二维硫化钼基原子晶体材料的化学气相沉积法制备及其器件

二维过渡族金属硫属化合物因其带隙具有强烈的层数依赖性而在电子器件方面具有广泛的应用前景.其中单层二硫化钼(MoS₂)是该系列材料中最典型的一种直接带隙半导体,它具有优异的光、电、磁、热和力学性能.二维MoS₂有望在光电探测、光伏器件、场效应晶体管、存储器件、谷电子和自旋器件、温差电器件、微纳机电器件和系统等方面得以广泛应用.化学气相沉积(CVD)法已成为制备二维过渡族金属硫属化合物如MoS₂、MoSe₂、WS₂和WSe₂等原子层薄膜的主要手段,尤其科学界利用CVD法对二维MoS₂材料进行了深入的制备探索,通过该方法制备的MoS₂薄膜在电子和光电器件方面已经有广泛研究.本文将从二维MoS₂的基本物性出发,详细介绍CVD法制备MoS₂的各种工艺过程,如热分解硫代硫酸盐法、硫化Mo(MoO_3-x)薄膜制备法、MoO_3-x粉体与硫属前驱体气相合成法和钼箔表面直接硫化法,并介绍了基于MoS₂的二维异质结构筑方法.在制备材料的基础上,详细阐述了二维MoS₂在场效应晶体管、光电探测器、柔性电子器件以及异质结器件方面的应用,并展望了二维材料在半导体器件中的应用前景.     

二维硫化钼的溶液法制备及其复合材料在光、电催化领域的应用

作为二维（2D）过渡金属硫族化合物（TMDs）的成员之一,MoS₂因其独特的物理化学性质及在自然界中丰富的含量成为目前研究最广泛的一种半导体。凭借超薄的层状结构和可调控的禁带宽度,单层和多层的二维MoS₂纳米材料在众多研究领域都备受关注。基于溶液法的合成工艺（如超声辅助液相剥离和湿化学合成法）有望实现大规模、高产量地制备二维MoS₂纳米材料,更重要的是,基于溶液法合成的二维MoS₂纳米材料便于作为模板或者载体来制备功能性复合纳米材料,有利于进一步提升其在相关应用中的性能。本文重点介绍了基于溶液制备二维MoS₂纳米材料的各种合成方法,同时特别关注了溶液法制备的二维MoS₂复合纳米材料及其在光、电催化方面的应用,并展望了溶液法合成二维MoS₂及其复合材料的应用前景和挑战。     

金属相1T´ MoS2增强类石墨相C3N4的可见光催化性能

通过煅烧和静电自组装的方法制备了1T′ MoS₂超薄纳米片和类石墨烯相氮化碳(g-C₃N₄)纳米片的复合材料. 该材料在光催化实验中展现出6.24 μmol?g^?1?h^?1的产氢速率, 优于贵金属铂修饰的g-C₃N₄纳米片的性能(4.64 μmol?g^?1?h^?1). 此外, 该复合材料在光催化降解有机染料甲基橙的实验中表现出0.19 min^?1的催化速率, 而纯g-C₃N₄纳米片只有0.053 min^?1的催化速率. 材料光催化性能的提升可归结于1T′MoS₂ 和g-C₃N₄之间的协同效应, 包括光吸收的增强以及因1T′MoS₂优异电子导电性而得到的高效电荷分离.     

二硫化钼薄膜的刻蚀方法及其应用

过渡金属硫化物因能带结构与层数具有明显的依赖关系而受到广泛关注,尤其是二维二硫化钼（MoS₂）薄膜因其优良的光电性能而成为研究热点。目前,化学气相沉积法（CVD）和剥离法已成为制备MoS₂薄膜的主要方法,但这两种方法均存在难以精确控制MoS₂层数的问题,研究证实通过刻蚀手段能够对MoS₂薄膜层数进行进一步加工,从而得到单层或特定层数的样品。本文综述了基于不同刻蚀原理的MoS₂薄膜刻蚀技术的国内外研究进展,分析讨论了不同刻蚀技术对刻蚀后MoS₂薄膜质量的影响,介绍了MoS₂刻蚀方法在场效应晶体管（FET）以及其他光电器件领域的实际应用和发展前景,最后对将来研究中需要着力解决的问题进行了展望。     

类石墨烯二硫化钨薄膜的化学气相沉积法制备及其应用

类石墨烯过渡金属硫属化合物如MoS₂、WS₂、MoSe₂、WSe₂等因为具有层数依赖的带隙结构而受到了广泛关注。尤其是本征态的WS₂为双极性半导体,它同时具有n型和p型电输运特性,有望在电子电路、存储器件、光电探测和光伏器件方面得以广泛应用。近年来,化学气相沉积技术已经被广泛用于制备大面积二维硫属化合物(如MoS₂, MoSe₂, WS₂ 和WSe₂)原子层薄膜。目前关于其他二维材料体系的综述文献介绍较多,但是针对WS₂介绍的综述文献还鲜有报道。因此,本文综述了类石墨烯WS₂薄膜的化学气相沉积法制备和相关器件的国内外研究进展,讨论了WS₂薄膜的化学气相沉积法制备机理及生长因素如硫粉含量、载气的成分、反应温度、基底材料等对薄膜成膜质量的影响,介绍了WS₂薄膜在晶体管、光电器件及与其他二维材料构成的异质结构器件的最新研究成果,并对可能存在的问题进行了分析和述评。     

石墨烯/MoS2异质结的界面相互作用及其肖特基调控的理论研究

本文基于第一性原理方法,系统研究了外电场对石墨烯/MoS₂范德瓦耳斯异质结界面相互作用及其电子性质的影响.计算结果表明石墨烯和MoS₂之间通过微弱的范德瓦耳斯力结合形成异质结,石墨烯/MoS₂异质结的能带基本上是单层石墨烯和单层MoS₂能带结构的简单叠加并形成了N型肖特基势垒;由于异质结的石墨烯层的电子向MoS₂层转移,导致石墨烯表面带正电,MoS₂表面带负电,在异质结内部形成了方向由石墨烯指向MoS₂的内建电场.此外,对异质结施加不同强度的负电场时,体系的接触类型逐渐由N型肖特基接触类型转变为欧姆接触;对异质结施加不同强度的正电场时,体系的P型肖特基势垒呈降低趋势,体系的N型肖特基势垒呈现先缓慢升高再急剧下降的特点,在电场强度提高至5.0 V·nm^-1附近时,接触类型由N型肖特基接触转变为P型肖特基接触.此项工作将对相关二维场效应晶体管的设计提供参考.     

花状Zn-MOF衍生碳@MoS2复合材料制备及吸波性能

采用Zn-MOF(MOF为金属有机骨架)制备纳米多孔碳材料,通过自组装法将多孔碳与花状MoS₂结合,制备出具有规整有序结构的花状Zn-MOF衍生碳@MoS₂复合吸波材料。基于Zn-MOF衍生纳米多孔碳的高孔隙率、大比表面积,MoS₂的花状结构引起的电磁波多次反射和散射,以及MoS₂和Zn-MOF衍生碳之间存在的强极化效应、良好的阻抗匹配和协同作用,Zn-MOF衍生碳@MoS₂在频率为9.28 GHz时的最佳反射损耗达到-49.68 dB,表现出优异的电磁波吸收性能。     

基于层状二硫化钼纳米片比色检测亚锡离子

在醋酸/醋酸钠缓冲溶液(pH=4.5)中, 亚锡离子对层状二硫化钼(MoS₂)纳米片催化过氧化氢(H₂O₂)氧化邻苯二胺(OPD)的显色反应有很强的抑制作用, 据此构建了一种检测亚锡离子的比色传感器. 实验结果表明, 与不加MoS₂纳米片的OPD/H₂O₂比色传感体系相比, MoS₂/OPD/H₂O₂体系检测亚锡离子的灵敏度显著提高, 线性范围变宽. 在优化的条件下, MoS₂/OPD/H₂O₂传感体系检测亚锡离子的线性范围为0.02~3.0 μmol/L, 检出限为8 nmol/L (S/N=3). 该传感体系对检测亚锡离子具有高的选择性, 可用于湖水中亚锡离子的检测.     

液相剥离石墨烯的电化学传感应用

石墨烯是一种新型二维碳材料,其比表面积大、导电性好、催化活性高、吸附能力强,是构筑高性能电化学传感器的理想材料。相对于石墨烯常用的氧化还原制备方法而言,液相剥离法具有过程简单、可控性强、高效环保以及对石墨烯结构破坏小等特点,在电化学传感领域备受关注。基于本课题组及国内外学者近年来的相关工作,本文重点综述了三种液相剥离石墨烯制备方法的原理,包括超声剥离、液相球磨剥离和电化学剥离,以及他们在电化学传感中的应用进展,并对未来研究进行了展望。     

金箔上单层MoS2的控制生长及电催化析氢应用

金属衬底上单层MoS₂的可控批量制备是探索其微观形貌、新奇物理化学特性以及潜在应用的重要前提. 最近, 我们利用低压化学气相沉积的方法, 在多晶金箔上实现了高质量、大面积/大批量、畴区尺寸可调(从几百纳米到几十微米)单层MoS₂的可控制备; 利用低能电子显微/衍射实现了直接生长的单层MoS₂畴区取向和畴区边界的原位识别; 利用金箔上合成的纳米尺寸MoS₂作为电催化析氢反应的催化剂, 实现了高效的析氢效果(塔菲尔斜率约61 mV/dec, 交换电流密度约38.1 μA/cm²). 本文将以这些研究成果为主线, 系统地阐述金箔上单层MoS₂的可控制备和转移、畴区的原位识别以及在电催化析氢反应中的应用, 并对该领域的未来发展趋势和所面临的挑战进行简要的展望.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.