Silver Surface-Assisted Dehydrobrominative Cross-Coupling between Identical Aryl Bromides.

Cross-coupling reactions represent an indispensable tool in chemical synthesis. An intriguing challenge in this field is to achieve selective cross-coupling between two precursors with similar reactivity or, to the limit, the identical molecules. Here we report an unexpected dehydrobrominative cross-coupling between 1,3,5-tris(2-bromophenyl)benzene molecules on silver surfaces. Using scanning tunneling microscopy, we examine the reaction process at the single-molecular level, quantify the selectivity of the dehydrobrominative cross-coupling, and reveal the modulation of selectivity by substrate lattice-related catalytic activity or molecular assembly effect. Theoretical calculations indicate that the dehydrobrominative cross-coupling proceeds via regioselective C-H bond activation of debrominated TBPB and subsequent highly selective C-C coupling of the radical-based intermediates. The reaction kinetics plays an important role in the selectivity for the cross-coupling. This work not only expands the toolbox for chemical synthesis but also provides important mechanistic insights into the selectivity of coupling reactions on the surface.

An ultralight, pulverization-free integrated anode toward lithium-less lithium metal batteries.

The high-capacity advantage of lithium metal anode was compromised by common use of copper as the collector. Furthermore, lithium pulverization associated with "dead" Li accumulation and electrode cracking deteriorates the long-term cyclability of lithium metal batteries, especially under realistic test conditions. Here, we report an ultralight, integrated anode of polyimide-Ag/Li with dual anti-pulverization functionality. The silver layer was initially chemically bonded to the polyimide surface and then spontaneously diffused in Li solid solution and self-evolved into a fully lithiophilic Li-Ag phase, mitigating dendrites growth or dead Li. Further, the strong van der Waals interaction between the bottommost Li-Ag and polyimide affords electrode structural integrity and electrical continuity, thus circumventing electrode pulverization. Compared to the cutting-edge anode-free cells, the batteries pairing LiNi0.8Mn0.1Co0.1O2 with polyimide-Ag/Li afford a nearly 10% increase in specific energy, with safer characteristics and better cycling stability under realistic conditions of 1× excess Li and high areal-loading cathode (4 milliampere hour per square centimeter).

A Fully Amorphous, Dynamic Cross-Linked Polymer Electrolyte for Lithium-Sulfur Batteries Operating at Subzero-Temperatures.

Solid-state lithium-sulfur batteries have shown prospects as safe, high-energy electrochemical storage technology for powering regional electrified transportation. Owing to limited ion mobility in crystalline polymer electrolytes, the battery is incapable of operating at subzero temperature. Addition of liquid plasticizer into the polymer electrolyte improves the Li-ion conductivity yet sacrifices the mechanical strength and interfacial stability with both electrodes. In this work, we showed that by introducing a spherical hyperbranched solid polymer plasticizer into a Li+ -conductive linear polymer matrix, an integrated dynamic cross-linked polymer network was built to maintain fully amorphous in a wide temperature range down to subzero. A quasi-solid polymer electrolyte with a solid mass content >90 % was prepared from the cross-linked polymer network, and demonstrated fast Li+ conduction at a low temperature, high mechanical strength, and stable interfacial chemistry. As a result, solid-state lithium-sulfur batteries employing the new electrolyte delivered high reversible capacity and long cycle life at 25 °C, 0 °C and -10 °C to serve energy storage at complex environmental conditions.

Refined Electrolyte and Interfacial Chemistry toward Realization of High-Energy Anode-Free Rechargeable Sodium Batteries.

Anode-free rechargeable sodium batteries represent one of the ultimate choices for the 'beyond-lithium' electrochemical storage technology with high energy. Operated based on the sole use of active Na ions from the cathode, the anode-free battery is usually reported with quite a limited cycle life due to unstable electrolyte chemistry that hinders efficient Na plating/stripping at the anode and high-voltage operation of the layered oxide cathode. A rational design of the electrolyte toward improving its compatibility with the electrodes is key to realize the battery. Here, we show that by refining the volume ratio of two conventional linear ether solvents, a binary electrolyte forms a cation solvation structure that facilitates flat, dendrite-free, planar growth of Na metal on the anode current collector and that is adaptive to high-voltage Na (de)intercalation of P2-/O3-type layered oxide cathodes and oxidative decomposition of the Na2C2O4 supplement. Inorganic fluorides, such as NaF, show a major influence on the electroplating pattern of Na metal and effective passivation of plated metal at the anode-electrolyte interface. Anode-free batteries based on the refined electrolyte have demonstrated high coulombic efficiency, long cycle life, and the ability to claim a cell-level specific energy of >300 Wh/kg.

Unraveling the Dynamic Processes of Methanol Electrooxidation at Isolated Rhodium Sites by In Situ Electrochemical Scanning Tunneling Microscopy.

Materials with isolated single-atom Rh-N4 sites are emerging as promising and compelling catalysts for methanol electrooxidation. Herein, we carried out an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of the dynamic processes of methanol absorption and catalytic conversion in the rhodium octaethylporphyrin (RhOEP)-catalyzed methanol oxidation reaction at the molecular scale. The high-contrast RhOEP-CH3OH complex formed by methanol adsorption was visualized distinctly in the STM images. The Rh-C adsorption configuration of methanol on isolated rhodium sites was identified on the basis of a series of control experiments and theoretical simulation. The adsorption energy of methanol on RhOEP was obtained from quantitative analysis. In situ ECSTM experiments present an explicit description of the transformation of the intermediate species in the catalytic process. By qualitatively evaluating the rate constants of different stages in the reaction at the microscopic level, we considered the CO transformation/desorption as the critical step for determining the reaction dynamics. Methanol adsorption was found to be correlated with RhOEP oxidation in the initial stage of the reaction, and the dynamic information was revealed unambiguously by in situ potential step experiments. This work provides microscopic results for the catalytic mechanism of Rh-N4 sites for methanol electrooxidation, which is instructive for the rational design of the high-performance catalyst.

Potential Controllable Redox Couple for Mild and Efficient Lithium Recovery from Spent Batteries.

The prosperity of the lithium-ion battery market is dialectically accompanied by the depletion of corresponding resources and the accumulation of spent batteries. It is an urgent priority to develop green and efficient battery recycling strategies for helping ease resources and environmental pressures at the current stage. Here, we propose a mild and efficient lithium extracting strategy based on potential controllable redox couples. Active lithium in the spent battery without discharging is extracted using a series of tailored aprotic solutions comprised of polycyclic aromatic hydrocarbons and ethers. This ensures a safe yet efficient recycling process with nearly ≈100 % lithium recovery. We further investigate the Li+ -electron concerted redox reactions and the effect of solvation structure on kinetics during the extraction, and broaden the applicability of the Li-PAHs solution. This work can stimulate new inspiration for designing novel solutions to meet efficient and sustainable demands in recycling batteries.

Blood Loss in Operation Is Independently Predictive of Postoperative Ventriculoperitoneal Shunt in Pediatric Patients With Posterior Fossa Tumors.

BACKGROUND: To identify the risk factors for postoperative hydrocephalus and the need for ventriculoperitoneal (VP) shunt after posterior fossa tumor (PFT) resection in pediatric patients and establish a predictive model. METHODS: A total of 217 pediatric patients (≤14 years old) with PFTs who underwent tumor resection from November 2010 to December 2020 were divided into a VP shunt group (n = 29) and non-VP shunt group (n = 188). Univariate and multivariate logistic regression were performed. A predictive model was established based on the independent predictors. Receiver operating characteristic curves were generated to determine the cutoff values and areas under the curve (AUCs). The Delong test was performed to compare the AUCs. RESULTS: Age less than three years (P = 0.015, odds ratio [OR] = 3.760), blood loss (BL) (P = 0.002, OR = 1.601), and locations at fourth ventricle (P < 0.001, OR = 7.697) were the independent predictors. The predictive model was as follows: total score = age (<3; yes = 2, no = 0) + BL + tumor locations (fourth ventricle; yes = 5, no = 0). The AUC of our model was higher than those of age less than three years, BL, locations at the fourth ventricle, and compound factors (age <3 + locations) (0.842 vs 0.609, 0.734, 0.732, and 0.788, respectively). The cutoff values of the model and BL were 7.5 points and 2.75 U, respectively. CONCLUSIONS: BL, age less than three years, and tumors at the fourth ventricle were independent predictors. Model scores over 7.5 points predict a high risk.

Chemical-Mechanical Robustness of Single-Crystalline Ni-Rich Cathode Enabled by Surface Atomic Arrangement Control.

Layered transition metal oxide cathodes have been one of the dominant cathodes for lithium-ion batteries with efficient Li+ intercalation chemistry. However, limited by the weak layered interaction and unstable surface, mechanical and chemical failure plagues their electrochemical performance, especially for Ni-rich cathodes. Here, adopting a simultaneous elemental-structural atomic arrangement control based on the intrinsic Ni-Co-Mn system, the surface role is intensively investigated. Within the invariant oxygen sublattice of the crystal, a robust surface with the synergistic concentration gradient and layered-spinel intertwined structure is constructed on the model single-crystalline Ni-rich cathode. With mechanical strain dissipation and chemical erosion suppression, the cathode exhibits an impressive capacity retention of 82 % even at the harsh 60 °C after 150 cycles at 1 C. This work highlights the coupling effect of structure and composition on the chemical-mechanical properties, and the concept will spur more researches on the cathodes that share the same sublattice.

Surface Lattice Modulation through Chemical Delithiation toward a Stable Nickel-Rich Layered Oxide Cathode.

Nickel-rich layered oxides (NLOs) are considered as one of the most promising cathode materials for next-generation high-energy lithium-ion batteries (LIBs), yet their practical applications are currently challenged by the unsatisfactory cyclability and reliability owing to their inherent interfacial and structural instability. Herein, we demonstrate an approach to reverse the unstable nature of NLOs through surface solid reaction, by which the reconstructed surface lattice turns stable and robust against both side reactions and chemophysical breakdown, resulting in improved cycling performance. Specifically, conformal La(OH)3 nanoshells are built with their thicknesses controlled at nanometer accuracy, which act as a Li+ capturer and induce controlled reaction with the NLO surface lattices, thereby transforming the particle crust into an epitaxial layer with localized Ni/Li disordering, where lithium deficiency and nickel stabilization are both achieved by transforming oxidative Ni3+ into stable Ni2+. An optimized balance between surface stabilization and charge transfer is demonstrated by a representative NLO material, namely, LiNi0.83Co0.07Mn0.1O2, whose surface engineering leads to a highly improved capacity retention and excellent rate capability with a strong capability to inhibit the crack of NLO particles. Our study highlights the importance of surface chemistry in determining chemical and structural behaviors and paves a research avenue in controlling the surface lattice for the stabilization of NLOs toward reliable high-energy LIBs.

Mitigating Swelling of the Solid Electrolyte Interphase using an Inorganic Anion Switch for Low-temperature Lithium-ion Batteries.

In overcoming the Li+ desolvation barrier for low-temperature battery operation, a weakly-solvated electrolyte based on carboxylate solvent has shown promises. In case of an organic-anion-enriched primary solvation sheath (PSS), we found that the electrolyte tends to form a highly swollen, unstable solid electrolyte interphase (SEI) that shows a high permeability to the electrolyte components, accounting for quickly declined electrochemical performance of graphite-based anode. Here we proposed a facile strategy to tune the swelling property of SEI by introducing an inorganic anion switch into the PSS, via LiDFP co-solute method. By forming a low-swelling, Li3 PO4 -rich SEI, the electrolyte-consuming parasitic reactions and solvent co-intercalation at graphite-electrolyte interface are suppressed, which contributes to efficient Li+ transport, reversible Li+ (de)intercalation and stable structural evolution of graphite anode in high-energy Li-ion batteries at a low temperature of -20 °C.

Evolution of Br⋯Br contacts in enantioselective molecular recognition during chiral 2D crystallization.

Halogen-mediated interactions play an important role in molecular recognition and crystallization in many chemical and biological systems, whereas their effect on homochiral versus heterochiral recognition and crystallization has rarely been explored. Here we demonstrate the evolution of Br⋯Br contacts in chiral recognition during 2D crystallization. On Ag(100), type I contacts prevail at low coverage and lead to homochiral recognition and the formation of 2D conglomerates; whereas type II contacts mediating heterochiral recognition are suppressed at medium coverage and appear in the racemates induced by structural transitions at high coverage. On Ag(111), type I contacts dominate the 2D crystallization and generate 2D conglomerates exclusively. DFT calculations suggest that the energy difference between type I and type II contacts is reversed upon adsorption due to the substrate induced mismatch energy penalty. This result provides fundamental understanding of halogen-mediated interactions in molecular recognition and crystallization on surface.

Probing the Synergistic Effects of Mg2+ on CO2 Reduction Reaction on CoPc by In Situ Electrochemical Scanning Tunneling Microscopy.

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg2+ in CO2 reduction reaction (CO2RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO2 environment, high-contrast species are observed in the adlayer and assigned to the CO2 adsorption on CoPc. Furthermore, the contrast of the CO2-bound complex is higher in Mg2+-containing electrolytes than in Mg2+-free electrolytes, indicating the formation of the CoPc-CO2-Mg2+ complex. The surface coverage of adsorbed CO2 is positively correlated with the Mg2+ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg2+) > 30 mM. The potential step experiment indicates the higher CO2 adsorption dynamics in Mg2+-containing electrolytes than without Mg2+. The rate constants of CO2 adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.

Epidemiologic Correlation and Drug Resistance Analysis of Pathogenic Bacteria in Different Open Limb Injury External Conditions.

OBJECTIVE: To study the epidemiological correlation and drug resistance of external factors of infection caused by open injury of limbs to pathogens. METHODS: This experiment is a retrospective study. We took the geographical location and climate of Nanchang, Jiangxi Province, China as the background, analyzed 2017 strains of pathogens from 1589 patients with limb trauma infection in a University Affiliated Hospital from 2012 to 2017. Patients were divided into three groups according to the type of incision: I, In-hospital infection of clean limb incision, II, In-hospital infection with open injury, III, Community infection with open injury of the limb. Groups II and Groups III were divided into six subgroups according to the causes of trauma, including: accidents from non-motor vehicles, machinery, cutting/piercing, pedestrian injuries, struck by/against, pedal cycles, and other injuries. We found eight common pathogens of orthopedic infection, which were mainly divided into Gram-positive bacteria (G+, mainly including Staphylococcus) and Gram-negative bacteria (G-, mainly Enterobacteriaceae). The relationship between main pathogens and damage mechanism, apparent temperature and relative humidity was discussed in this study. SPSS v22.0 was used for statistical analysis of the data. Friedman's two-way ANOVA was used to analyze the difference between the injury mechanism and incidence of pathogenic bacteria. Linear regression was used to determine the trend between the incidence of major pathogens and seasonal temperature and humidity. The level of significance was set as P < 0.05. RESULTS: There was no significant difference in the distribution of pathogens between Groups II and Groups III (P>0.05). The drug resistance of Groups III was significantly higher than that of Groups II and Groups I. G+ bacteria were resistant to cephalosporin, ceftriaxone and other cephalosporins and erythromycin and other macrolides. They were sensitive to vancomycin and linezolid. G- were resistant to the first- and the second-generation cephalosporins, including cefotetan and cefazolin, and ampicillin and other penicillins, while they were sensitive to third-generation cephalosporins, such as ceftazidime, as well as to levofloxacin and other quinolones, meropenem, and other beta-lactamases. The correlation between the injury mechanism and infection of pathogenic bacteria was not significant. The monthly average apparent temperature and relative humidity were correlated with the infection rate of pathogenic bacteria. CONCLUSION: In open injury of extremities, apparent temperature and relative humidity is an important risk factor for infection by pathogenic bacteria and the drug resistance of pathogenic bacteria in out-of-hospital infection was lower than that of hospital infection.

Kinetic Origin of Planar Gliding in Single-Crystalline Ni-Rich Cathodes.

Single-crystalline Ni-rich cathodes with high capacity have drawn much attention for mitigating cycling and safety crisis of their polycrystalline analogues. However, planar gliding and intragranular cracking tend to occur in single crystals with cycling, which undermine cathode integrity and therefore cause capacity degradation. Herein, we intensively investigate the origin and evolution of the gliding phenomenon in single-crystalline Ni-rich cathodes. Discrete or continuous gliding forms are revealed with new surface exposure including the gliding plane (003) and reconstructed (-108) under surface energy drive. It is also demonstrated that the gliding process is the in-plane migration of transition metal ions, and reducing oxygen vacancies will increase the migration energy barrier by which gliding and microcracking can be restrained. The designed cathode with less oxygen deficiency exhibits outstanding cycling performance with an 80.8% capacity retention after 1000 cycles in pouch cells. Our findings provide an insight into the relationship between defect control and chemomechanical properties of single-crystalline Ni-rich cathodes.

Interfacial Evolution of the Solid Electrolyte Interphase and Lithium Deposition in Graphdiyne-Based Lithium-Ion Batteries.

All-carbon graphdiyne (GDY)-based materials have attracted extensive attention owing to their extraordinary structures and outstanding performance in electrochemical energy storage. Straightforward insights into the interfacial evolution at GDY electrode/electrolyte interface could crucially enrich the fundamental comprehensions and inspire targeted regulations. Herein, in situ optical microscopy and atomic force microscopy monitoring of the GDY and N-doped GDY electrodes reveal the interplay between the solid electrolyte interphase (SEI) and Li deposition. The growth and continuous accumulation of the flocculent-like SEI is directly tracked at the surface of GDY electrode. Moreover, the nanoparticle-shaped SEI homogeneously propagates at the interface when N configurations are involved, providing a critical clue for the N-doping effects of stabilizing interfaces and homogenizing Li deposition. This work probes into the dynamic evolution and structure-reactivity correlation in detail, creating effective strategies for GDY-based materials optimization in lithium-ion batteries.

Electrocatalytic Hydrogen Oxidation in Alkaline Media: From Mechanistic Insights to Catalyst Design.

With the potential to circumvent the need for scarce and cost-prohibitive platinum-based catalysts in proton-exchange membrane fuel cells, anion-exchange membrane fuel cells (AEMFCs) are emerging as alternative technologies with zero carbon emission. Numerous noble metal-free catalysts have been developed with excellent catalytic performance for cathodic oxygen reduction reaction in AEMFCs. However, the anodic catalysts for hydrogen oxidation reaction (HOR) still rely on noble metal materials. Since the kinetics of HOR in alkaline media is 2-3 orders of magnitude lower than that in acidic media, it is a major challenge to either improve the performance of noble metal catalysts or to develop high-performance noble metal-free catalysts. Additionally, the mechanisms of alkaline HOR are not yet clear and still under debate, further hampering the design of electrocatalysts. Against this backdrop, this review starts with the prevailing theories for alkaline HOR on the basis of diverse activity descriptors, i.e., hydrogen binding energy theory and bifunctional theory. The design principles and recent advances of HOR catalysts employing the aforementioned theories are then summarized. Next, the strategies and recent progress in improving the antioxidation capability of HOR catalysts, a thorny issue which has not received sufficient attention, are discussed. Moreover, the significance of correlating computational models with real catalyst structure and the electrode/electrolyte interface is further emphasized. Lastly, the remaining controversies about the alkaline HOR mechanisms as well as the challenges and possible research directions in this field are presented.

Anion Doping for Layered Oxides with a Solid-Solution Reaction for Potassium-Ion Battery Cathodes.

The development of potassium-ion batteries (PIBs) is challenged by the shortage of stable cathode materials capable of reversibly hosting the large-sized K+ (1.38 Å), which is prone to cause severe structural degradation and complex phase evolution during the potassiation/depotassiation process. Here, we identified that anionic doping of the layered oxides for PIBs is effective to combat their capacity fading at high voltage (>4.0 V). Taking P2-type K2/3Mn7/9Ni1/9Ti1/9O17/9F1/9 (KMNTOF) as an example, we showed that the partial substitution of O2- by F- enlarged the interlayer distance of the K2/3Mn7/9Ni1/9Ti1/9O2 (KMNTO), which becomes more favorable for fast K+ transition without violent structural destruction. Meanwhile, based on the experimental data and theoretical results, we identified that the introduction of F- anions effectively increased the redox-active Mn cationic concentration by lowering the average valence of the Mn element, accordingly providing more reversible capacity derived from the Mn3+/4+ redox couple, rather than oxygen redox. This anionic doping strategy enables the KMNTOF cathode to deliver a high reversible capacity of 132.5 mAh g-1 with 0.53 K+ reversible (de)intercalation in the structure. We expect that the discovery provides new insights into structural engineering for pursuing stable cathodes to facilitate the future applications of high-performance PIBs.

Advancing to 4.6 V Review and Prospect in Developing High-Energy-Density LiCoO2 Cathode for Lithium-Ion Batteries.

Layered LiCoO2 (LCO) is one of the most important cathodes for portable electronic products at present and in the foreseeable future. It becomes a continuous push to increase the cutoff voltage of LCO so that a higher capacity can be achieved, for example, a capacity of 220 mAh g-1 at 4.6 V compared to 175 mAh g-1 at 4.45 V, which is unfortunately accompanied by severe capacity degradation due to the much-aggravated side reactions and irreversible phase transitions. Accordingly, strict control on the LCO becomes essential to combat the inherent instability related to the high voltage challenge for their future applications. This review begins with a discussion on the relationship between the crystal structures and electrochemical properties of LCO as well as the failure mechanisms at 4.6 V. Then, recent advances in control strategies for 4.6 V LCO are summarized with focus on both bulk structure and surface properties. One closes this review by presenting the outlook for future efforts on LCO-based lithium ion batteries (LIBs). It is hoped that this work can draw a clear map on the research status of 4.6 V LCO, and also shed light on the future directions of materials design for high energy LIBs.

Selective Extraction of Transition Metals from Spent LiNix Coy Mn1-x-y O2 Cathode via Regulation of Coordination Environment.

The complexity of chemical compounds in lithium-ion batteries (LIBs) results in great difficulties in the extraction of multiple transition metals, which have similar physicochemical characteristics. Here, we propose a novel strategy for selective extraction of nickel, cobalt, and manganese from spent LiNix Coy Mn1-x-y O2 (NCM) cathode through the regulation of coordination environment. Depending on adjusting the composition of ligand in transition metal complexes, a tandem leaching and separation system is designed and finally enables nickel, cobalt, and manganese to enrich in the form of NiO, Co3 O4 , and Mn3 O4 with high recovery yields of 99.1 %, 95.1 %, and 95.3 %, respectively. We further confirm that the combination of different transition metals with well-designed ligands is the key to good selectivity. Through our work, fine-tuning the coordination environment of metal ions is proved to have great prospects in the battery recycling industry.

Constructing Stable Chromenoquinoline-Based Covalent Organic Frameworks via Intramolecular Povarov Reaction.

Chemically stable chromenoquinoline (CQ)-based covalent organic frameworks (COFs) were constructed by postsynthetic conversion of imine COFs. The key step of an intramolecular Povarov reaction can transform a preintegrated alkyne group to bridge the benzene rings on both sides of the imine linkage via chemical bonds, affording a ladder-type CQ linkage. This novel approach achieves a high cyclization degree of 80-90%, which endows the CQ-COFs with excellent chemical stability toward strong acid, base, and redox reagents. The synthetic approach can be applied to various monomers with different symmetries and functional core moieties. The absorption and fluorescence intensities of CQ-COFs are sensitive to acid, which allows for dual-mode sensing of strongly acidic environments.