Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis.

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO2 possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO2 catalyst containing metallic Ru─Ru interactions (m-RuO2) is reported, which maintains stability in practical PEMWE for 100 h at 60 °C and 1 A cm-2. Experimental and theoretical investigations suggest that the presence of Ru─Ru interactions significantly increases the energy barrier for the formation of RuO2(OH)2, which is a key intermediate for Ru dissolution, and hence substantially mitigates the electrochemical corrosion of m-RuO2. Meanwhile, the Ru4d band center downshifts, accordingly, ensuring the high OER activity, and the participation of lattice oxygen in the OER is also suppressed at the Ru─Ru sites, further contributing to the enhanced durability. Interestingly, such enhanced stability is also dependent on the size of metallic Ru─Ru cluster, where the energy barrier is further increased for Ru3, but is decreased for Ru5. These results highlight the significance of local coordination structure modulation on the electrochemical stability of RuO2 and open a feasible avenue toward the development of robust OER electrocatalysts for high-performance PEMWE.

Electron Manipulation and Surface Reconstruction of Bimetallic Iron-Nickel Phosphide Nanotubes for Enhanced Alkaline Water Electrolysis.

Developing high-efficiency and stable bifunctional electrocatalysts for water splitting remains a great challenge. Herein, NiMoO4 nanowires as sacrificial templates to synthesize Mo-doped NiFe Prussian blue analogs are employed, which can be easily phosphorized to Mo-doped Fe2xNi2(1-x)P nanotubes (Mo-FeNiP NTs). This synthesis method enables the controlled etching of NiMoO4 nanowires that results in a unique hollow nanotube architecture. As a bifunctional catalyst, the Mo-FeNiP NTs present lower overpotential and Tafel slope of 151.3 (232.6) mV at 100 mA cm-2 and 76.2 (64.7) mV dec-1 for HER (OER), respectively. Additionally, it only requires an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water splitting and can steadily operate for 200 h at 100 mA cm-2. First-principles calculations demonstrate that Mo doping can effectively adjust the electron redistribution of the Ni hollow sites to optimize the hydrogen adsorption-free energy for HER. Besides, in situ Raman characterization reveals the dissolving of doped Mo can promote a rapid surface reconstruction on Mo-FeNiP NTs to dynamically stable (Fe)Ni-oxyhydroxide layers, serving as the actual active species for OER. The work proposes a rational approach addressed by electron manipulation and surface reconstruction of bimetallic phosphides to regulate both the HER and OER activity.

Lithium Borohydride Nanorods: Self-Assembling Growth and Remarkable Hydrogen Cycling Properties.

Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.

Linearly Interlinked Fe-Nx -Fe Single Atoms Catalyze High-Rate Sodium-Sulfur Batteries.

Linearly interlinked single atoms offer unprecedented physiochemical properties, but their synthesis for practical applications still poses significant challenges. Herein, linearly interlinked iron single-atom catalysts that are loaded onto interconnected carbon channels as cathodic sulfur hosts for room-temperature sodium-sulfur batteries are presented. The interlinked iron single-atom exhibits unique metallic iron bonds that facilitate the transfer of electrons to the sulfur cathode, thereby accelerating the reaction kinetics. Additionally, the columnated and interlinked carbon channels ensure rapid Na+ diffusion kinetics to support high-rate battery reactions. By combining the iron atomic chains and the topological carbon channels, the resulting sulfur cathodes demonstrate effective high-rate conversion performance while maintaining excellent stability. Remarkably, even after 5000 cycles at a current density of 10 A g-1 , the Na-S battery retains a capacity of 325 mAh g-1 . This work can open a new avenue in the design of catalysts and carbon ionic channels, paving the way to achieve sustainable and high-performance energy devices.

Polymeric Electronic Shielding Layer Enabling Superior Dendrite Suppression for All-Solid-State Lithium Batteries.

LiBH4 is one of the most promising candidates for use in all-solid-state lithium batteries. However, the main challenges of LiBH4 are the poor Li-ion conductivity at room temperature, excessive dendrite formation, and the narrow voltage window, which hamper practical application. Herein, we fabricate a flexible polymeric electronic shielding layer on the particle surfaces of LiBH4. The electronic conductivity of the primary LiBH4 is reduced by 2 orders of magnitude, to 1.15 × 10-9 S cm-1 at 25 °C, due to the high electron affinity of the electronic shielding layer; this localizes the electrons around the BH4- anions, which eliminates electronic leakage from the anionic framework and leads to a 68-fold higher critical electrical bias for dendrite growth on the particle surfaces. Contrary to the previously reported work, the shielding layer also ensures fast Li-ion conduction due to the fast-rotational dynamics of the BH4- species and the high Li-ion (carrier) concentration on the particle surfaces. In addition, the flexibility of the layer guarantees its structural integrity during Li plating and stripping. Therefore, our LiBH4-based solid-state electrolyte exhibits a high critical current density (11.43 mA cm-2) and long cycling stability of 5000 h (5.70 mA cm-2) at 25 °C. More importantly, the electrolyte had a wide operational temperature window (-30-150 °C). We believe that our findings provide a perspective with which to avoid dendrite formation in hydride solid-state electrolytes and provide high-performance all-solid-state lithium batteries.

Oxygen-regulated spontaneous solid electrolyte interphase enabling ultra-stable solid-state Na metal batteries.

Solid-state sodium metal batteries utilizing inorganic solid electrolytes (SEs) hold immense potentials such as intrinsical safety, high energy density, and environmental sustainability. However, the interfacial inhomogeneity/instability at the anode-SE interface usually triggers the penetration of sodium dendrites into the electrolyte, leading to short circuit and battery failure. Herein, confronting with the original nonuniform and high-resistance solid electrolyte interphase (SEI) at the Na-Na3Zr2Si2PO12 interface, an oxygen-regulated SEI innovative approach is proposed to enhance the cycling stability of anode-SEs interface, through a spontaneous reaction between the metallic sodium (containing trace amounts of oxygen) and the Na3Zr2Si2PO12 SE. The oxygen-regulated spontaneous SEI is thin, uniform, and kinetically stable to facilitate homogenous interfacial Na+ transportation. Benefitting from the optimized SEI, the assembled symmetric cell exhibits an ultra-stable sodium plating/stripping cycle for over 6600 h under a practical capacity of 3 mAh cm-2. Quasi-solid-state batteries with Na3V2(PO4)3 cathode deliver excellent cyclability over 500 cycles at a rate of 0.5 C (1 C = 117 mA cm-2) with a high capacity retention of 95.4%. This oxygen-regulated SEI strategy may offer a potential avenue for the future development of high-energy-density solid-state metal batteries.

Differentiating attack-defense performance for starting and bench players during the Tokyo Olympics men's basketball competition.

This study aimed to explore the differences in attack-defense performance between the top and bottom teams for starting and bench players during the Tokyo Olympics men's basketball competition, to determine the relationship between the attack-defense performance of starting and bench players and the final competition rankings, as well as with each performance indicator. The rank-sum ratio (RSR) comprehensive evaluation was employed to describe the attack-defense performance of starting and bench players. Additionally, an independent sample t-test, Spearman Rho Correlation, and Pearson Correlation were conducted to test the differences and relationships between the various variables at a 0.05 level of significance, respectively. The results indicated that the top four teams showed significant differences in the attack-defense performance of their starting players compared to the bottom four teams (p = 0.021), mainly in terms of 3-point shooting percentage (p = 0.042) and free throw shooting percentage (p = 0.044). Besides that, the attack-defense ranks of both starting players (p = 0.004, r = 0.757) and bench players (p = 0.020, r = 0.658) had a significant correlation with the final rankings. Points per game, 2-point field goal percentage, and assists had a statistically significant (p<0.01) and strong positive correlation (0.70

Ir-Sn pair-site triggers key oxygen radical intermediate for efficient acidic water oxidation.

The anode corrosion induced by the harsh acidic and oxidative environment greatly restricts the lifespan of catalysts. Here, we propose an antioxidation strategy to mitigate Ir dissolution by triggering strong electronic interaction via elaborately constructing a heterostructured Ir-Sn pair-site catalyst. The formation of Ir-Sn dual-site at the heterointerface and the resulting strong electronic interactions considerably reduce d-band holes of Ir species during both the synthesis and the oxygen evolution reaction processes and suppress their overoxidation, enabling the catalyst with substantially boosted corrosion resistance. Consequently, the optimized catalyst exhibits a high mass activity of 4.4 A mgIr-1 at an overpotential of 320 mV and outstanding long-term stability. A proton-exchange-membrane water electrolyzer using this catalyst delivers a current density of 2 A cm-2 at 1.711 V and low degradation in an accelerated aging test. Theoretical calculations unravel that the oxygen radicals induced by the π* interaction between Ir 5d-O 2p might be responsible for the boosted activity and durability.

Adsorption Site Regulations of [W-O]-Doped CoP Boosting the Hydrazine Oxidation-Coupled Hydrogen Evolution at Elevated Current Density.

Hydrazine oxidation reaction (HzOR) assisted hydrogen evolution reaction (HER) offers a feasible path for low power consumption to hydrogen production. Unfortunately however, the total electrooxidation of hydrazine in anode and the dissociation kinetics of water in cathode are critically depend on the interaction between the reaction intermediates and surface of catalysts, which are still challenging due to the totally different catalytic mechanisms. Herein, the [W-O] group with strong adsorption capacity is introduced into CoP nanoflakes to fabricate bifunctional catalyst, which possesses excellent catalytic performances towards both HER (185.60 mV at 1000 mA cm-2) and HzOR (78.99 mV at 10,00 mA cm-2) with the overall electrolyzer potential of 1.634 V lower than that of the water splitting system at 100 mA cm-2. The introduction of [W-O] groups, working as the adsorption sites for H2O dissociation and N2H4 dehydrogenation, leads to the formation of porous structure on CoP nanoflakes and regulates the electronic structure of Co through the linked O in [W-O] group as well, resultantly boosting the hydrogen production and HzOR. Moreover, a proof-of-concept direct hydrazine fuel cell-powered H2 production system has been assembled, realizing H2 evolution at a rate of 3.53 mmol cm-2 h-1 at room temperature without external electricity supply.

Nanoparticulate ZrNi: In Situ Disproportionation Effectively Enhances Hydrogen Cycling of MgH2.

High thermal stability and sluggish absorption/desorption kinetics are still important limitations for using magnesium hydride (MgH2) as a solid-state hydrogen storage medium. One of the most effective solutions in improving hydrogen storage properties of MgH2 is to introduce a suitable catalyst. Herein, a novel nanoparticulate ZrNi with 10-60 nm in size was successfully prepared by co-precipitation followed by a molten-salt reduction process. The 7 wt % nano-ZrNi-catalyzed MgH2 composite desorbs 6.1 wt % hydrogen starting from ∼178 °C after activation, lowered by 99 °C relative to the pristine MgH2 (∼277 °C). The dehydrided sample rapidly absorbs ∼5.5 wt % H2 when operating at 150 °C for 8 min. The remarkably improved hydrogen storage properties are reasonably ascribed to the in situ formation of ZrH2, ZrNi2, and Mg2NiH4 caused by the disproportionation reaction of nano-ZrNi during the first de-/hydrogenation cycle. These catalytic active species are uniformly dispersed in the MgH2 matrix, thus creating a multielement, multiphase, and multivalent environment, which not only largely favors the breaking and rebonding of H-H bonds and the transfer of electrons between H- and Mg2+ but also provides multiple hydrogen diffusion channels. These findings are of particularly scientific importance for the design and preparation of highly active catalysts for hydrogen storage in light-metal hydrides.

Synergized Tricomponent All-Inorganics Solid Electrolyte for Highly Stable Solid-State Li-Ion Batteries.

Garnet-type oxide Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) features superior ionic conductivity and good stability toward lithium (Li) metal, but requires high-temperature sintering (≈1200 °C) that induces high fabrication cost, poor mechanical processability, and high interface resistance. Here, a novel high-performance tricomponent composite solid electrolyte (CSE) comprising LLZTO-4LiBH4 /xLi3 BN2 H8 is reported, which is prepared by ball milling the LLZTO-4LiBH4  mixture followed by hand milling with Li3 BN2 H8 . Green pellets fabricated by heating the cold-pressed CSE powders at 120 °C offer ultrafast room-temperature ionic conductivity (≈1.73 × 10-3  S cm-1  at 30 °C) and ultrahigh Li-ion transference number (≈0.9999), which enable the Li|Li symmetrical cells to cycle over 1600 h at 30 °C with only 30 mV of overpotential. Moreover, the Li|CSE|TiS2  full cells deliver 201 mAh g-1  of capacity with long cyclability. These outstanding performances are due to the low open porosity in the electrolyte pellets as well as the high intrinsic ionic conductivity and easy deformability of Li3 BN2 H8 .

Rubus chingii Hu relieved the polycystic ovary syndrome with enhanced insulin sensitivity through inhibiting TXNIP/NLRP3 inflammasome signaling.

BACKGROUND: Polycystic ovary syndrome (PCOS) is one of the most prevalent endocrine disorders in gynecology with severe metabolic abnormalities. Therefore, identifying effective treatments and drugs for PCOS is important. We aimed to investigate effect of the traditional Chinese medicine (TCM) Rubus chingii Hu (R. chingii) on ovarian function and insulin resistance (IR) of PCOS rat models, and to explore the underlying mechanisms. METHODS: A PCOS rat model was established by subcutaneous injection of dehydroepiandrosterone (DHEA) solution for 20 days. PCOS rats were randomly divided into a control group (CON), model group (MOD), metformin group (MET), TCM R. chingii group (RCG), and RCG + Ad-TXNIP groups. After 28 days of treatment, the samples were collected for subsequent experiments. RESULTS: R. chingii treatment alleviated hormone imbalance and IR while improving ovarian pathology in the PCOS model. R. chingi inhibited the activation of the thioredoxin-interacting protein (TXNIP)/NOD-like receptor family pyrin domain containing 3 (NLRP3) inflammasome in the ovarian tissue of PCOS rats. Furthermore, TXNIP overexpression hindered the protective effect of R. chingii intervention in PCOS rats, as evidenced by the increase of homeostasis model assessment of insulin resistance (HOMA-IR), luteinizing hormone (LH), testosterone (T), C-reactive protein (CRP) levels, and atretic follicles. CONCLUSION: R. chingii intervention improved ovarian polycystic development by suppressing the TXNIP/NLRP3 inflammasome, which may be an effective treatment for PCOS.

In-Situ-Generated Electron-Blocking LiH Enabling an Unprecedented Critical Current Density of Over 15 mA cm-2 for Solid-State Hydride Electrolytes.

LiBH4 is a promising solid-state electrolyte (SE) due to its thermodynamic stability to Li. However, poor Li-ion conductivities at room temperature, low oxidative stabilities, and severe dendrite growth hamper its application. In this work, a partial dehydrogenation strategy is adopted to in situ generate an electronic blocking layer dispersed of LiH, addressing the above three issues simultaneously. The electrically insulated LiH reduces the electronic conductivity by two orders of magnitude, leading to a 32.0-times higher critical electrical bias for dendrite growth on the particle surfaces than that of the counterpart. Additionally, this layer not only promotes the Li-ion conductance by stimulating coordinated rotations of BH4 - and B12 H12 2- , contributing to a Li-ion conductivity of 1.38 × 10-3 S cm-1 at 25 °C, but also greatly enhances oxidation stability by localizing the electron density on BH4 - , extending its voltage window to 6.0 V. Consequently, this electrolyte exhibits an unprecedented critical current density (CCD) of 15.12 mA cm-2 at 25 °C, long-term Li plating and stripping stability for 2700 h, and a wide temperature window for dendrite inhibition from -30 to 150 °C. Its Li-LiCoO2 cell displays high reversibility within 3.0-5.0 V. It is believed that this work provides a clear direction for solid-state hydride electrolytes.

An injectable nanocomposite alginate-Ca2+ hydrogel for melittin-assisted Ca2+-overload and photothermal cancer therapy.

An injectable nanocomposite alginate-Ca2+ hydrogel embedded with melittin and polyaniline nanofibers was fabricated for Ca2+-overload and photothermal combination cancer therapy. Melittin disrupts the cell membranes and enhances Ca2+ influx significantly, improving Ca2+-overload treatment, while the polyaniline nanofibers endow the hydrogel with glutathione (GSH) depletion and photothermal ability.

A rare presentation of central pontine myelinolysis secondary to hyperglycaemia.

BACKGROUND: Central pontine myelinolysis (CPM) is a rare demyelinating disorder caused by the loss of myelin in the center of the basis pontis. CPM typically occurs with rapid correction of severe chronic hyponatremia and subsequent disturbances in serum osmolality. Although hyperglycaemia is recognized as a pathogenetic factor in serum osmolality fluctuations, CPM is rarely seen in the context of diabetes. CASE PRESENTATION: A 66-year-old Chinese male presented with a history of gait imbalance, mild slurred speech and dysphagia for two weeks. MRI showed the mass lesions in the brainstem, and laboratory examinations showed high blood glucose and HbA1c, as well as increased serum osmolality. The patient was diagnosed with CPM secondary to hyperosmolar hyperglyceamia and received insulin treatment as well as supportive therapy. After six weeks of followup, the patient had fully recovered to a normal state. CONCLUSION: CPM is a potentially fatal neurological condition and can occur in uncontrolled diabetes mellitus. Early diagnosis and timely treatment are crucial for improving the prognosis.

Construction of Inorganic/Organic Hybrid Layer for Stable Na Metal Anode Operated under Wide Temperatures.

Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.

Molecular Engineering on Solvation Structure of Carbonate Electrolyte toward Durable Sodium Metal Battery at -40 °C.

Carbonate electrolytes have excellent chemical stability and high salt solubility, which are ideally practical choice for achieving high-energy-density sodium (Na) metal battery at room temperature. However, their application at ultra-low temperature (-40 °C) is adversely affected by the instability of solid electrolyte interphase (SEI) formed by electrolyte decomposition and the difficulty of desolvation. Here, we designed a novel low-temperature carbonate electrolyte by molecular engineering on solvation structure. The calculations and experimental results demonstrate that ethylene sulfate (ES) reduces the sodium ion desolvation energy and promotes the forming of more inorganic substances on the Na surface, which promote ion migration and inhibit dendrite growth. At -40 °C, the Na||Na symmetric battery exhibits a stable cycle of 1500 hours, and the Na||Na3 V2 (PO4 )3 (NVP) battery achieves 88.2 % capacity retention after 200 cycles.

Diversity of platinum-sites at platinum/fullerene interface accelerates alkaline hydrogen evolution.

Membrane-based alkaline water electrolyser is promising for cost-effective green hydrogen production. One of its key technological obstacles is the development of active catalyst-materials for alkaline hydrogen-evolution-reaction (HER). Here, we show that the activity of platinum towards alkaline HER can be significantly enhanced by anchoring platinum-clusters onto two-dimensional fullerene nanosheets. The unusually large lattice distance (~0.8 nm) of the fullerene nanosheets and the ultra-small size of the platinum-clusters (~2 nm) leads to strong confinement of platinum clusters accompanied by pronounced charge redistributions at the intimate platinum/fullerene interface. As a result, the platinum-fullerene composite exhibits 12 times higher intrinsic activity for alkaline HER than the state-of-the-art platinum/carbon black catalyst. Detailed kinetic and computational investigations revealed the origin of the enhanced activity to be the diverse binding properties of the platinum-sites at the interface of platinum/fullerene, which generates highly active sites for all elementary steps in alkaline HER, particularly the sluggish Volmer step. Furthermore, encouraging energy efficiency of 74% and stability were achieved for alkaline water electrolyser assembled using platinum-fullerene composite under industrially relevant testing conditions.

Dual-Atom Support Boosts Nickel-Catalyzed Urea Electrooxidation.

Nickel-based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by the inevitable self-oxidation reaction of Ni species (NSOR) during the UOR. Here, we proposed an interface chemistry modulation strategy to trigger the occurrence of UOR before the NSOR via constructing a 2D/2D heterostructure that consists of ultrathin NiO anchored Ru-Co dual-atom support (Ru-Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on the surface of Ru-Co DAS/NiO. Consequently, the fabricated catalyst exhibits outstanding UOR activity with a low potential of 1.288 V at 10 mA cm-2 and remarkable long-term durability for more than 330 h operation. DFT calculations and spectroscopic characterizations demonstrate that the favorable electronic structure induced by this unique heterointerface endows the catalyst energetically more favorable for the UOR than the NSOR.

Topologically Porous Heterostructures for Photo/Photothermal Catalysis of Clean Energy Conversion.

As a straightforward way to fix solar energy, photo/photothermal catalysis with semiconductor provides a promising way to settle the energy shortage and environmental crisis in many fields, especially in clean energy conversion. Topologically porous heterostructures (TPHs), featured with well-defined pores and mainly composed by the derivatives of some precursors with specific morphology, are a major part of hierarchical materials in photo/photothermal catalysis and provide a versatile platform to construct efficient photocatalysts for their enhanced light absorption, accelerated charges transfer, improved stability, and promoted mass transportation. Therefore, a comprehensive and timely review on the advantages and recent applications of the TPHs is of great importance to forecast the potential applications and research trend in the future. This review initially demonstrates the advantages of TPHs in photo/photothermal catalysis. Then the universal classifications and design strategies of TPHs are emphasized. Besides, the applications and mechanisms of photo/photothermal catalysis in hydrogen evolution from water splitting and COx hydrogenation over TPHs are carefully reviewed and highlighted. Finally, the challenges and perspectives of TPHs in photo/photothermal catalysis are also critically discussed.