High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

Manipulating oxygenate adsorption on N-doped carbon by coupling with CoSn alloy for bifunctional oxygen electrocatalyst

Highly active bifunctional oxygen electrocatalysts accelerate the development of high-performance Zn-air battery,but suffer from the mismatched activities of oxygen evolution reaction(OER)and oxygen reduced reaction(ORR).Herein,highly integrated bifunctional oxygen electrocatalysts,cobalt-tin alloys coated by nitrogen doped carbon(CoSn@NC)are prepared by MOFs-derived method.In this hybrid catalyst,the binary CoSn nanoalloys mainly contribute to highly active OER process while the Co(or Sn)-N-C serves as ORR active sites.Rational interaction between CoSn and NC donates more rapid reaction kinetics than Pt/C(ORR)and IrO_(2)(OER).Such CoSn@NC holds a promise as air-cathode electrocatalyst in Zn-air battery,superior to Pt/C+IrO_(2)catalyst.First-principles calculations predict that CoSn alloys can upgrade charge redistribution on NC and promote the transfer to reactants,thus optimizing the adsorption strength of oxygen-containing intermediates to boost the overall reactivity.The tuning of oxygenate adsorption by interactions between alloy and heteroatom-doped carbon can guide the design of bifunctional oxygen electrocatalysts.

Nitrogen-doped hierarchical few-layered porous carbon for efficient electrochemical energy storage

Large surface area,high conductivity,and rich active site of carbon electrode materials are necessary characteristics for energy storage devices.However,high conductivity and high nitrogen doping of carbon electrode materials are difficult to coordinate.Here,a facile method via the carbonization of nitrogen-containing Schiff base polymer has been developed to prepare high conductivity and high nitrogen-doped hierarchical porous carbon.The organic components with a benzene ring structure in the polymer promote the formation of more sp^(2)-graphitized carbon,which is beneficial for the improvement of electrical conductivity.Nitrogen-doped hierarchical porous carbon calcined at 900℃ under the NH3 atmosphere possesses high nitrogen content of 7.48 at%,a large specific surface area of 1613.2m2/g,and high electrical conductivity of 2.7 S/cm.As electrode materials in an aqueous-based supercapacitor,nitrogen-doped hierarchical porous carbon exhibits superior specific capacitance of 385 F/g at 1 A/g as well as excellent rate performance(242 and 215 F/g at a current density of 100 and 200 A/g,respectively).In addition,the specific capacitance of electrode measured in a two-electrode system is 335 F/g at 1 A/g,and the long-term cycling stability can be achieved with more than 94%initial capacitance after 10000 cycles.The constructed symmetric supercapacitor delivers high energy density and high power density.The outstanding electrochemical performances combined with the novel and scalable synthetic approach make the nitrogen‐doped hierarchical porous carbon potential electrode material for electrochemical devices.

Electronic structure and spatial inhomogeneity of iron-based superconductor FeS

Iron-based superconductor family FeX(X=S,Se,Te)has been one of the research foci in physics and material science due to their record-breaking superconducting temperature(FeSe film)and rich physical phenomena.Recently,FeS,the least studied Fe X compound(due to the difficulty in synthesizing high quality macroscopic crystals)attracted much attention because of its puzzling superconducting pairing symmetry.In this work,combining scanning tunneling microscopy and angle resolved photoemission spectroscopy(ARPES)with sub-micron spatial resolution,we investigate the intrinsic electronic structures of superconducting FeS from individual single crystalline domains.Unlike FeTe or FeSe,FeS remains identical tetragonal structure from room temperature down to 5 K,and the band structures observed can be well reproduced by our ab-initio calculations.Remarkably,mixed with the 1×1 tetragonal metallic phase,we also observe the coexistence of √5×√5 reconstructed insulating phase in the crystal,which not only helps explain the unusual properties of FeS,but also demonstrates the importance of using spatially resolved experimental tools in the study of this compound.

Metal cyanamides: Open-framework structure and energy conversion/storage applications

Metal cyanamides are an emerging class of functional materials with potential applications in sustainable energy conversion and storage technologies such as catalysis,supercapacitors,photoluminescence and next-gen batteries.The[NCN]^(2-)as the anion,which is isolobal with[O]^(2-)endows metal cyanamides with similar physicochemical properties as oxides and chalcogenides.Whereas the unique quasI-linear structure and electronic resonance between[N=C=N]^(2-)and[N-C≡N]^(2-)of[NCN]entity bring out superior properties beyond oxides and chalcogenides.In this review,we present research status,challenges,and the recent striking progress on the metal cyanamides in the synthesis and applications.Specifically,the characteristic structures,physicochemical properties,synthetic methods with corresponding merits/demerits and latest applications in energy conversion and storage of cyanamides are summarized.The detailed outlooks for the new compounds design,morphology manipulation and potential applications are also exhibited.

Chemical proteomics:terra incognita for novel drug target profiling

The growing demand for new therapeutic strategies in the medical and pharmaceutic fields has resulted in a pressing need for novel druggable targets.Paradoxically,however,the targets of certain drugs that are already widely used in clinical practice have largely not been annotated.Because the pharmacologic effects of a drug can only be appreciated when its interactions with cellular components are clearly delineated,an integrated deconvolution of drug-target interactions for each drug is necessary.The emerging field of chemical proteomics represents a powerful mass spectrometry(MS)-based affinity chromatography approach for identifying proteome-wide small molecule-protein interactions and mapping these interactions to signaling and metabolic pathways.This technique could comprehensively characterize drug targets,profile the toxicity of known drugs,and identify possible off-target activities.With the use of this technique,candidate drug molecules could be optimized,and predictable side effects might consequently be avoided.Herein,we provide a holistic overview of the major chemical proteomic approaches and highlight recent advances in this area as well as its potential applications in drug discovery.

SiO2 stabilizes electrochemically active nitrogen in few-layer carbon electrodes of extraordinary capacitance

Pyrrolic and pyridinic N dopants can dramatically increase the electrochemical activities of carbon and conducting polymers.Although N-doped conducting polymers suffer from rapid degradation,their carbon counterpart of extraordinary capacitance has remarkable rate performance and cycling endurance thanks to carbon’s excellent electrical conductivity.But high nitrogen content and high electrical conductivity are difficult to achieve in a high-surface-area carbon,because the high chemical vapor deposition(CVD)temperature required for obtaining high conductivity also destabilizes under-coordinated pyrrolic and pyridinic nitrogen and tends to lower the surface area.Here we resolve this dilemma by using SiO2 as an effective N-fixation additive,which stabilizes the N-rich nano few-layer sp2-carbon construct in1000℃CVD.This enables a scalable sol-gel/CVD fabrication process for few-layer carbon electrodes of extraordinary capacitance(690 F g^-1).The electrodes have excellent rate performance and can maintain90%of their initial capacitance after 30,000 cycles,thus potentially suitable for practical applications.

Unlocking efficient energy storage via regulating ion and electron-active subunits:an(SbS)_(1.15)TiS_(2)superlattice for large and fast Na^(+)storage

Alloying-type metal sulfides with high sodiation activity and theoretical capacity are promising anode materials for high energy density sodium ion batteries.However,the large volume change and the migratory and aggregation behavior of metal atoms will cause severe capacity decay during the charge/discharge process.Herein,a robust and conductive TiS_(2)framework is integrated with a high-capacity SbS layer to construct a single phase(SbS)_(1.15)TiS_(2)superlattice for both high-capacity and fast Na^(+)storage.The metallic TiS_(2)sublayer with high electron activity acts as a robust and conductive skeleton to buffer the volume expansion caused by conversion and alloying reaction between Na+and SbS sublayer.Hence,high capacity and high rate capability can be synergistically realized in a single phase(SbS)_(1.15)TiS_(2)superlattice.The novel(SbS)_(1.15)TiS_(2)anode has a high charge capacity of 618 mAh g^(-1)at 0.2 C and superior rate performance and cycling stability(205 mAh g^(-1)at 35 C after 2,000 cycles).Furthermore,in situ and ex situ characterizations are applied to get an insight into the multi-step reaction mechanism.The integrity of robust Na-Ti-S skeleton during(dis)charge process can be confirmed.This superlattice construction idea to integrate the Na^(+)-active unit and electron-active unit would provide a new avenue for exploring high-performance anode materials for advanced sodium-ion batteries.

In-situ construction of PDOL electrolyte with dual-reinforced stable interface for high-voltage lithium metal batteries

In-situ polymerized electrolytes significantly enhance the interfacial compatibility of lithium metal batteries(LMBs). Typically,in-situ polymerized 1,3-dioxolane(PDOL) exhibits low interfacial resistance, yet still suffers from low ionic conductivity and a narrow electrochemical stability window(ESW). Here, an ultra-stable PDOL-based polymer electrolyte is developed by incorporating plasticizers of tetramethylene sulfone(TMS) and fluorinated ethylene carbonate(FEC) into the 3D cross-linked network, achieving a significant enhancement in the transport capacity and efficiency of Li-ion. The ionic conductivity reaches3.63×10^(-4)S cm^(-1)even at room temperature, and the transference number(tLi^(+)) is even higher at 0.85. Furthermore, the ESW of this electrolyte can be increased to 4.5 V with the addition of TMS, which forms a thin and robust antioxidant cathode-electrolyte interface(CEI) on the surface of high-voltage LiCoO_(2). FEC generates an inorganic-rich solid-electrolyte interface(SEI) on the Li anode, which effectively inhibits the growth of lithium dendrites. Benefiting from the aforementioned advantages, the highvoltage lithium metal battery demonstrates outstanding long-cycle stability, with 93.2% capacity retention after 200 cycles. This work offers a straightforward and accessible method for the practical implementation of high energy density in-situ polymerized solid-state LMBs.

通过引入天然氨基酸基团来设计高容量、长寿命钠离子电池用有机分子电极

有机电极具有结构可设计性强、容量大、可容纳大离子等优点.然而,在钠离子电池中,有机电极材料的容量仍然很低,且其在有机电解质中的高溶解度导致其寿命较短.如何通过化合物设计来提高其性能一直是研究人员关注的问题.本研究通过简单方法将氨基酸接枝到有机化合物上,提高了其容量和循环稳定性.首先,氨基酸之间的氢键使其形成更稳定的层状结构;氨基酸基团在有机电极材料和羧甲基纤维素粘合剂之间形成分子间相互作用,降低界面阻力,显著提高循环稳定性,使得钠离子电池循环次数超过2000次.其次,实验和计算结果表明,氨基酸基团提供了Na^(+)转运途径和额外的可逆存储位点,从而提高了比容量(~300 mA h g^(-1)).本策略可以启发未来钠离子电池的有机分子设计.

Observation of room‐temperature out‐of‐plane switchable electric polarization in supported 3R‐MoS_(2) monolayers

Two‐dimensional(2D)ferroelectrics have attracted considerable attention due to their potential in the development of devices of miniaturization and multifunction.Although several van der Waals(vdW)‐layered materials show ferroelectricity,the experimental demonstrations of ferroelectric behavior in monolayers are very limited.Here we report the observation of room‐temperature out‐of‐plane switchable electric polarization in supported MoS_(2) monolayers exfoliated from 3R‐stacked bulk crystals under ambient conditions.Using in situ piezoelectric force microscopy and Kelvin probe force microscopy in a glovebox,we reveal that trapped water/ice molecules are responsible for this switchable electric polarization and this conclusion is strongly supported by theoretical simulations.It is worth noting that the water/ice trapping in the monolayers exfoliated from 2H‐stacked MoS_(2) crystals is not as much as that in 3R monolayers and,consequently,the out‐of‐plane electric polarization is missing there.Our findings indicate that monolayers with a trapped single layer of polar molecules might be emerging alternatives to 2D ferroelectrics.Furthermore,the stacking sequences may bring new properties and applications to 2D vdW materials not only when we stack them up but also when we thin them down.

mTOR/miR-145-regulated exosomal GOLM1 promotes hepatocellular carcinoma through augmented GSK-3b/MMPs

Golgi membrane protein 1(GOLM1/GP73)is a serum marker of hepatocellular carcinoma(HCC).We have previously shown that mTOR promoted tumorigenesis of HCC through stimulating GOLM1 expression.In this study,we demonstrated that the mammalian target of rapamycin(mTOR)was a negative regulator of microRNA-145(miR-145)expression.miR-145 inhibited GOLM1 expression by targeting a coding sequence of GOLM1 gene.GOLM1 and miR-145 were inversely correlated in human HCC tissues.GOLM1-enriched exosomes activated the glycogen synthase kinase-3β/matrix metalloproteinases(GSK-3β/MMPs)signaling axis of recipient cells and accelerated cell proliferation and migration.In contrast,miR-145 suppressed tumorigenesis and metastasis.We suggest that mTOR/miR-145/GOLM1 signaling pathway should be targeted for HCC treatment.

One-Step High-Temperature-Synthesized Single-Atom Platinum Catalyst for Efficient Selective Hydrogenation

Although single-atom catalysts significantly improve the atom utilization efficiency,the multistep preparation procedures are complicated and difficult to control.Herein,we demonstrate that one-step in situ synthesis of the single-atom Pt anchored in single-crystal MoC(Pt_(1)/MoC)by using facile and controllable arc-discharge strategy under extreme conditions.The high temperature(up to 4000℃)provides the sufficient energy for atom dispersion and overall stability by forming thermodynamically favourable metal-support interactions.The high-temperature-stabilized Pt1/MoC exhibits outstanding performance and excellent thermal stability as durable catalyst for selective quinoline hydrogenation.The initial turnover frequency of 3710 h^(-1)is greater than those of previously reported samples by an order of magnitude under 2 MPa H_(2)at 100℃.The catalyst also shows broad scope activity toward hydrogenation containing unsaturated groups of C=C,C=N,and C=O.The facile,one-step,and fast arc-discharge method provides an effective avenue for single-atom catalyst fabrication that is conventionally challenging.

Doped, conductive SiO_(2) nanoparticles for large microwave absorption

Although many materials have been studied for the purpose of microwave absorption,SiO_(2) has never been reported as a good candidate.In this study,we present for the first time that doped,microwave conductive SiO_(2) nanoparticles can possess an excellent microwave absorbing performance.A large microwave reflection loss(RL)of−55.09 dB can be obtained.The large microwave absorption originates mainly from electrical relaxation rather than the magnetic relaxation of the incoming microwave field.The electrical relaxation is attributed to a large electrical conductivity that is enabled by the incorporation of heterogeneous(N,C and Cl)atoms.The removal of the magnetic susceptibility only results in a negligible influence of the microwave absorption.In contrast,the removal of the heterogeneous atoms leads to a large decrease in the electrical conductivity and microwave absorption performance.Meanwhile,the microwave absorption characteristics can be largely adjusted with a change of the thickness,which provides large flexibility for various microwave absorption applications.

Microwave absorption of aluminum/hydrogen treated titanium dioxide nanoparticles

Interactions between incident electromagnetic energy and matter are of critical importance for numerous civil and military applications such as photocatalysis,solar cells,optics,radar detection,communications,information processing and transport et al.Traditional mechanisms for such interactions in the microwave frequency mainly rely on dipole rotations and magnetic domain resonance.In this study,we present the first report of the microwave absorption of Al/H2 treated TiO_(2) nanoparticles,where the A_(l)/H_(2) treatment not only induces structural and optical property changes,but also largely improves the microwave absorption performance of TiO_(2) nanoparticles.Moreover,the frequency of the microwave absorption can be finely controlled with the treatment temperature,and the absorption efficiency can reach optimal values with a careful temperature tuning.A large reflection loss of
58.02 dB has been demonstrated with 3.1mm TiO_(2) coating when the treating temperature is 700℃.The high efficiency of microwave absorption is most likely linked to the disordering-induced property changes in the materials.Along with the increased microwave absorption properties are largely increased visiblelight and IR absorptions,and enhanced electrical conductivity and reduced skin-depth,which is likely related to the interfacial defects within the TiO_(2) nanoparticles caused by the Al/H2 treatment.

家族性子宫肌瘤相关VEGFR1胚系突变对mTOR抑制剂敏感

子宫肌瘤是女性生殖道系统最为常见的良性肿瘤,目前其发病机制尚不明确.本研究通过对一个多发性子宫肌瘤家系全外显子测序研究,发现了血管内皮生长因子受体1(VEGFR1)中P801Q的杂合胚系突变.该突变位于VEGFR1的近膜结构(JM)域,通过3D同源性建模预测该突变会损害JM区域的自抑制功能.此外,该突变体激活了培养细胞和肌瘤样本中的mTOR信号和MAPK信号通路.mTOR抑制剂雷帕霉素(西罗莫司)和MAPK抑制剂曲美替尼优先抑制VEGFR1P801Q表达细胞的增殖,家系先证者术后参加了西罗莫司预防肿瘤复发的临床试验,应用西罗莫司2年无复发,且无明显不良反应.综上,本研究揭示了VEGFR1介导的mTOR和MAPK信号通路在家族性子宫肌瘤发生中的关键作用.鉴于mTOR抑制剂有治疗子宫肌瘤和保留生育功能的潜力,雷帕霉素有望靶向治疗部分子宫肌瘤病人.

Introducing sulfur vacancies and in-plane SnS_(2)/SnO_(2) heterojunction in SnS_(2) nanosheets to promote photocatalytic activity

Due to the relatively sluggish charge carrier separation in metal sulfides,the photocatalytic activity of them is still far lower than expected.Herein,sulfur vacancies and in-plane SnS_(2)/SnO_(2) heterojunction were successfully introduced into the SnS_(2) nanosheets through high energy ball-milling.These defective structures were studied by the electron paramagnetic resonance,Raman spectra,X-ray photoelectron spectroscopy,and high-resolution transmission electron microscope analyses.The sulfur vacancies and in-plane heterojunctions strongly accelerate the separation of photoexcited electron-hole pairs,as confirmed by the photo luminesce nce emission spectra and time-resolved photoluminescence decay spectra.The introduction of sulfur vacancies and in-plane heterojunction in SnS_(2) nanosheets results in roughly six times higher photodegrading rate for methyl orange and four times higher photocatalytic reduction rate of Cr6+than those of pure SnS_(2) nanosheets.

Electrodes with Electrodeposited Water-excluding Polymer Coating Enable High-Voltage Aqueous Supercapacitors

Aqueous supercapacitors are powerful energy sources,but they are limited by energy density that is much lower than lithium-ion batteries.Since raising the voltage beyond the thermodynamic potential for water splitting(1.23 V)can boost the energy density,there has been much effort on water-stabilizing salvation additives such as Li_(2)SO_(4) that can provide an aqueous electrolyte capable of withstanding~1.8 V.Guided by the first-principles calculations that reveal water can promote hydrogen and oxygen evolution reactions,here,we pursue a new strategy of covering the electrode with a dense electroplated polymerized polyacrylic acid,which is an electron insulator but a proton conductor and proton reservoir.The combined effect of salvation and coating expands the electrochemical window throughout pH 3 to pH 10 to 2.4V for both fast and slow proton-mediated redox reactions.This allows activated carbon to quadruple the energy density,a kilogram of nitrogen-doped graphene to provide 127 Watt-hour,and both to have improved endurance because of suppression of water-mediated corrosion.Therefore,aqueous supercapacitors can now achieve energy densities quite comparable to that of a lithium-ion battery,but at 100 times the charging/discharging speed and cycle durability.

TiO_(2)示例赝电容电极材料的设计规则:离子吸附,扩散和电子传输

高性能赝电容的发展需要从电子转移、电解质离子吸附和扩散方面全面理解电极材料.本论文结合第一性原理与转移矩阵法,以TiO_(2)为原型,通过引入各种缺陷,即氧缺陷(V_(O))和共掺杂缺陷(V_(O)+N_(O)),在综合考虑以上因素后获得了较高的赝电容.与本征TiO_(2)(300 F g^(-1))相比,有缺陷的TiO_(2)产生的赝电容高达1700 F g^(-1).此外,缺陷会使得表面能带弯曲减小电子传输势垒,H离子在TiO_(2)-V_(O)中显示出比在TiO_(2)-V_(O)+N_(O)中高得多的势垒,表明在共掺杂体系中H扩散更容易.这项工作为电解质离子的吸附和扩散以及缺陷对电子传输的影响提供了见解,对于下一代超级电容器电极材料的设计和优化具有重要意义.

In situ annealing effects on magnetic properties and variable-range hopping of iron-based ladder material BaFe2S3

All iron-based superconductors,regardless of their detailed crystal structure,share the same conductive Fe_2X_2(X=As,P,Se,and S)layers as the crucial structural unit[1-8].In the Fe_2X_2 layers,edge-shared FeX_4 tetrahedra form a square lattice in quasi-two-dimensional(quasi-2D)planes.One may wonder what kind of properties will be manifested in the quasi-one-dimensional(quasi-1D)counterparts exhibiting an identical coordination as the above-mentioned