The understanding of nucleation and growth of metals on a planar support at the atomic level is critical for both surface science research and heterogeneous catalysis studies. In this dissertation, two planar substrates, including graphene and ultra-thin silica film were employed for supported model catalysts studies. The structure and stability of several catalytically important metals supported on these two substrates were thoroughly investigated using scanning tunneling microscopy (STM) coupled with other traditional surface science techniques. In the study of the graphene/Ru(0001) system, the key factors that govern the growth and distribution of metals on the graphene have been studied based on different behaviors of five transition metals, namely Pt, Rh, Pd, Co, and Au supported on the template of a graphene moire pattern formed on Ru(0001). Both metal-carbon (M-C) bond strength and metal cohesive energies play significant roles in the cluster formation process and the M-C bond strength is the most important factor that affects the morphology of clusters at the initial stages of growth. Interestingly, Au exhibits two-dimensional (2-D) structures that span several moire unit cells. Preliminary data obtained by dosing molecular oxygen onto CO pre-covered Au islands suggest that the 2-D Au islands catalyze the oxidation of CO. Moreover, graphene/Ru(0001) system was modified by introducing transition metals, oxygen or carbon at the interface between the graphene and Ru(0001). Our STM results reveal that the geometric and/or electronic structure of graphene can be adjusted correspondingly. In the study of the silica thin film system, the structure of silica was carefully investigated and our STM images favor for the [SiO4] cluster model rather than the network structure. The nucleation and adsorption of three metals, namely Rh, Pt and Pd show that the bond strength between the metal atom and Si is the key factor that determines the nucleation sites at the initial stages of metal deposition. The annealing effect studies reveal that Rh and Pt atoms diffuse beneath the silica film and form the 2-D islands that are covered with a silica thin film. In contrast, the formation of Pd silicide was observed upon annealing to high temperatures.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2008. / Includes bibliographical references.

Thesis (M. S.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Dickson, Robert; Committee Member: Brown, Ken; Committee Member: Curtis, Jennifer; Committee Member: Payne, Christine; Committee Member: Perry, Joseph.

No description available.

<p> A series of chiral transition metal clusters of the type MCo2(CO)6C-CO2R, where M = Co(CO)3, (C5H5)Mo(CO)2, (i-Pr-C5H4)Mo(CO)2 or (indenyl)Mo(CO)2 and R =menthyl or exo-bornyl have been synthesized and characterized using FAB mass spectrometry and high field NMR techniques. The isopropyl Cp and the indenyl ligands served as NMR probes to detect the chirality created by the incorporation of the terpenoidal capping group.</p> <p> The tricobalt clusters were treated with the bidentate ligands arphos, Ph2AsCH2CH2PPh2 and diphos, Ph2PCH2CH2PPh2. Treatment with arphos yields a pair of diastereomers which are interconverted via the migration of the Ph2As terminus of the arphos ligand from one cobalt vertex to another. This fluxionality was monitored by variable-temperature 31P NMR spectroscopy. The diphos cluster is not a fluxional molecule. However, the Co(CO)2P vertices are diastereotopic and give two signals in the 31P NMR. Thus, diphos serves as a convenient probe for chirality. </p> <p> In the case where M = Co(CO)3 , the two remaining cobalt vertices are diatereotopic and are, in principle, not equally susceptible to attack by an incoming ligand. To test for chiral discrimination, these molecules have been treated with several different phosphines. If the reaction were to proceed with any degree of selectivity, the 31P NMR spectrum ought to show resonances of unequal intensity. Such results have been obtained when a bulky phosphine, such as tricyclohexylphosphine, has been employed.</p> / Thesis / Master of Science (MSc)

No description available.

Small silver nanoclusters are synthesized using polycytosines as matrices. Different size silver nanoclusters ranging from Ag1 to Ag7 exhibit bright emission maxima at blue (480nm), green (525nm), red (650nm), and IR (720nm) wavelengths with varying the excitation wavelengths. With electrophoresis, correlation of emission with mass spectra, the Ag cluster sizes are identified with blue emitters as Ag5, green emitters as Ag4, red emitters as Ag3, and IR emitters as Ag2. Ag4 and Ag5 appear to be partially oxidized while Ag2 and Ag3 are likely fully reduced. Silver cluster stability and their dynamics are observed from silver clusters encapsulated by polycytosine (Cm:Agn). From length study of polycytosine, the longer the polycytosine is, the more stable the larger clusters such as Ag5 are. In time-dependent optical measurements, isosbestic points are observed from Cm:Agn by converting red and IR species into blue and green species, while in the case of temperature-dependent optical properties, with increasing temperature, the blue (oxidized Ag5) and green (oxidized Ag4) emitters convert into the red (Ag3) and IR (Ag2) emitters. NaCl-dependent optical measurements support the assignments of oxidized and fully reduced silver emitters. Circular dichroism (CD) is used to investigate conformational changes in Cm and Cm:Agn with varying conditions (time, temperature and NaCl) and the studies indicate that no conformational changes in Cm:Agn are observed from the time and temperature, while the conformational changes in Cm:Agn are observed from the NaCl studies. From pH-dependent emission study of Cm:Agn, the silver nanocluster dynamics slow down at high pH. Using confocal microscopy technique, single molecules on IR species, C12:Ag2 are investigated and demonstrate that C12:Ag2 is brighter and more photostable than Cy5 which is known to be one of the best IR dyes. With low excitation power, molecules can be monitored for hours, giving bright blinking free, stable fluorescence. The photophysics of this new dye make it a promising candidate for single molecule studies in biological applications.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

包含少於1000 個原子的金屬納米顆粒會與此金屬的常規尺寸材料有很大差別。它們擁有一些特殊的物理和化學的性質，因而在過去的二十年中吸引了大量的研究工作。但是由於尺寸太小，對於這些納米結構的深入和全面的研究十分困難。掃描隧道顯微鏡方法是一種強大的研究此類問題的技術。它擁有的極強的空間分辨力和原子操縱的能力使得我們可以獲得一些納米顆粒的細緻信息。在這篇論文中，我將報道我的關於在半導體Si(111)-(7x7)的重構表面的貴金屬（銀/金）顆粒的研究。 / 我首先研究了在Si(111)-(7x7)上的金屬顆粒的製備方法。使用熱蒸發方法，我製備了在Si(111)-(7x7)上的金屬顆粒。在研究了這些金屬顆粒在半元胞中的的整體生長過程之後，我的研究集中在本論文的主要目標--獨立的銀納米顆粒上。通過仔細觀察記錄單個銀原子的擴散過程，我們確認了Ag3‐Ag13 顆粒中的原子數目。這些掃描隧道顯微鏡的圖像同時也指出了這些顆粒的動態性質，包括自發跳動、分解和與鄰近的單個Ag 原子的合成。為了獲得對這些Ag 顆粒的控制，我們找到了一種垂直操縱單個Ag 原子的方法。在樣品的表面，掃描隧道顯微鏡的針尖通過特定的程序被用來抓起和放下單個Ag 原子。它被用來組裝和拆裝Ag的顆粒。各種Ag 顆粒在半元胞中被組裝，同時我們發現單個半元胞中的最大的顆粒是Ag25。同時這項技術被用來組裝複雜的Ag 顆粒的圖形。 / 使用上面這些操縱的技術（熱蒸發方法和原子操縱方法），我們細緻的研究了顆粒的兩方面性質：第一，我們發現對於單個元胞中的Ag 顆粒都存在着顯著的電學的整流效應，同時我們比較了它們各自的特點。通過實驗測量和第一性原理計算，我們發現這種電學整流效應源自電子態密度的耦合效應。當這些顆粒在平面內連接起來從而增加橫向的尺寸時，這種顆粒的整流效應將會繼續存在；但當顆粒形成多層Ag 的結構即垂直方向尺寸增加時，這個整流效應將會消失。另外一個所研究的性質是所有的Ag顆粒都存在一種對周圍單個Ag原子的吸引作用，從而讓自身長大的過程。這一過程對於Ag 顆粒的生長起到了至關重要的作用。我們選擇了幾個有代表性的顆粒，通過原子操縱的方法測量了它們與一個鄰近的Ag 原子的融合過程。測量的結果說明一個顆粒的存在通常會降低一個鄰近Ag 原子向此顆粒擴散的勢壘高度，同時也會影響此單個原子在靠近此顆粒的吸附位上的吸附能。 / Metal nanoclusters with less than 1000 atoms differ very much from their bulk counterparts. They possess many unique chemical and physical properties and have attracted extensive studies during the past two decades. However, in-depth and comprehensive researches of these structures are difficult for their small size. Scanning tunneling microscopy (STM) is a versatile technique to study the nanostructures. Its extreme powerful spatial resolution as well as its atomic manipulation capability enabled us to obtain the detailed information of some nano-clusters. In this thesis, I report on my studies on the noble metal (mainly Ag) clusters on the reconstructed Si(111)-(7x7) surface. / I firstly studied the fflbrication methods of the metal clusters on the Si(111)-(7x7) surface. By thermal deposition, I fabricated Ag clusters on Si(111)-( 7x7). After studying the overall growth process of the Ag clusters in half unit cells, I focused on the main target of this thesis: individual Ag clusters. By carefully observing the diffusion process of the Ag atoms on the surface, we identified of the number of atoms inside Ag3-Ag13 clusters. The STM images also showed the dynamic behaviors of each cluster, including self-hopping, dissociation and association with nearby Ag atoms. For a better controllability, a vertical manipulation technique was developed to transfer single Ag atoms across difference locations on the Si(111)-(7x7) surface. The STM tip was used to pick up or drop off metal atoms from or to the sud"ace following specific procedures. The assembly and disassembly of Ag clusters were achieved by this method. Various Ag clusters were built and the largest occupation of a FRUC was found to be 25 Ag atoms. This technique was demonstrated to be able to manipulate Au atoms and to assemble Au clusters. / With the developed fabrication methods, by thermal deposition as well as by atomic manipulation, two properties of the clusters were studied carefully: first, a prominent electrical rectifying behavior was observed for all the Ag clusters. Their individual behaviors were compared with each other. A combination of experimental measurements and first principle calculations unveiled the mechanism of the electronic rectifying behaviors to be a wave function coupling effect. The rectifying behavior for the clusters was found to persist when clusters connected laterally, whereas to disappear when the vertical size of the cluster increased to form multiple Ag layers. The second property studied is that all the clusters are found to attract nearby single Ag atoms to grow larger. This behavior plays a critical role in the growth process of the Ag clusters. we chose several typical Ag clusters and measured the merging process with single neighboring Ag atoms by atomic manipulation. The results indicate that the presence of a Ag cluster will mostly reduce the diffusion barrier of a single Ag atom in the neighboring half unit cells to diffuse to the cluster and even affect / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Ming, Fangfei = 在Si(111)-(7x7)表面的金屬納米顆粒的製備和性質 / 明方飛. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 116-122). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Ming, Fangfei = Zai Si(111)-(7x7) biao mian de jin shu na mi ke li de zhi bei he xing zhi / Ming Fangfei. / Chapter 1 --- Introduction: metal nano-clusters on semiconductor surfaces --- p.2 / Chapter 1.1 --- Background and Motivation --- p.2 / Chapter 1.1.1 --- Nano-science and nano-technology --- p.2 / Chapter 1.1.2 --- Metal nano-clusters --- p.3 / Chapter 1.2 --- Scanning tunneling microscopy (STM) --- p.6 / Chapter 1.2.1 --- Introduction to STM --- p.6 / Chapter 1.2.2 --- Basic components of STM --- p.7 / Chapter 1.2.3 --- STM working modes --- p.9 / Chapter 1.2.4 --- STM experiments in this thesis --- p.11 / Chapter 1.3 --- Substrate: the Si(111)-(7 x 7) reconstruction surface --- p.12 / Chapter 1.3.1 --- Atomic Structure --- p.12 / Chapter 1.3.2 --- Preparation in ultra high vacuum --- p.14 / Chapter 1.4 --- Growth of Ag on Si(111)-(7 x 7) at room temperature --- p.14 / Chapter 1.4.1 --- Growth method --- p.15 / Chapter 1.4.2 --- Adsorption and diffusion of single Ag atoms --- p.17 / Chapter 1.4.3 --- Forming Ag clusters --- p.20 / Chapter 1.4.4 --- Forming Ag islands --- p.23 / Chapter 1.5 --- Conclusion --- p.25 / Chapter 2 --- Individual Ag clusters: size, dynamics and stability --- p.27 / Chapter 2.1 --- Introduction --- p.27 / Chapter 2.2 --- Experiment --- p.29 / Chapter 2.3 --- Results and discussion --- p.31 / Chapter 2.3.1 --- Growth kinetics --- p.31 / Chapter 2.3.2 --- STrvr images of typical Ag structures Intra-HUC diffusion --- p.33 / Chapter 2.3.3 --- Inter-HUC diffusion --- p.37 / Chapter 2.3.4 --- Inter-HUC diffusion & identification of the number of atoms inside each cluster --- p.38 / Chapter 2.3.5 --- Stability of Ag structures. --- p.45 / Chapter 2.4 --- Conclusion --- p.49 / Chapter 3 --- Assembling and disassembling Ag/ Au clusters by atomic manipulation --- p.51 / Chapter 3.1 --- Introduction --- p.51 / Chapter 3.2 --- Experiment --- p.54 / Chapter 3.3 --- Results and disscussion --- p.55 / Chapter 3.3.1 --- Basic procedures for manipulating a single Ag atom --- p.55 / Chapter 3.3.2 --- Assembly of Ag clusters --- p.58 / Chapter 3.3.3 --- Disassembly of Ag clusters --- p.66 / Chapter 3.3.4 --- Assembly of Ag cluster patterns --- p.70 / Chapter 3.3.5 --- Comparison with the manipulation of Au atoms --- p.71 / Chapter 3.3.6 --- STrvr tip for atomic manipulation --- p.74 / Chapter 3.4 --- Conclusion --- p.75 / Chapter 4 --- Study on the electronic properties of the Ag clusters --- p.76 / Chapter 4.1 --- Introduction --- p.76 / Chapter 4.2 --- Experiment --- p.78 / Chapter 4.2.1 --- Experimental parameters. --- p.78 / Chapter 4.2.2 --- Precise tip positioning --- p.79 / Chapter 4.2.3 --- First principle calculation parameters --- p.80 / Chapter 4.3 --- Results and Discussion --- p.81 / Chapter 4.3.1 --- Grow Ag clusters --- p.81 / Chapter 4.3.2 --- I-V of the clusters. --- p.82 / Chapter 4.3.3 --- Theoretical calculation --- p.88 / Chapter 4.3.4 --- Transition from cluster to bulk in I-V. --- p.91 / Chapter 4.4 --- Conclusion --- p.94 / Chapter 5 --- Dynamics of Ag atoms near an interacting Ag cluster --- p.95 / Chapter 5.1 --- Introduction --- p.95 / Chapter 5.2 --- Results and Discussion --- p.97 / Chapter 5.2.1 --- Different Ag clusters and their orientations --- p.97 / Chapter 5.2.2 --- Association time measurement --- p.99 / Chapter 5.2.3 --- Energy barrier and diffusion prefactor --- p.101 / Chapter 5.2.4 --- Influenced intra-HUC diffusion --- p.105 / Chapter 5.2.5 --- Energy diagram --- p.107 / Chapter 5.3 --- Conclusion --- p.109 / Chapter 6 --- Conclusion and Future Work --- p.111 / Chapter 6.1 --- Conclusion --- p.111 / Chapter 6.2 --- Future work --- p.113 / Bibliography --- p.116

This thesis presents a number of largely independent forays into developing an understanding of the unique chemistry of transition metal clusters. The first chapter of this thesis represents an initial foray into mapping the chemical reactivity of transition metal clusters - a monumental task that will doubtless continue for some time. The small slice undertaken in this work investigates the reactivity with CO of a series of the smallest possible metal clusters; 4d (Nb - Ag) homonuclear metal trimers. In Chapter 2, two known transition metal clusters were studied using CASSCF (MCSCF) and MRCI methods, only to find that DFT methods provided more accurate Ionisation Potentials (IPs). Thus Chapter 3 was devoted to optimising a density functional to predict IPs. As clusters get larger, the number of possible structures grows rapidly too large for human intuition to handle, thus Chapter 4 is devoted to the use of an automated stochastic algorithm, “Kick”, for structure elucidation. Chapter 5 improves on this algorithm, by permitting chemically sensible molecular fragments to be defined and used. Chapter 6 then comes full circle and uses the new Kick algorithm to investigate the reaction of CO with a series of mono-substituted niobium tetramers (i.e. Nb₃X). / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1350246 / Thesis (Ph.D.) - University of Adelaide, School of Chemistry and Physics, 2009