氧掺入MoS2调节芳香硝基化合物选择性转氢还原

芳香胺类化合物及其衍生物是一类重要的有机合成中间体,广泛应用于染料、农药、医药及其他精细化学品.目前催化芳香硝基化合物还原制备芳香胺的多相催化体系多使用含有d6-d10贵金属以及高活性Ni的催化剂.为了提高反应的选择性,金属纳米颗粒的尺寸控制、合金效应、金属载体强相互作用、溶剂以及添加剂的筛选等不同手段被采用.考虑到该类催化剂复杂的制备方法以及易氧化的性质,近年来稳定高效的非贵金属体系的开发得到了广泛关注.MoS2是一类重要的高温加氢催化剂,不饱和的Mo位点(CUS Mo)被认为在催化过程中起到了关键性作用.但是理论与实践已经证明,作为代表性的二维材料,MoS2的活性位点多集中于层状结构的边楞结构处.占有最大暴露面积的基面结构因为稳定的Mo-S化学键组成在化学反应中多表现为催化惰性.通过剥离的手段可以有效提升活性位点的数目,但新增的活性位点仍然多集中于层状结构的边楞结构处而不是基面.在MoS2与MoO2结构中Mo-S和Mo-O的键长不同,同时S和O的配位形式也不同.可以预见的是,如果MoS2结构中的一部分S元素被O元素取代,在这样的材料中将会出现大量缺陷以及活性CUS Mo结构.结合先前关于硫化钼材料的制备方法,我们通过部分硫化还原[Mo7O24]6-前驱物的方法制备了氧掺杂的MoS2材料(标记为O-MoS2).通过XRD,XPS,Raman和EDX等表征发现,不同的Mo-O结构存在于O-MoS2材料中.HRTEM表征结果显示,O-MoS2表面存在着丰富的结构缺陷.EXAFS结果显示,O-MoS2材料中可能含有四配位以及五配位的CUS Mo结构.以甲酸铵还原硝基苯为探针反应检测了CUS Mo结构.发现O-MoS2可以在水相条件下高效催化芳香硝基化合物还原生成相应的芳香胺,且催化剂稳定,可以多次循环使用.结合对照不同催化剂的NH3-TPD数据以及MoS2结构模型,我们发现O-MoS2材料中含有丰富的CUS Mo结构,这些CUS Mo结构更多地存在于材料的基面而非边楞结构.我们认为,对于该类掺杂MoS2材料的制备及结构表征将有利于拓宽MoS2催化剂从高温气相反应到温和液相反应中的应用.     

非平衡磁控溅射沉积MoS2-Ti复合薄膜结构与磨擦摩损性能研究

采用非平衡磁控溅射法制备出不同Ti含量的MoS2-Ti复合薄膜并对其结构进行表征,采用显微硬度仪测量MoS2-Ti复合薄膜的显微硬度,在球-盘摩擦磨损试验机上评价其在大气中的摩擦磨损性能.结果表明:不同Ti含量的MoS2-Ti复合薄膜呈岛状生长模式,断面呈致密细柱状,结晶状态均为无定形态;薄膜的显微硬度随Ti含量增加而升高;MoS2-Ti复合薄膜在大气中的摩擦磨损性能优于MoS2薄膜,掺杂适当Ti可以使MoS2-Ti复合薄膜的摩擦曲线波动减小,耐磨寿命提高,在本试验研究范围内,含30%Ti复合薄膜的耐磨寿命最长,当Ti掺杂量达到50%时MoS2-Ti复合薄膜失去润滑性能.     

二硫化钼粉晶表面氧化机理研究

人们都采用Ａｒ＾＋刻蚀法轰击样品表面以表征其元素的深度分布和价态。这种分析方法的缺点是容易导致大多数化合物被还原而使表面层的真空组成受到破坏。因此，利用具有非破坏性特点的Ｘ射线光电子谱的角度分辨技术，对ＭｏＳ２粉晶表面几个分子层内的原子浓度分布作了深度剖析和元素氧化状态的表征，以考察其氧化反应机理。     

Distance Synergy of MoS2-Confined Rhodium Atoms for Highly Efficient Hydrogen Evolution

Perturbing the electronic structure of the MoS₂ basal plane by confining heteroatoms offers the opportunity to trigger in-plane activity for the hydrogen evolution reaction (HER). The key challenge consists of inducing the optimum HER activity by controlling the type and distribution of confined atoms. A distance synergy of MoS₂-confined single-atom rhodium is presented, leading to an ultra-high HER activity at the in-plane S sites adjacent to the rhodium. By optimizing the distance between the confined Rh atoms, an ultra-low overpotential of 67 mV is achieved at a current density of 10 mA cm⁻² in acidic solution. Experiments and first-principles calculations demonstrate a unique distance synergy between the confined rhodium atoms in tuning the reactivity of neighboring in-plane S atoms, which presents a volcanic trend with the inter-rhodium distance. This study provides a new strategy to tailor the activity of MoS₂ surface via modulating the distance between confined single atoms.     

Distance Synergy of MoS2‐Confined Rhodium Atoms for Highly Efficient Hydrogen Evolution

Perturbing the electronic structure of the MoS₂ basal plane by confining heteroatoms offers the opportunity to trigger in‐plane activity for the hydrogen evolution reaction (HER). The key challenge consists of inducing the optimum HER activity by controlling the type and distribution of confined atoms. A distance synergy of MoS₂‐confined single‐atom rhodium is presented, leading to an ultra‐high HER activity at the in‐plane S sites adjacent to the rhodium. By optimizing the distance between the confined Rh atoms, an ultra‐low overpotential of 67 mV is achieved at a current density of 10 mA cm^?2 in acidic solution. Experiments and first‐principles calculations demonstrate a unique distance synergy between the confined rhodium atoms in tuning the reactivity of neighboring in‐plane S atoms, which presents a volcanic trend with the inter‐rhodium distance. This study provides a new strategy to tailor the activity of MoS₂ surface via modulating the distance between confined single atoms.     

Rapid Discrimination of Bacterial Drug Resistivity by Array-Based Cross-Validation Using 2D MoS2

The precise discrimination of microbes based on family, class and drug resistivity is essential for the early diagnosis of infectious diseases. Information about the type and strength of drug resistivity can help the analyst to prescribe a suitable antibiotic at the proper dosage to completely eradicate microbes without giving them a chance to gain further resistance. Herein, we propose a sensor array based on the use of cationic two-dimensional MoS₂ units and green fluorescence protein as building blocks. Cationic surfaces of receptors with various functionality were suitable for tunable interaction with anionic surfaces of microbes. The array successfully discriminates six different bacterial strains. The versatile ability of the receptors to bind with the wild-type as well as the corresponding ampicillin-resistant strain contributed significantly to rapid detection with high sensitivity. The optimized array was able to classify five different types and three different extents of drug-resistant variants of Escherichia coli by using bacteria cells and lysates. Finally, we have introduced the cross identification method using both bacteria cells and lysates and we found a great enhancement of detection in sensitivity and accuracy. This is the first report of this approach, which can be extended to many other methods for better accuracy in array-based detection.     

制备工艺对MoS2粘结固体润滑涂层微动磨损寿命的影响

在不同载荷和位移振幅条件下,考察了2种基体材料表面MoS2粘结固体润滑涂层的微动磨损性能,深入分析了基体表面预处理、涂层厚度及涂层固化温度等对涂层微动磨损寿命的影响.结果表明,通过提高基体材料硬度、增加涂层厚度、对基体表面进行喷砂预处理以及对涂层进行高温固化等均可不同程度地提高涂层的微动磨损寿命,其中高温固化对涂层磨损寿命的影响最显著;而基体表面喷砂处理对高温固化涂层磨损寿命的影响减弱.喷砂42CrMo基体表面涂覆的经高温固化的厚16±1μm的MoS2粘结固体润滑涂层的抗微动磨损性能最佳.