Co/CoO heterojunction rich in oxygen vacancies introduced by O_(2) plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.

One-pot topotactic synthesis of Ti^(3+) self-doped 3D TiO_2 hollow nanoboxes with enhanced visible light response

Ti^（3＋） self-doped anatase three-dimensional（3D） TiO_2 hollow nanoboxes were synthesized via a topological transformation process involving template participation by a facile one-pot hydrothermal treatment with an ethanol solution of zinc powder and TiOF_2. It is worth noting that the 3D TiO_2 hollow nanoboxes are assembled from six single-crystal nanosheets and have dominant exposure of the {001} facets. It is found from EPR spectra that adding zinc powder is an environment-friendly and effective strategy to introduce Ti^（3＋） and oxygen vacancy（Ov） into the bulk of 3D hollow nanoboxes rather than the surface, which is responsible for their enhanced visible photocatalytic properties.The photocatalytic activity was evaluated by measuring the formation rate of hydroxide free radicals using 7-hydroxycoumarin as a probe. The sample prepared with zinc/TiOF_2 mass ratio of0.25 exhibited the highest RhB photodegradation activity under visible-light irradiation with a degradation rate of 96%, which is 4.0-times higher than that of pure TiO_2. The results suggest a novel approach to construct in-situ 3D hierarchical TiO_2 hollow nanoboxes doped with Ti^（3＋） and Ov without introducing any impurity elements for superior visible-light photocatalytic activity.

西门子推出新型Nanobox及Nanopanel PC

西门子全新推出Nanobox PC Simatic IPC227E和Nanopanel PC Simatic IPC277E共2款产品,是结构极其紧凑、坚固耐用的新一代工业用设备。Simatic IPC227E箱式PC分为有PCIe插槽和无PCIe插槽2种型号。Simatic IPC277E是面板式PC,配备有7-19英寸的宽屏触控显示屏。这2款PC内置的英特尔双核和四核赛扬处理器结构紧凑、性能卓越。2种型号的PC产品体积最小可达0.001 m3。

Engineering CuMn Prussian blue analog-shelled nanobox for efficient electrochemical reduction of nitrate to ammonia

Electrocatalytic nitrate reduction reaction(ENRR)for ammonia synthesis is a promising strategy to relieve nitration contamination,as well as an alternative to the Haber-Bosch process.Prussian blue analogs(PBAs)are expected to be an electrocatalytic material with superior performance owing to their abundant active sites and open channel structure.However,most reported PBA materials possess low nitrate conversion and ammonia yield rates,which has led to a hindrance in their research of ENRR.Herein,CuMn-PBA-shelled nanoboxes(CuMn-PBA SNBs)synthesized through tannic acid etching and cation exchange approaches are demonstrated for efficient ammonia production.The optimal CuMn-PBA SNBs electrode achieves a high nitrate conversion of 91.33%and ammonia selectivity of 98.87%in a 0.2 mol·L^(-1)Na_(2)SO_(4) solution with100×10^(-6) NO_(3)^(-)-N at-1.4 V vs.SCE.Furthermore,the CuMn-PBA SNB s electrode exhibits exceptional stability throughout a 30 h electrocatalytic process.The outstanding electrochemical performance is attributed to the unique hollow nanobox structure with abundant active sites and high-throughput transport pathways for ions'aspects.

3D multicore-shell CoSn nanoboxes encapsulated in porous carbon as anode for lithium-ion batteries

Due to its high theoretical capacity and appropriate potential platform,tin-based alloy materials are expected to be a competitive candidate for the next-generation high performance anodes of lithium-ion batteries.Nevertheless,the immense volume change during the lithium-ion insert process leads to severe disadvantages of structural damage and capacity fade,which limits its practical application.In this work,a three-dimensional(3 D)multicore-shell hollow nanobox encapsulated by carbon layer is obtained via a three-step method of hydrothermal reaction,annealing and alkali etching.During the electrochemical reactions,the CoSn@void@C nanoboxes provide internal space to compensate the volumetric change upon the lithiation of Sn,while the inactive component of Co acts as chemical buffers to withstand the anisotropic expansion of nanoparticles.Owing to the above-mentioned advantages,the elaborated anode delivers an excellent capacity of 788.2 m Ah/g at 100 m A/g after 100 cycles and considerable capacity retention of 519.2 mAh/g even at a high current density of 1 A/g after 300 cycles.The superior stability and high performance indicate its capability as promising anodes for lithium-ion batteries.

Rational construction of hollow nanoboxes for long cycle life alkali metal ion batteries

Hollow nanostructures are extremely attractive in energy storage and show broad application prospects.But the preparation method is accompanied by a complicated process.In this article,the CoZn-based hol-low nanoboxes with electrochemical synergy are prepared in a simple way.This structure can effectively shorten the transmission distance of ions and electrons,and alleviate the volume expansion during the cycle.In particular,bimetallic oxides are rich in oxygen vacancies,providing more active sites for electro-chemical reactions.In addition,the stepwise oxidation-reduction reaction can also improve the volume change of the electrode material.According to the kinetic analysis and density functional theory(DFT)calculation,it is confirmed that the synergistic effect of the bimetallic oxide can accelerate the reaction kinetics.Based on these characteristics,the electrode exhibits stable cycle performance and long cycle life in alkali metal ion batteries,and can provide reversible capacities of 302.1(LIBs,2000 cycles),172.5(SIBs,10000 cycles)and 109.6(PIBs,5000 cycles)mA h g^(-1)at a current density of 1.0 A g^(-1),respectively.In ad-dition,by assembling(LiCoO_(2)//CoZn-O_(2))and(Na_(3)V_(2)(PO_(4))_(3)//CoZn-O_(2))full-cells,the practical application value is demonstrated.The sharing of this work introduces a simple way to synthesize hollow nanoboxes,and shows excellent electrochemical performance,which can also be expanded in other areas.

Enhanced visible photocatalytic activity of TiO_2 hollow boxes modified by methionine for RhB degradation and NO oxidation

Hierarchical TiO2 hollow nanoboxes(TiO2‐HNBs)assembled from TiO2 nanosheets(TiO2‐NSs)show improved photoreactivity when compared with the building blocks of discrete TiO2‐NSs.However,TiO2‐HNBs can only be excited by ultraviolet light.In this paper,visible‐light‐responsive N and S co‐doped TiO2‐HNBs were prepared by calcining the mixture of cubic TiOF2 and methionine(C5H11NO2S),a N‐and S‐containing biomacromolecule.The effect of calcination temperature on the structure and performance of the TiO2‐HNBs was systematically studied.It was found that methionine can prevent TiOF2‐to‐anatase TiO2 phase transformation.Both N and S elements are doped into the lattice of TiO2‐HNBs when the mixture of TiOF2 and methionine undergoes calcination at 400°C,which is responsible for the visible‐light response.When compared with that of pure 400°C‐calcined TiO2‐HNBs(T400),the photoreactivity of 400°C‐calcined methionine‐modified TiO2‐HNBs(TM400)improves 1.53 times in photocatalytic degradation of rhodamine‐B dye under visible irradiation(?>420 nm).The enhanced visible photoreactivity of methionine‐modified TiO2‐HNBs is also confirmed by photocatalytic oxidation of NO.The successful doping of N and S elements into the lattice of TiO2‐HNBs,resulting in the improved light‐harvesting ability and efficient separation of photo‐generated electron‐hole pairs,is responsible for the enhanced visible photocatalytic activity of methionine‐modified TiO2‐HNBs.The photoreactivity of methionine modified TiO2‐HNBs remains nearly unchanged even after being recycled five times,indicating its promising use in practical applications.

Amorphous CoSnO_3@rGO nanocomposite as an efficient cathode catalyst for long-life Li-O_2 batteries

An amorphous CoSnO3@rGO nanocomposite fabricated using a surfactant‐assisted assembly method combined with thermal treatment served as a catalyst for non‐aqueous lithium‐oxygen(Li‐O2)batteries.In contrast to the specific surface area of the bare CoSnO3 nanoboxes(104.3 m2 g–1),the specific surface area of the CoSnO3@rGO nanocomposite increased to approximately 195.8 m2 g–1 and the electronic conductivity also improved.The increased specific surface area provided more space for the deposition of Li2O2,while the improved electronic conductivity accelerated the decomposition of Li2O2.Compared to bare CoSnO3,the overpotential reduced by approximately 20 and 60 mV at current densities of 100 and 500 mA g?1 when CoSnO3@rGO was used as the catalyst.A Li‐O2 battery using a CoSnO3@rGO nanocomposite as the cathode catalyst cycled indicated a superior cyclic stability of approximately 130 cycles at a current density of 200 mA g–1 with a limited capacity of 1000 mAh g–1,which is 25 cycles more than that of the bare amorphous CoSnO3 nanoboxes.

氧化镍空心壳材料的合成及其气敏特性测定

通过化学合成方法得到分散均匀的氧化亚铜方块,在此基础上以其作为硬模板采用模板技术,以六水合二氯化镍为金属源,通过"协同刻蚀"的方法获得氢氧化镍空心壳材料,并进一步热处理得到氧化镍空心壳材料。经过透射电子显微镜(TEM),并结合广角X射线衍射等手段,证实所得材料为空心氧化镍材料。通过在旁热式气敏元件表面简单涂抹的办法制得气敏器件,并对其正丁醇气敏性能进行了测定。研究结果表明,该种材料在250℃下对正丁醇具有较好的敏感性,这表明该种材料是一种非常有前途的功能材料,有望获得广泛应用。

新型金纳米材料在过氧化氢传感器中的应用

合成了新型的金纳米盒子材料,在金电极上通过金硫键自组装的方法修饰金纳米,再通过自组装和浸渍的方法修饰细胞色素c（Cyt c）,构建了基于Cyt c的直接电子传递的H2O2电化学传感器,所得传感器的灵敏度为4.4A/（mol/L）,线性范围为4.7×10-6~8.0×10-3 mol/L,检测限为1.5×10-6 mol/L。并将以金纳米盒子为基底的传感器与传统的电沉积金纳米,以及金纳米溶胶传感器做了对比,实验结果表明新型的金纳米盒子所修饰的传感器具有更好的灵敏度、更宽的线性范围及更低的检测限。

可控式citZ基因纳米盒的设计与研究

DNA分子具有自我识别的特殊能力,DNA折纸术就是利用这一特性进行核酸纳米材料精准设计和组装的一种新技术。研究者可以利用与DNA脚手架链互补的订书钉链,将长链核酸折叠成与预设模型一致的纳米结构。DNA折纸术最早是2006年由Rothemund提出,一直以来,人们利用M13mp18单链线性DNA进行各种纳米图形的自组装。为了寻找更多的核酸材料进行DNA折纸研究,本文以枯草芽孢杆菌(Bacillus.subtilis 168)cit Z基因序列为研究对象,采用改进的DAEDALUS软件,引入"锁钥"结构设计,利用"从下向上"的方法使DNA分子进行自组装,设计出三维体积为50.71nm×50.71nm×50.71nm的cit Z基因纳米盒,只有遇到可识别的基因和匹配的"钥匙"时,才可能打开盖子,释放盒中的内容物。这种核酸纳米材料还可以通过调节DNA序列长度调节盒子的内部空间,有望成为一种新型的靶向药物运送载体。

SPR增强贵金属M嵌入空盒TiO_(2)纳米反应器制备及其可见光降解RhB

为寻求更高效、对可见光强响应的光催化材料,制定出一项嵌入型纳米空盒光反应器的合成新技术,先采用拓扑相变法和空氛烧结法合成空盒状TiO_(2)(TiO_(2)-HNBs),然后将贵金属M以肖特基结嵌入TiO_(2)-HNBs制备纳米反应器,再对持久性有机污染物(Persistent Organic Pollutant,POPs)(模型染料为罗丹明B)进行可见光降解测试。结果显示,这种嵌入型纳米空盒光反应器表现出非常优异的光催化性能。与P25相比,光降解效率提高4至5倍,尤其是嵌入Au纳米棒的纳米空盒光反应器(Au-NRs/TiO_(2)-HNBs,TR),150min对RhB的降解效率可达98.5%。这得益于TiO_(2)空盒形貌优化以及贵金属M的表面等离子体共振效应(Surface Plasmon Resonance,SPR),在可见光响应下,金属产生的热电子能量高,易克服肖特基势垒从金属纳米颗粒转移到TiO_(2)导带上,有效转移和分离光生电子-空穴对。同时光催化活性与金属粒子的形貌密切相关,TR嵌入型纳米空盒光反应器表现出最高的催化活性。

Mg^(2+)掺杂TiO_2空盒子的制备及其光催化性能

为了解决纳米TiO_2带隙宽、电子-空穴对容易复合等问题,掺杂Mg^(2+)对TiO_2进行研究。以Ti(OC_4H_9)_4作为钛源,通过水热法制备Mg^(2+)掺杂TiO_2空盒子(Mg^(2+)@TiO_2)。采用透射电镜、X射线衍射及紫外漫反射对样品进行表征,探讨Mg^(2+)掺杂前后对其结构、性能等方面的影响。通过可见光催化降解有机污染物罗丹明B实验,证明了Mg^(2+)掺杂后的TiO_2纳米材料能够有效降解有机污染物罗丹明B,具有较高的光催化性能。

高性能氮掺杂中空碳纳米盒的制备及其在钠离子负极中的应用

碳基材料由于价格低廉、导电性良好及无毒安全等优势,成为钠离子电池中具有吸引力的负极材料,研究表明通过构筑利于电荷传输的动力学结构和引入杂原子进行掺杂,可改善其储钠离子的性能。采用模板法制备了氮掺杂中空碳纳米盒(NHCC),独特的中空纳米盒结构一方面能提供与电解质更大的接触面积,另一方面有利于离子的高效稳定传输。此外,NHCC材料引入氮原子能有效增加碳基材料的缺陷结构,为钠离子的储存提供更多的活性位点。研究结果表明,NHCC材料在电化学性能方面表现出优良的倍率性能(在电流密度2000 mA·g^(-1)下容量为220.7 mAh·g^(-1))和良好的循环性能(在电流密度200 mA·g^(-1)下循环400次后的可逆容量为255.7 mAh·g^(-1)),同时通过动力学分析可得NHCC材料的表面赝电容行为有利于钠离子的存储。因此,氮掺杂中空碳纳米盒可为钠离子电池碳基负极材料提供新思路。

Ultra-fast microwave aided synthesis of gold nanocages and structural maneuver studies

Gold nanocages （AuNcgs） are well-studied, hollow, metallic nanostructures that have fascinated researchers in the fields of nanotechnology, materials science, photoelectronics, biotechnology, and medical science for the last decade. However, the time-consuming synthesis of AuNcgs has limited their widespread use in materials science and nano-biotechnology. A novel, ultra-fast, simple, and highly convenient method for the production of AuNcgs using microwave heating is demonstrated herein. This quick method of AuNcg synthesis requires mild laboratory conditions for large-scale production of AuNcgs. The microwave heating technique offers the advantage of precise mechanical control over the temperature and heating power, even for the shortest reaction period （i.e., seconds）. Microwave-synthesized AuNcgs were compared with conventionally synthesized AuNcgs. Structural maneuver studies employing the conventionally produced AuNcgs revealed the formation of screw dislocations and a shift in the lattice plane. Detailed characterization of the microwave-generated AuNcgs was performed using high resolution transmission electron microscopy （HRTEM）, scanning electron microscopy （SEM）, X-ray powder diffraction （XRD）, and spectroscopic techniques.