Al2O3忆阻器中氧空位对阻值转换性能的影响研究

忆阻器能够在外加电压下实现高阻态与低阻态的转换,在存储器件及仿神经网络计算等方面有着重要的应用。本文通过在Si衬底上制备得到Pt-Al2O3-Pt的金属-绝缘层-金属结构的忆阻器器件,研究了氧空位对阻值转换性能的影响。利用原子层沉积技术工艺控制生长不同氧空位浓度的Al2O3薄膜,测量并比较其Ⅰ—Ⅴ循环曲线,发现仅有在氧空位浓度较高情况下忆阻器才能够实现在高阻态和低阻态之间的转换。本文实验结果表明氧空位对于实现阻值转换性能有着重要的影响,对生长制备忆阻器器件有着重要意义。     

多级孔芳香骨架材料的合成及固载硫脲催化剂的研究

合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台.     

Insights into the efficient charge separation over Nb2O5/2D-C3N4 heterostructure for exceptional visible-light driven H2 evolution

Two-dimensional carbon nitride(2 D-C₃ N₄)nanosheets are promising materials in photocatalytic water splitting,but still suffer from easy agglomeration and fast photogene rated electron-hole pairs recombination.To tackle this issue,herein,a hierarchical Nb₂ O₅/2 D-C₃ N₄ heterostructure is precisely constructed and the built-in electric field between Nb₂O₅ and 2 D-C₃ N₄ can provide the driving force to separate/transfer the charge carriers efficiently.Moreover,the strongly Lewis acidic Nb₂O₅ can adsorb TEOA molecules on its surface at locally high concentrations to facilitate the oxidation reaction kinetics under irradiation,resulting in efficient photogene rated electrons-holes separation and exceptional photocatalytic hydrogen evolution.As expected,the champion Nb₂O₅/2 D-C₃N₄ heterostructure achieves an exceptional H2 evolution rate of 31.6 mmol g^-1 h^-1,which is 213.6 times and 4.3 times higher than that of pristine Nb₂O₅ and2 D-C₃N₄,respectively.Moreover,the champion heterostructure possesses a high apparent quantum efficiency(AQE)of 45.08%atλ=405 nm and superior cycling stability.Furthermore,a possible photocatalytic mechanism of the energy band alignment at the hetero-interface is proposed based on the systematical characterizations accompanied by density functional theory(DFT)calculations.This work paves the way for the precise construction of a high-quality heterostructured photocatalyst with efficient charge separation to boost hydrogen production.     

Is it universal that the layered-spinel structure can improve electrochemical performance?

The introduction of spinel phase to form the layered-spinel structure(LSS)is an effective way to improve the electrochemical performance of Li-and Mn-rich layered oxides(LMR).But is this structure universal for all LMR systems?In this work,different Mn/Ni ratio systems with the LSS are discussed in detail.It is found that,high discharge capacity(200.8 mA h g^-1 at 1C rate;1C=250 mA h g^-1)as well as high capacity-retention(94%at 1C rate after 100 cycles)can be achieved by forming the LSS for low-Ni system(Mn/Ni=5.0).However,the capacity retention decreases severely in the high-Ni system(Mn/Ni=3.5,2.6).For example,when the ratio of Mn/Ni is 3.5,the capacity-retention of the layered-spinel sample was only 65.8%,compared to the 83%of the original LMR sample.The Ex-situ XRD,XPS,and HRTEM results demonstrate that the introduction of spinel phase in high-Ni system accelerates the transition and collapse of the crystal structure.This work provides guidance for optimizing the proportions of elements and the design of structures for the LMR.     

基于抛光基材的热蒸镀铜箔生长高平整单层石墨烯薄膜

在石墨烯的化学气相沉积工艺中,铜箔是决定石墨烯薄膜质量的重要因素。传统铜箔由于制备工艺的限制,存在大量的缺陷,导致石墨烯薄膜的成核密度较高。本工作选用抛光铝板、抛光不锈钢板、微晶玻璃和SiO₂/Si作为基材,用热蒸镀法制备了不同粗糙度的铜箔,并详细讨论了以该系列铜箔生长高平整度石墨烯薄膜的条件及铜箔对石墨烯薄膜品质的影响。实验结果表明,铜箔以(111)取向为主,与基材分离后,表面具有纳米级平整度。在生长石墨烯后,从SiO₂/Si剥离的铜箔成核密度是4种基材中最小的。同时,从SiO₂/Si剥离的铜箔晶体结构变化最不明显,具有良好的结晶性,表面几乎不存在铜晶界缺陷。当压强为3 000 Pa,氢气和甲烷流速分别为300 mL/min和0.5 mL/min时,可以获得约1 mm横向尺寸的石墨烯单晶晶畴。     

1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系

催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向.     

水热法制备二氧化锡/钨酸铋复合光催化材料及其催化活性研究

本文用水热法制备了正交晶系的纳米球状结构的二氧化锡和正交晶系的由片状聚集成球状结构的钨酸铋,并且对二者进行了复合,制备出了二氧化锡/钨酸铋复合光催化材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积测试仪(BET)、紫外可见分光光度计等技术对复合样品的结构、形貌、比表面积、孔容孔径和光学性质进行了表征。用碘钨灯模拟太阳光,分别以二氧化锡、钨酸铋和二氧化锡/钨酸铋复合材料为催化剂降解罗丹明B(RhB),研究所制备的二氧化锡/钨酸铋复合材料的光催化活性。光催化90 min时二氧化锡、钨酸铋和二氧化锡/钨酸铋对罗丹明B的降解率分别是9%、22%和30%。实验结果表明,在可见光下,二氧化锡/钨酸铋复合材料的光催化活性要高于单一的二氧化锡和钨酸铋。     

A Triphenylphosphonium Functionalized AIE Conjugated Macrocyclic Tetramal&mide for Mitochondrial-targeting Bioimaging

Developme nt of subcellular orga nelle-targeted bioimagi ng probes is of great imports nee in the field of early detection of diseases and exploring the behaviors of subcellular organelles.Herein,we present a triphenyIphosphonium functionalized conjugated macrocyclic tetramaleimide(TPP-CMT)as a mitochondrial-targeting bioimaging probe.The core of TPP-CMT is obtained by connecting two pyrenes and two benzenes through four maleimides.This unique structure endows TPP-CMT with exceptional far red/near-i nfirared aggregati on-induced emissi on(FR/NIR-AIE)characteristics.TPP-CMT is an excelle nt fluoresce nt emitter in most solve nts and eve n in solid states.The qua ntum yield of TPP-CMT was higher tha n 27% when dissolved in comm on middle-polarity orga nic solve nt and this value remained at 28.2% in its solid state.The in troducti on of four triphe ny Iphosph onium on maleimide positions endows TPP-CMT with mitochondrial-targeting ability.Thanks to the FR/NIR-AIE characteristics and the mitochondri-al-targeti ng ability,this well-desig ned fluoresce nt probe was successfully employed for mitochondrial targeti ng bioimaging of HeLa and HepG2 cells.