Reversible Oxygen Redox Chemistry in High-Entropy P2-Type Manganese-Based Cathodes via Self-Regulating Mechanism.

The irreversible oxygen-redox reactions in the high-voltage region of sodium-layered cathode materials lead to poor capacity retention and structural instability during cycling, presenting a significant challenge in the development of high-energy-density sodium-ion batteries. This work introduces a high-entropy design for layered Na0.67Li0.1Co0.1Cu0.1Ni0.1Ti0.1Mn0.5O2 (Mn-HEO) cathode with a self-regulating mechanism to extend specific capacity and energy density. The oxygen redox reaction was activated during the initial charging process, accompanied by the self-regulation of active elements, enhancing the ionic bonds to form a vacancy wall near the TM vacancies and thus preventing the migration of transition metal elements. Systematic in situ/ex situ characterizations and theoretical calculations comprehensively support the understanding of the self-regulation mechanism of Mn-HEO. As a result, the Mn-HEO cathode exhibits a stable structure during cycling. It demonstrates almost zero strain within a wide voltage range of 2.0-4.5 V with a remarkable specific capacity (177 mAh g-1 at 0.05 C) and excellent long-term cycling stability (87.6% capacity retention after 200 cycles at 2 C). This work opens a new pathway for enhancing the stability of oxygen-redox chemistry and revealing a mechanism of crystal structure evolution for high-energy-density layered oxides.

Ag1+ incorporation via a Zr4+-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCO2RR-to-CO activity.

Attaining meticulous dominion over the binding milieu of catalytic metal sites remains an indispensable pursuit to tailor product selectivity and elevate catalytic activity. By harnessing the distinctive attributes of a Zr4+-anchored thiacalix[4]arene (TC4A) metalloligand, we have pioneered a methodology for incorporating catalytic Ag1+ sites, resulting in the first Zr-Ag bimetallic cluster, Zr2Ag7, which unveils a dualistic configuration embodying twin {ZrAg3(TC4A)2} substructures linked by an {AgSal} moiety. This cluster unveils a trinity of discrete Ag sites: a pair ensconced within {ZrAg3(TC4A)2} subunits and one located between two units. Expanding the purview, we have also crafted ZrAg3 and Zr2Ag2 clusters, meticulously mimicking the two Ag site environment inherent in the {ZrAg3(TC4A)2} monomer. The distinct structural profiles of Zr2Ag7, ZrAg3, and Zr2Ag provide an exquisite foundation for a precise comparative appraisal of catalytic prowess across three Ag sites intrinsic to Zr2Ag7. Remarkably, Zr2Ag7 eclipses its counterparts in the electroreduction of CO2, culminating in a CO faradaic efficiency (FECO) of 90.23% at -0.9 V. This achievement markedly surpasses the performance metrics of ZrAg3 (FECO: 55.45% at -1.0 V) and Zr2Ag2 (FECO: 13.09% at -1.0 V). Utilizing in situ ATR-FTIR, we can observe reaction intermediates on the Ag sites. To unveil underlying mechanisms, we employ density functional theory (DFT) calculations to determine changes in free energy accompanying each elementary step throughout the conversion of CO2 to CO. Our findings reveal the exceptional proficiency of the bridged-Ag site that interconnects paired {ZrAg3(TC4A)2} units, skillfully stabilizing *COOH intermediates, surpassing the stabilization efficacy of the other Ag sites located elsewhere. The invaluable insights gleaned from this pioneering endeavor lay a novel course for the design of exceptionally efficient catalysts tailored for CO2 reduction reactions, emphatically underscoring novel vistas this research unshrouds.

Concentration-Gradient Structural LiFe0.5Mn0.5PO4/C Prepared via Co-precipitation Reaction for Advanced Lithium-Ion Batteries.

The intrinsically low electronic conductivity and slow ion diffusion kinetics limit further development of olivine LiFexMn1-xPO4 cathode materials. In this paper, with the aim of improving the performance of such materials and alleviating the Jahn-Taller effect of Mn3+ ion, a bimetallic oxalate precursor with gradient distribution of elemental concentration followed with an efficient process is applied to synthesize LiFe0.5Mn0.5PO4 nanocomposite. The results shown that with certain structural modulation of the precursor, the discharge capacity of synthesized LiFe0.5Mn0.5PO4 increased from 149 mAh g-1 to 156 mAh g-1 at 0.1 C, the cycling capacity was also remarkably improved. the Fe0.5Mn0.5C2O4 ⋅ 2H2O-1 precursor with gradient distribution of elemental concentration effectively restricts the reaction between electrode material and electrolyte, thereby alleviates the dissolution of Mn3+ ion, reduces the decay of capacity and improves the stability of the material.

Reconstructing interfacial manganese deposition for durable aqueous zinc-manganese batteries.

Low-cost, high-safety, and broad-prospect aqueous zinc-manganese batteries (ZMBs) are limited by complex interfacial reactions. The solid-liquid interfacial state of the cathode dominates the Mn dissolution/deposition process of aqueous ZMBs, especially the important influence on the mass and charge transfer behavior of Zn2+ and Mn2+. We proposed a quasi-eutectic electrolyte (QEE) that would stabilize the reversible behavior of interfacial deposition and favorable interfacial reaction kinetic of manganese-based cathodes in a long cycle process by optimizing mass and charge transfer. We emphasize that the initial interfacial reaction energy barrier is not the main factor affecting cycling performance, and the good reaction kinetics induced by interfacial deposition during the cycling process is more conducive to the stable cycling of the battery, which has been confirmed by theoretical analysis, quartz crystal microbalance with dissipation monitoring, depth etching X-ray photon-electron spectroscopy, etc. As a result, the QEE electrolyte maintained a stable specific capacity of 250 mAh g-1 at 0.5 A g-1 after 350 cycles in zinc-manganese batteries. The energy density retention rate of the ZMB with QEE increased by 174% compared to that of conventional aqueous electrolyte. Furthermore, the multi-stacked soft-pack battery with a cathodic mass load of 54.4 mg maintained a stable specific capacity of 200 mAh g-1 for 100 cycles, demonstrating its commercial potential. This work proves the feasibility of adapting lean-water QEE to the stable aqueous ZMBs.

Balanced Interfacial Ion Concentration and Migration Steric Hindrance Promoting High-Efficiency Deposition/Dissolution Battery Chemistry.

The solid-liquid transition reaction lays the foundation of electrochemical energy storage systems with high capacity, but realizing high efficiency remains a challenge. Herein, in terms of thermodynamics and dynamics, this work demonstrates the significant role of both interfacial H+ concentration and Mn2+ migration steric hindrance for the high-efficiency deposition/dissolution chemistry of zinc-manganese batteries. Specially, the introduction of formate anions can buffer the generated interfacial H+ to stabilize interfacial potential according to the Nernst equation, which stimulates high capacity. Compared with acetate and propionate anions, the formate anion also provides high adsorption density on the cathode surface to shield the electrostatic repulsion due to the small spatial hindrance. Particularly for the solvated Mn2+ , the formate-anion-induced lower energy barrier of the rate-determining step during the step-by-step desolvation process results in lower polarization and higher electrochemical reversibility. In situ tests and theoretical calculations verify that the electrolyte with formate anions achieve a good balance between ion concentration and ion-migration steric hindrance. It exhibits both the high energy density of 531.26 W h kg-1  and long cycle life of more than 300 cycles without obvious decay.

A theoretical study of the monolayer-protected gold cluster Au317(SR)110.

Significant efforts have been made to uncover the structures of monolayer-protected gold nanoclusters. However, the synthesis, crystallization, and structural analysis of gold nanoclusters with over 300 metal atoms is a grand challenge. In this work, a new gold nanocluster containing 317 gold atoms and 110 thiolate (SH) ligands (referred to as Au317(SH)110) is theoretically studied, which is larger in size than the formerly reported Au279(SR)84 cluster. The stability of the Au317(SH)110 cluster is studied based on calculations of the averaged cluster formation energy (Eave), indicating that Au317(SH)110 has good structural stability and that the SPhCOOH (p-MBA) ligand is a good candidate for stabilizing the cluster. The calculation of density of state and the time-dependent density functional theory (TD-DFT) calculations of the optical absorption properties show that Au317(SH)110 is in a metallic state.

Highly Effective Trapping-Conversion Interface Based on Nickel-Modified Versatile Carbon Skeleton Enabled High-Performance Li-S Battery.

The development of comprehension in the mechanism of lithium-sulfur (Li-S) batteries creates more opportunities and potential for the application of interlayer. However, the viable design of versatile interlayer to retard the shuttling effects and improve the sluggish kinetics is still a focus and paramount challenge. Herein, we present a tentacles-like metallic nickel-modified and nitrogen-doped carbon skeleton (NCS) to serve as adsorbent and catalyst in the lithium-sulfur battery (LSBs). The carbonized skeleton and derived carbon tubes jointly construct conductive networks and adequate ion pathways. Meanwhile, abundant metallic nickel nanoparticles synergistically build a multifunctional interface with polar networks for the fixation and conversion of polysulfides, giving rise to significant improvement of cyclic stability and reaction kinetics of LSBs. As a result, the Li-S batteries using NCS as an interlayer could possess superior electrochemical performance including cyclic stability, high specific capacity (1204.8 mAh g-1 at 0.2C, 998.7 mAh g-1 at 1C), and good Coulombic efficiency. More importantly, even with the areal sulfur loading of up to 6.1 and 7.5 mg cm-2, it still demonstrates superior electrochemical performance with the areal capacity of 4.2 and 5.9 mAh cm-2 with steady cycling, respectively. In conclusion, we confirm this work provides a promising way to explore and expand the application of metal nanoparticles in interlayers for advanced Li-S batteries.

Angiotensin-converting enzyme I/D polymorphism and acute respiratory distress syndrome.

BACKGROUND: Some studies have assessed the association between angiotensin-converting enzyme (ACE) I/D polymorphism and acute respiratory distress syndrome (ARDS) risk. However, the results have been inconclusive and contradictory. Therefore, we performed a meta-analysis to investigate the association between ACE I/D polymorphism and ARDS risk. METHODS: All relevant studies were searched using PubMed and EMBASE. Odds ratios (ORs) and corresponding 95% confidence intervals (CIs) were estimated using random-effects models or fixed-effects models. RESULTS: A total of 14 studies with 5218 subjects were included in this meta-analysis. We found that ACE I/D polymorphism significantly associated with an increased ARDS risk (OR=1.57; 95% CI 1.30-1.89; P<0.00001). In the subgroup analysis by race, Caucasians with ACE I/D polymorphism showed increased ARDS risk (OR=1.63; 95% CI 1.32-2.02; P<0.00001). However, Asians with this polymorphism did not show significantly increased ARDS risk (OR=1.31; 95% CI 0.90-1.90; P=0.95). In the subgroup analysis by age group, adults showed increased ARDS risk (OR=1.60; 95% CI 1.32-1.93; P<0.00001), while pediatric patients did not have increased ARDS risk (OR=1.15; 95% CI 0.57-2.30; P=0.70). CONCLUSIONS: This meta-analysis suggested that ACE I/D polymorphism might contribute to the susceptibility for ARDS.

[Identification of Ligesticum chuanxiong by X-ray diffraction Fourier pattern method].

OBJECTIVE: To establish a new identification and analysis method of Chinese medicinal materia Ligesticum chuanxiong Hort. METHODS: Powder X-ray diffraction Fourier pattern. RESULTS: Experiments and analysis were carried out on five samples. The standard X-ray diffraction Fourier pattern and characteristic diffraction peaks of Ligesticum chuanxiong Hort. were obtained. CONCLUSION: This method can be used for identification of Ligesticum chuanxiong Hort.