Vanadium-based polyanionic compounds as cathode materials for sodium-ion batteries:Toward high-energy and high-power applications

Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of low energy&power density and short cycling lifespan owing to the heavy mass and large radius of Na⁺.Vanadium-based polyanionic compounds have advantageous characteristic of high operating voltage,high ionic conductivity and robust structural framework,which is conducive to their high energy&power density and long lifespan for SIBs.In this review,we will overview the latest V-based polyanionic compounds,along with the respective characteristic from the intrinsic crystal structure to performance presentation and improvement for SIBs.One of the most important aspect is to discover the essential problems existed in the present V-based polyanionic compounds for high-energy&power applications,and point out most suitable solutions from the crystal structure modulation,interface tailoring and electrode configuration design.Moreover,some scientific issues of V-based polyanionic compounds shall be also proposed and related future direction shall be provided.We believe that this review can serve as a motivation for further development of novel V-based polyanionic compounds and drive them toward high energy&power applications in the near future.     

Total synthesis of TRADD death domain with arginine N-GlcNAcylation by hydrazide-based native chemical ligation

TNFR1-associated death domain protein(TRADD)with arginine N-GlcNAcylation is a novel and structurally unique posttranslational modification(PTM)glycoprotein that blocks the formation of death-inducing signaling complex(DISC),orchestrating host nuclear factorκB(NF-κB)signaling in entero-pathogenic Escherichia coli(EPEC)-infected cells.This particular glycosylated modification plays an extremely vital role for the effective colonization and pathogenesis of pathogens in the gut.Herein we describe the total synthesis of TRADD death domain(residues 195-312)with arginine235 NGlcNAcylation(Arg-GIcNAc TRADD(195-312)).Two longish peptidyl fragments of the wild-type primary sequence were obtained by robust,microwave-assisted,highly efficient,solid-phase peptide synthesis(SPPS),the N-GlcNAcylated sector was built by total synthesis and attached specifically to resinbound peptide with an unprotected ornithine residue via silver-promoted on-resin guanidinylation,ArgGlcNAc TRADD(195-312)was constructed by hydrazide-based native chemical ligation(NCL).The facile synthetic strategy is expected to be generally applicable for the rapid synthesis of other proteins with Arg-GIcNAc modification and to pave the way for the related chemically biological study.     

Steam activation of Fe-N-C catalyst for advanced power performance of alkaline hydrazine fuel cells

Alkaline hydrazine liquid fuel cells(AHFC) have been highlighted in terms of high power performance with non-precious metal catalysts.Although Fe-N-C is a promising non-Pt electrocatalyst for oxygen reduction reaction(ORR),the surface density of the active site is very low and the catalyst layer should be thick to acquire the necessary number of catalytic active sites.With this thick catalyst layer,it is important to have an optimum pore structure for effective reactant conveyance to active sites and an interface structure for faster charge transfer.Herein,we prepare a Fe-N-C catalyst with magnetite particles and hierarchical pore structure by steam activation.The steam activation process significantly improves the power performance of the AHFC as indicated by the lower IR and activation voltage losses.Based on a systematic characterization,we found that hierarchical pore structures improve the catalyst utilization efficiency of the AHFCs,and magnetite nanoparticles act as surface modifiers to reduce the interracial resistance between the electrode and the ion-exchange membrane.     

Combined QSAR/QSPR,Molecular Docking,and Molecular Dynamics Study of Environmentally Friendly PBDEs with Improved Insulating Properties

To improve the insulating properties of polybrominated diphenyl ethers(PBDEs), we studied the molecular structures and energy gap(Eg) values of 209 PBDEs using a three-dimensional quantitative structure-activity relationship(3D-QSAR) model, molecular docking, and molecular dynamics. We also analyzed the interaction mechanisms of PBDEs using a 2D-QSAR model, molecular substitution characteristics, and molecular docking. The 3D-QSAR model showed that the 2-, 4-, 5-, and 6-positions significantly influenced the PBDE insulating properties. Using BDE-34 as a template molecule, we designed six derivatives with 0.47%-28.44% higher insulation tlian BDE-34. Compared with BDE-34, the stability and flame retardancy of the above six derivatives were not adversely affected. These derivatives, except for 2,6-cyanomethyl-BDE, 2-cyanomethyl-BDE, and 2-aniinomethyl-BDE, were more toxic and biodegradable than BDE-34, but showed weaker bioaccumulation and migration abilities than BDE-34. Mechanism analysis showed that the highest occupied orbital energy, the most negative charge, and the dipole moment were the main quantitative parameters that aflected the PBDE insulating properties. PBDE insulation gradually decreased as the number of Br atoms increased. The level of similarity between the substitution patterns on the two benzene rings was significantly correlated with PBDE insulation, with hydrophobic groups having a more significant efiect on PBDE insulation.     

Novel fusiform core-shell-MOF derived in tact metal@carb on composite:An efficient cathode catalyst for aqueous and solid-state Zn-air batteries

Owing to the varied mechanisms of ORR/OER,exploiting cost-effective bifunctional catalysts with robust ORR/OER activities and excellent performances in Zn-air batteries is still a challenge.In this work,the Co/CoO@NSC bifunctional catalyst is obtained by using Zn-MOF@Co-MOF as self-template.The Co/CoO@NSC composite has interconnected porous architecture with in tact metal@carb on structure,exhibiting superior electrocatalytic activities toward ORR and OER that can be comparable with the Pt/C and RuO₂ catalysts,respectively.The Co/CoO@NSC-based aqueous Zn-air battery achieves a high specific capacity(759.7 mAh/g)and energy density(990.5 Wh/kg),and ultra-long rechargeable property(more than 400 h/1200 cycles).The Co/CoO@NSC-based solid-state Zn-air battery also delivers an excellent performance with a long cycle life(more than 143 h/858 cycles).Most importantly,the newly synthesized and recharged Co/CoO@NSC-based solid-state Zn-air battery can be used to light up a 2 V LED lamp for more than 28 h,demonstrating the superior practicability as rechargeable power source.     

Ultra-small nanodots coated with oligopeptides providing highly negative charges to enhance osteogenic differentiation of hBMSCs better than osteogenic induction medium

For bone regenerative engineering,it is a promising method to form skeletal tissues differentiating from human bone morrow mesenchyme stem cells(hBMSCs).However,it is still a critical challenge to efficiently control ostogenesis and clearly reveal the influence factor.To this end,the fluorescent gold nanodots(Au NDs) with highly negative charges as osteogenic induction reagent are successfully synthesized,which display better than commercial osteogenic induction medium through the investigations of ALP activity(2.5 folds) and cytoskeleton staining(1.5 folds).Two kinds of oligopeptides with different bio-structures(cysteine,Cys and glutathione,GSH) are selected for providing surficial charges on Au NDs.It is revealed that Au-Cys with more negative charges(-51 mV) play better role than Au-GSH(-19 mV) in osteogenic differentiation,when both of them have same size(~2 nm),sphere shape and show similar cell uptake amount.To explore deeply,osteogenesis related signaling pathways are monitored,revealing that the enhancement of osteogenic differentiation was through autophagy signaling pathway triggered by Au-Cys.And the promotion of highly negative charges in osteogenic diffe rentiation was further proved via sliver nanodots(Ag NDs,Ag-Cys and Ag-GSH) and carbon nanodots(CDs,Cys-CDs and GSH-CDs).This work indicates part of insights during hBMSCs differentiation and provides a novel strategy in osteogenic differentiation process.     

Recent progress of thin-film photovoltaics for indoor application

Indoor photovoltaics have attracted increasing attentions owing to their great potential in supplying energy for low power devices under indoor light in our daily life.The third generation thin-film solar cells,including dye-sensitized solar cells,perovskite solar cells and organic solar cells,have made rapid progress from the aspect of materials design to photovoltaic performance.This review provides an overview on the recent advances in the development of indoor photovoltaic technologies based on the third generation solar cells.The design principles of advanced thin-film indoor photovoltaics were also summarized according to the characteristics of indoor light and the advantages of the third generation solar cells.Finally,after summarizing the current research progress,the perspective on this topic is provided.     

C-S coupling with nitro group as leaving group via simple inorganic salt catalysis

An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution(S_NAr)reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described.Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields.We also showed that the present method allows access to 3 drug examples in a short reaction time.Finally,mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step additionelimination mechanism.     

Visualizing phase transition of upper critical solution temperature (UCST) polymers with AIE

The stimuli-responsive polymers with upper critical solution temperatures(UCST) are highly attractive for drug delivery applications. However, the phase transition process of UCST polymer is usually characterized by turbidity measurement and electron microscopy, which are significantly restricted by low sensitivity and static observation. In contrary, the fluorescence technique has significant advantages in terms of high sensitivity, easy operation, and dynamic observation. However, the conventional fluorophores suffer from the drawbacks of aggregation-caused quenching(ACQ) after being encapsulated by UCST polymers, which are not suitable for direct visualization of the phase transition process. To tackle this challenge, we herein developed a series of UCST polymers based on polyacrylamides decorated with bile acid and aggregation-induced emission(AIE)-active tetraphenylethene(TPE) groups, which can be used for direct fluorescence monitoring of the phase transition process. Moreover, the AIE-active UCST polymers can serve as drug carriers, which can not only monitor the drug release process under thermal stimuli, but also verify the drug release by fluorescence recovery after thermal stimuli. It is expected that the AIE-active UCST polymers with self-monitoring ability are promising for biomedical applications.     

A highly stable membrane with hierarchical structure for wide pH range flow batteries

A membrane with high stability and ion conductivity in wide pH range is essential for energy storage devices.Here,we report a novel membrane with hierarchical core-shell structure,which demonstrates high stability and ion conductivity,simultaneously under a wide pH range applications.Spectral characterizations and theoretical calculation indicate that the non-solvent induces the chain segment configuration and eventually leads to polymer-polymer phase separation,thus forming hierarchical porous core-shell structure.Benefiting from this structure,an acidic vanadium flow battery(VFB)with such a membrane shows excellent performance over 400 cycles with an energy efficiency(EE)of above 81%at current density of 120 mA cm^-2 and an alkaline zinc-iron flow battery(AZIFB)delivers a cycling stability for more than 200 cycles at 160 mA cm^-2,along with an EE of above 82%.This paper provides a cost-effective and simple way to fabricate membranes with high performance for variety of energyrelated devices.     

超临界水中含碳酸根羟基磷灰石的快速连续合成

Carbonated hydroxyapatites(CHA) were rapidly and continuously synthesized in supercritical water by using a tubular reactor. The effects of reaction time and the ratio of PO₄^3-/CO₃^2- on the apatite structure were investigated by using XRD, FTIR and TEM. Results showed that 30 seconds were enough to produce fully crystalline CHA nano-rods, ca. 20×70 nm in size, at 380 ℃ and 24 MPa. When the ratio of PO₄^3-/CO₃^2- was not less than 1, the CO₃^2- ions mainly substituted for PO₄^3- in apatite structure; but CO₃^2- ions could react with Ca²⁺ to form CaCO₃ phase when the ratio of PO₄^3-/CO₃^2- was less than 1.     

焙烧温度对合成LiFePO4的产物组成和电化学性能的影响

以FePO4为前驱体, 采用碳热还原法合成了LiFePO4/C复合正极材料; 通过TG-DTA、FTIR、XRD 等技术研究了反应历程, 分析了不同焙烧温度下产物的组成及杂相存在的原因, 并测试了其电化学性能. 研究表明, 300 ℃下LiFePO4已作为主要的相存在, 显示了较低的成相温度; 300、400、500 ℃下样品中存在一定量的杂相Li3PO4和Fe2O3, 600 ℃得到纯相的LiFePO4, 而在700 ℃下出现了焦磷酸盐Li4P2O7, 这些杂相的存在影响了其电化学性能, 600 ℃样品具有最佳的电化学性能, 其在0.1C下首次放电容量达146 mAh·g-1, 循环15 次后容量还保持为141 mAh·g-1.     

以葡聚糖为模板控制合成文石型碳酸钙

依据生物矿化的基本原理,在动态条件下以葡聚糖为模板,采用仿生的方法控制合成了具有独特形貌并含有少量葡聚糖的碳酸钙复合材料.用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外吸收光谱(FTIR)和电导率测定等手段对所得的复合碳酸钙进行了形貌与结构表征.结果表明,所得CaCO₃为文石晶型,外貌类似菜叶.进一步的研究发现,在CaCO₃结晶过程中葡聚糖与CaCO₃之间存在超分子相互作用,并讨论了这种作用的可能机理.     

金属盐对O2/CO2煤粉混燃钙基脱硫反应的影响

利用添加剂调制改性的方法，考察了以碳酸钠为代表的金属盐对石灰石微观结构的影响，得出调制改性优化了石灰石的物理结构，并在离子比γ为15∶1的加入量效果最佳。在此基础上，借助定硫仪比较了O2-CO2气氛下调制前后石灰石对燃煤SO2释放的影响，并对燃烧产物进行灰熔点分析及灰成分的XRD测试。实验结果表明，在不影响煤粉燃烧结渣特性的前提下，改性后的石灰石可以更有效地抑制SO2的排放，固硫效果在1 000 ℃时达到最佳。     

无添加剂条件下文石型碳酸钙晶须制备及影响因素研究

在不加任何结晶控制剂或模板条件下,以CaCl2和Na2CO3为原料,利用复分解反应法制备了具有较好形貌和高长径比,且分布均一的文石型碳酸钙晶须,并利用扫描电镜(SEM)、X-射线粉末衍射(PXRD)和傅里叶转换红外光谱图(FT-IR)等手段对其进行了表征。研究了浓度、滴加速度、反应温度、搅拌速度以及滴加方式等因素对碳酸钙晶须的影响。结果表明最佳制备工艺为:CaC12溶液与Na2CO3溶液的浓度为0.05 mol.L-1,溶液滴加速度为1 mL.min-1,反应体系温度为80℃,搅拌速度为250 r.min-1。     

碳酸钙微米球的制备与表征

采用醋酸钙和碳酸钠为原料,在反应温度为5℃和柠檬酸三钠质量百分浓度为15%的条件下,采用沉淀法合成出了粒度为1～4μm、分散性好的球形碳酸钙粉体。用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、红外光谱仪(IR)、原子力扫描探针显微镜(ASPM)、光学显微镜、粒度分析仪等对样品进行了表征,并用光学显微镜跟踪考察了碳酸钙微米球的形成过程。结果表明,碳酸钙微米球是由大量纳米级颗粒组装而成。     

碳酸钙/镍复合导电材料的原位合成及其抗静电性能

利用胶棉膜作为活性模板,制备出方解石型碳酸钙组装球,在其表面上将镍进行原位还原反应,首次成功获得了碳酸钙/镍复合导电材料,通过TEM、XRD、FT-IR和TG-DTA等测试技术对产物结构及性能进行了表征,并将产物应用于抗静电领域,制备成的抗静电涂料与用纯镍粉制备的涂料具有同等抗静电性能(电阻率为1.2×106 Ω·cm),并可以节省60%的镍。 该复合材料在导电和抗静电等领域具有应用前景,能够节省对镍的消耗。     

原位沉析法制备碳酸钙/壳聚糖三维复合材料的研究

将含有Ca²⁺的壳聚糖溶液与含有CO^2-₃的碱溶液用离子可渗透膜隔离,根据膜渗透原理,使膜内壳聚糖与碱液原位沉析,生成碳酸钙,得到具有高强度的碳酸钙(CaCO₃)/壳聚糖(CS) 三维复合材料. XRD测试结果表明,生成的碳酸钙以方解石晶型存在. 从SEM可以观察到碳酸钙颗粒尺寸约为5～10 μm,并且颗粒呈有序分布,它们以棒材的纵轴为中心,围绕中心呈环状分布. 对不同碳酸钙含量的复合棒材进行了弯曲性能测试,其弯曲强度随碳酸钙含量的增大先上升后下降. 在碳酸钙质量分数为10％时,弯曲强度达到最大值(约为113 MPa),弯曲模量为2.6 GPa.     

超细4A分子筛的超声波低温快速合成

在低温条件下用超声波快速合成了4A分子筛.产物分别用XRD,IR,SEM和DSC等进行了表征.结果表明,用超声波法合成4A分子筛的速度是常规法的24倍.合成产物的白度为95%,钙离子交换容量为335mgCaCO₃/g4A分子筛,平均粒径为280nm.与采用常规方法合成的产物相比,超声波法合成的产物热稳定性有所下降.     

阴离子氨基酸表面活性剂调控碳酸钙的仿生合成

室温下, 在乙醇或乙醇-水混合体系中, 利用氨基酸表面活性剂N-酰基十二烷基肌氨酸钠(Sar)调控合成碳酸钙, 采用SEM, XRD和FTIR等技术表征了反应产物. 在乙醇体系中, 首先形成多面体形状的文石, 然后逐渐转变为圆球状的无定形碳酸钙. 在乙醇-水混合体系中, 合成了花簇状多级结构碳酸钙晶体. 增加N-酰基十二烷基肌氨酸钠的用量有助于形成球霰石结构, 当n(Ca2+)∶n(Sar)=1∶1 时, 得到的花状碳酸钙为球霰石和方解石的混合物, 当n(Ca2+)∶n(Sar)=1∶2 时, 得到纯净的球霰石, 其形貌为大小较均一的单分散的球, 直径约为7 μm; 另外, 当n(Ca2+)∶n(Sar)=1∶1时, 混合溶剂中水和乙醇的体积比由1.5∶1依次增加为7∶3和3∶1时, 碳酸钙晶体的形貌由花状逐渐向球形过渡, 晶体中球霰石和方解石的含量也随之变化, 其中, 当水和醇的体积比为7∶3时, 产物主要为球霰石型晶体.