Exploration of single molecule events in a haloperoxidase and its biomimic: localization of halogenation activity

In situ observation of single oxidation/halogenation events by catalytically generated hypobromite species using single molecule fluorescence microscopy allows monitoring of the diffusion behavior of these halonium species from the catalyst into the bulk solution. The fluororgenic probe specifically reacts with hypohalites, yielding fluorescein that can be detected with single molecule sensitivity. It was found for two investigated catalysts (Curvularia verruculosa enzymes and tungstate-exchanged LDH crystals) that in steady-state conditions hypobromite is able to diffuse over 800 nm in the bulk solution before it oxidizes organic substrates.     

Morphology of large ZSM-5 crystals unraveled by fluorescence microscopy

Understanding the internal structure of ZSM-5 crystallites is essential for improving catalyst performance. In this work, a combination of fluorescence microscopy, AFM, SEM, and optical observations is employed to study intergrowth phenomena and pore accessibility in a set of five ZSM-5 samples with different crystal morphologies. An amine-functionalized perylene dye is used to probe acid sites on the external crystal surface, while DAMPI (4-(4-diethylaminostyryl)- N-methylpyridinium iodide) is used to map access to the straight channels in MFI from the outer surface. The use of these dyes is validated by studying the well-understood rounded-boat type ZSM-5 crystals. Next coffin-shaped ZSM-5 crystals are considered; we critically evaluate the seemingly conflicting 2-component and 3-component models that have been proposed to account for the hourglass structure in these crystals. The data prove that observation of an hourglass structure is essentially unrelated to a 90 degree rotation of the pyramidal crystal components under the (010) face. Hence, in perfectly formed coffin-shaped crystals, the straight channels can be accessed from (010). However, in other crystal batches, sections with a 90 degrees rotation can be found; they are indeed located inside the crystal sections under (010) but often only partially occupy these pyramidal components. In such a case, both straight and sinusoidal pores surface at the hexagonal face. The results largely support the 3-component model, but with the added notion that 90 degree rotated sections (as proposed in the 2-component model) are most likely to be formed inside the defect-rich, pyramidal crystal sections under the (010) faces.     

Fluorescence micro(spectro)scopy as a tool to study catalytic materials in action

Following its widespread use in biomedical research, fluorescence microscopy has recently been introduced in the catalysis field to study chemocatalytic processes with a high spatiotemporal resolution, a unique sensitivity down to the single molecule level and this under in situ conditions. This tutorial review is structured around the length scales that are currently accessible in fluorescence microscopy and discusses the different conceptual approaches that have been developed to study molecular concentration and dynamics like diffusion and catalytic conversion at these micron and sub-micron levels.     

过渡金属掺杂铈中晶格氧的活化

采用密度泛函理论计算研究了在铈表面掺杂的过渡金属(TM)离子对表面晶格氧原子活化的影响.为此,测定了经TM离子修饰的CeO2最稳定(111)表面终端的结构和稳定性.除了保持八面体氧配位的锆和铂掺杂剂外, TM掺杂剂在取代表面Ce离子时更倾向于正方形平面配位.除了Pt(1.14 eV)和Zr(正方形平面配位不稳定)外,所有TM掺杂剂的表面结构从八面体到正方形平面都很容易.通常,四价TM阳离子的离子半径比Ce^4+的小得多,从而导致了显著的拉伸应变晶格,并解释了氧空位形成能量的降低.除Zr外,当产生一个氧空位时,优先形成正方形平面结构.热力学分析表明, TM掺杂CeO2表面在典型环境催化条件下存在氧缺陷.一个具有实际意义的例子是锆掺杂CeO2(111)中的晶格氧容易活化,从而有利于CO氧化.研究结果强调了晶格氧活化的本质和TM掺杂剂在TM-铈固溶催化剂中的优选位置.