A general synthesis of inorganic nanotubes as high-rate anode materials of sodium ion batteries

Ino rganic tubular materials have an exceptionally wide range of applications,yet developing a simple and universal method to controllably synthesize them remains challenging.In this work,we report a vaporphase-etching hard-template method that can directly fabricate tubes on various thermally stable oxide and sulfide materials.This synthesis method features the introduction of a vapor-phase-etching process to greatly simplify the steps involved in preparing tubular materials and avoids complicated postprocessing procedures.Furthermore,the in-situ heating transmission electron microscopy(TEM)technique is used to observe the dynamic formation process of TiO_(2-x) tubes,indicating that the removal process of the Sb2S3 templates first experienced the Rayleigh instability,then vapor-phase-etching process.When used as an anode for sodium ion batteries,the TiO_(2-x) tube exhibits excellent rate performance of134.6 mA h g^(-1) at the high current density of 10 A g^(-1) and long-term cycling over 7000 cycles.Moreover,the full cell demonstrates excellent cycling performance with capacity retention of 98%after 1000 cycles,indicating that it is a promising anode material for batteries.This method can be expanded to the design and synthesis of other thermally-stable tubular materials such as ZnS,MoS_(2),and SiO_(2).

过渡金属单原子功能化碳载体促进碱性氢电催化反应动力学

碱性阴离子膜燃料电池和电解水制氢技术对氢能的高效循环利用非常关键.然而,碱性条件下析氢反应(HER)和氢氧化反应(HOR)动力学缓慢,大大降低了燃料电池和电解池的能量转换效率.因此,开发综合性能优异的电催化剂以提高碱性环境下HER和HOR动力学至关重要.传统电催化剂的一个典型设计思路是将活性材料负载于具有高导电性和大比表面积的碳载体上.一般来说,碳载体能够促进活性材料的均匀分散并显著增加其催化活性位点的暴露,但是碳载体本身往往很难参与电催化反应,导致复合催化剂活性位点单一,不利于高效催化涉及较多中间体的复杂反应(碱性条件下的HOR和HER).另一方面,当前电催化剂研究通常局限于调控活性材料和载体的界面结构或者专注于调控活性材料本征结构,对催化剂载体进行调控并作为助催化剂的研究尚不多见.本文采用过渡金属单原子对碳载体进行功能化及电子结构调控,并研究此类碳载体在碱性HER和HOR反应中的助催化作用.合成了一系列金属单原子修饰的碳载体M-N-C(过渡金属包括Mn,Fe,Co,Ni,Cu,Mo,Ag),并系统研究了M-N-C在Pt电催化HOR和HER中的作用.结果表明,过渡金属单原子修饰的碳载体的催化促进作用与过渡金属的电负性以及3d轨道电子填充度密切相关.一方面,不同过渡金属M与氧的亲和力不同,并可以通过界面M–O–Pt键调节Pt的电子结构.过渡金属电负性越小,Pt表面的电子密度则越大,有助于加速Had在Pt表面的结合/解离步骤,因此提升了HOR和HER反应速率.另一方面,过渡金属的3d轨道未填充程度越高,则越有利于增强其与氧2p轨道的耦合作用,所形成的M-N4结构对于水分子和OH_(ad)的吸附也大大增强,最终通过促进Volmer步骤加快氢的电催化反应速率.结果显示,除Cu和Ag单原子修饰的碳载体之外,其它几种过渡金属功能化的碳载体均能够通过促进Volmer反应步骤以加快碱性条件下Pt的HOR和HER电催化反应速率,其中效果最为显著的是锰单原子修饰的碳载体.Mn-N-C/Pt(1.48 mA cm_(Pt)^(–2))的质量比交换电流密度比商业化20%Pt/C(0.26 mA cm_(Pt)^(–2))提高了约4.7倍.综上所述,本工作证明了开发多功能碳载体用于异相催化反应的重要性,并且为未来开发高效电催化剂提供了新的思路.

Controlled on-chip fabrication of large-scale perovskite single crystal arrays for high-performance laser and photodetector integration

Metal halide perovskites possess intriguing optoelectronic properties,however,the lack of precise control of on-chip fabrication of the large-scale perovskite single crystal arrays restricts its application in integrated devices.Here,we report a space confinement and antisolvent-assisted crystallization method for the homogeneous perovskite single crystal arrays spanning 100 square centimeter areas.This method enables precise control over the crystal arrays,including different array shapes and resolutions with less than 10%-pixel position variation,tunable pixel dimensions from 2 to 8 pm as well as the in-plane rotation of each pixel.The crystal pixel could serve as a high-quality whispering gallery mode(WGM)microcavity with a quality factor of 2915 and a threshold of 4.14μJ cm^(-2).Through directly on-chip fabrication on the patterned electrodes,a vertical structured photodetector array is demonstrated with stable photoswitching behavior and the capability to image the input patterns,indicating the potential application in the integrated systems of this method.

General strategy for evaluating the d-band center shift and ethanol oxidation reaction pathway towards Pt-based electrocatalysts

The catalytic performance of Pt-based catalysts depends sensitively on their d-band centers.Nevertheless,there are still huge challenges to evaluate their d-band centers from experimental technologies,and modulate them to analyze their selectivity in ethanol oxidation reaction(EOR).Here,Pt1Au1alloy supported on the commercial carbon material(Pt_(1)Au_(1)/C)is employed as a typical example to investigate its d-band center shift of surface Pt,and as electrocatalysts to study its selectivity towards EOR.Significantly,a highly reliable in situ Fourier-transform infrared spectroscopy CO-probe strategy is developed to characterize the d-band center shift of surface Pt.The modified electronic effect and site effect of Pt_(1)Au_(1)/C dictated the adsorption configuration of intermediate species and the OH species coverage,thereby influencing its selectivity.More importantly,we developed a universal cyclic voltammetry peak differentiation fitting method as an electrochemical analysis technique to investigate CO_(2)selectivity,which is potentially extendable to other Pt-based electrocatalysts.

In Situ Investigation of the Phase Transition at the Surface of Thermoelectric PbTe with van der Waals Control

The structure of thermoelectric materials largely determines the thermoelectric characteristics.Hence,a better understanding of the details of the structural transformation process/conditions can open doors for new applications.In this study,the structural transformation of PbTe(a typical thermoelectric material)is studied at the atomic scale,and both nucleation and growth are analyzed.We found that the phase transition mainly occurs at the surface of the material,and it is mainly determined by the surface energy and the degree of freedom the atoms have.After exposure to an electron beam and high temperature,highdensity crystal-nuclei appear on the surface,which continue to grow into large particles.The particle formation is consistent with the known oriented-attachment growth mode.In addition,the geometric structure changes during the transformation process.The growth of nanoparticles is largely determined by the van der Waals force,due to which adjacent particles gradually move closer.During this movement,as the relative position of the particles changes,the direction of the interaction force changes too,which causes the particles to rotate by a certain angle.