteries.

Fabricating fiber-based electrodes with a large specific surface area while maintaining high flow permeability is a challenging issue in developing high-performance redox flow batteries. Here, a sponge-like microfiber carbon electrode is reported with a specific surface area of as large as 853.6 m2 g-1 while maintaining a fiber diameter in the range of 5-7 µm and a macropore size of ≈26.8 µm. The electrode is developed by electrospinning cross-linked poly(vinyl alcohol)-lignin-polytetrafluoroethylene precursors, followed by oxidation and pyrolysis. Applying the as-synthesized electrodes to a vanadium redox flow battery enables the battery to achieve an energy efficiency of 79.1% at the current density of 400 mA cm-2 and a capacity retention rate of 99.94% over 2000 cycles, representing one of the best battery performances in the open literature. The strategy to fabricate sponge-like porous carbon microfibers holds great promise for versatile applications in redox flow batteries and other energy storage systems.

A High-Capacity Polyethylene Oxide-Based All-Solid-State Battery Using a Metal-Organic Framework Hosted Silicon Anode.

Polyethylene oxide (PEO)-based solid electrolytes have been widely studied in all-solid-state lithium (Li) metal batteries due to their favorable interfacial contact with electrodes, facile fabrication, and low cost, but their inferior Li dendrite suppression capability renders low actual areal capacities of Li metal anodes. Here, we develop a high-capacity all-solid-state battery using a metal-organic framework hosted silicon (Si@MOF) anode and a fiber-supported PEO/garnet composite electrolyte. Si nanoparticles are embedded in the micro-sized MOF-derived carbon host, which efficiently accommodates the repeated deformation of Si over cycles while providing sufficient charge transfer pathways. As a result, the Si@MOF anode shows excellent interfacial stability toward the composite polymer electrolyte for over 1000 h and achieves a high reversible areal capacity of 3 mAh cm-2. The full cell using the LiFePO4 (LFP) cathode is able to deliver 135 mAh g-1 initially and maintains 73.1% of the capacity after 500 cycles at 0.5 C and 60 °C. More remarkably, the full cells with high LFP loadings achieve areal capacities of more than 2 mAh cm-2, exceeding most PEO-based ASSBs using metallic Li. Finally, the pouch cell using the proposed design exhibits decent electrochemical performance and high safety.

Highly porous carbon nanofiber electrodes for vanadium redox flow batteries.

The electrochemical performance of carbon nanofiber (CNF) electrodes in vanadium redox flow batteries (VRFBs) is enhanced by optimizing the morphological and physical properties of low-cost electrospun CNFs. The surface area, porosity and electrical conductivity of CNFs are tailored by modifying the precursor composition, especially the sacrificing agent, Fe(acac)3, in the polymer precursor and carbonization temperature. A highly porous structure with a large surface area is generated by the catalytic growth of graphitic carbon spheres surrounding the iron nanoparticles which are removed by an acid etching process. The graphitic carbon layers formed at a high carbonization temperature improve the electrical conductivity of CNFs. The large surface area of 349 m2 g-1 together with the abundant mesopore-dominant structure leads to high wettability and high activity for redox reactions of the electrode, giving rise to enhanced electrochemical performance in VRFBs. It delivers an energy efficiency (EE) of 91.4% at a current density of 20 mA cm-2 and 79.3% at 100 mA cm-2, and maintains an average EE of 72.5% after 500 charge/discharge cycles at 100 mA cm-2.

A Highly Reversible Zinc Anode for Rechargeable Aqueous Batteries.

Zinc metal holds a great potential as an anode material for next-generation aqueous batteries due to its suitable redox potential, high specific capacity, and low cost. However, the uncontrollable dendrite growth and detrimental side reactions with electrolytes hinder the practical application of this type of electrodes. To tackle the issues, an ultrathin (∼1 µm) sulfonated poly(ether ether ketone) (SPEEK) solid-electrolyte interphase (SEI) is constructed onto the Zn anode surface by a facile spin-coating method. We demonstrate that the polymeric SEI simultaneously blocks the water molecules and anions, uniformizes the ion flux, and facilitates the desolvation process of Zn2+ ions, thus effectively suppressing the side reactions and Zn dendrite formation. As a result, the newly developed Zn@SPEEK anode enables a symmetric cell to stably operate over 1000 cycles at 5 mA cm-2 without degradation. Moreover, with the Zn anode paired with a MnO2 cathode, the full cell exhibits an improved Coulombic efficiency (over 99% at 0.1 A g-1), a superior rate capability (127 mA h g-1 at 2 A g-1), and excellent cycling stability (capacity retention of 70% over 1000 cycles at 1 A g-1). This work provides a facile yet effective strategy to address the critical challenges in Zn anodes, paving the way for the development of high-performance rechargeable aqueous batteries.

A Passive Fuel Cell Fed with an Electrically Rechargeable Liquid Fuel.

Passive fuel cells, using diffusion and natural convection for fuel delivery, are regarded as promising candidates for powering portable devices including mobile phones and laptops. However, the performance of passive fuel cells which employ typical liquid alcohol fuels are still limited, which thereby greatly hampered their commercialization progress. Recently, a novel concept named the electrically rechargeable liquid fuel (e-fuel), with its rechargeability, cost-effectiveness, and superior reactivity, has attracted increasing attention. In this study, a passive fuel cell using the liquid e-fuel and the ambient air for electricity production is designed and fabricated. This passive fuel cell is demonstrated to achieve a peak power density of 116.2 mW cm-2 along with a stable operation for over 350 h, exhibiting great prospect for future applications.