An atomistic control of chemical bonds formation and cleavage holds the key to making molecular transformations more energy efficient and product selective. However, inherent scaling relations among binding strengths of adsorbates on various catalytic materials often give rise to volcano-shaped relationships between the catalytic activity and the affinity of critical intermediates to the surface. The optimal catalysts should bind the reactants 'just right', i.e., neither too strong nor too weak, which is the Sabatier's principle. It is extremely useful for searching promising catalysts, but also imposes serious constraints on design flexibility. Therefore, how to circumvent scaling constraints is crucial for advancing catalytic science. It has been shown that hot electrons can selectively activate the chemical bonds that are not responsive to phonon excitation, thus providing a rational approach beyond scaling limitation. Another emerging yet effective way to break the scaling constraint is single atom catalysis. Strong interactions of supported single atoms with supports dramatically affect the electronic structure of active sites, which reroutes mechanistic pathways of surface reactions. In my PhD research, we use CO oxidation reaction on metal-based active sites as a benchmark system to tailor mechanistic pathways through those two strategies 1) ultra-fast laser induced nonadiabatic surface chemistry and 2) oxide-supported single metal catalysis, with the aim to go beyond the Sabatier activity volcano in metal catalysis. / Doctor of Philosophy / Catalysis is the process of increasing the chemical reaction rate by lowering down the activation barrier. There are three different types of catalysis including enzyme, homogeneous, and heterogeneous catalysis. Heterogeneous catalytic reactions involve a sequence of elementary steps, e.g., adsorption of reactants onto the solid surface, transformation of adsorbed species, and desorption of the products. However, the existing scaling relations among binding energies of reaction intermediates on various catalytic materials lead to volcano-shaped relationships, which show the reaction activity versus the binding energy of critical intermediates. The optimal catalysts should bind the reaction intermediates neither too strong nor too weak. This is the Sabatier's principle, which provides useful guidance for searching promising catalysts. But it also imposes the constraint on the attainable catalytic performance. How to break the constraint to further improve the catalytic activity is an emerging problem. The recent studies have shown that the hot surface electrons on the metal surfaces induced by the ultra-fast laser can selectively activate the chemical bonds, thus providing a rational approach beyond scaling constraints. Another way to break the scaling constraint is single atom catalysis. The metal oxides are frequently used as the support to stabilize the single metal atoms. The strong interaction between the single metal atoms and the support affects the electronic structure of the catalysts. Thereby catalytic reactions on the single metal atoms catalyst are very different from that on metal surfaces. In my PhD research, we use CO oxidation reaction as a benchmark system, to tailor reaction pathways through those two strategies on 1) Ru(0001) under ultra-fast laser pulse and 2) Ir single metal atoms supported on spinel oxides, to go beyond Sabatier activity volcano in metal catalysis.

No description available.

Single atom catalysis is a relatively new form of heterogeneous catalysis. While single atom catalysts probably are already used in a lot of catalysis, their identification and characterization has only recently become common place. As we now have the ability to synthesis relatively pure systems consisting of single atoms and then to characterize them, there are many interesting questions that we can answer about them. In this work we will use a combination of several different types of characterizations such as kinetic measurements, diffuse reflectance infrared Fourier transform spectroscopy, extended x-ray absorption fine structure, and many more to better understand how single atoms react and how we can attempt to make such systems more active. The work here is primarily based around Ir single atoms and/or small clusters on three different supports MgAl2O4, TiO2, and CeO2. In each of these cases we attempt to understand how the Ir and the support catalytically oxidize CO into CO2 through a kinetic, and if possible, mechanistic study. Through these mechanistic studies we attempt to isolate the most important parameters of the catalyst so that we can create a more active catalyst. There are, of course, many different ways that we can use this information. The most obvious is by changing the catalyst support, but as the breadth of the research presented here will show, we can also optimize catalytic activity through using mixtures of single atoms with larger species as well as by changing the nuclearity of the said species, i.e., we can increase activity by controlling the size of the catalysts. However, in order to be able to control the activity in this way, we must 1) know how the size affects the activity and 2) know how the reaction conditions affect the size, i.e., we must establish the catalyst size is stable during reaction. Each of these topics are discussed to some extent here. Additionally, we also discuss how different sites of single atoms on the same support might differ and we show that we can create such different sites. On the whole, we have studied single atom and small cluster catalysis in many different directions based on systems of Ir for CO oxidation. This work is also performed with the intent to compare these Ir systems to similar systems of Rh, Pt, Pd, etc. However here we will only discuss the Ir pieces. / Doctor of Philosophy / In this work we study various properties of Ir single atom and subnanometer cluster catalysts for CO oxidation in hopes that we might be able to design a better catalyst with this information. A catalyst is a substance that facilitates a chemical reaction but is not consumed. For this work we will be considering the reaction of carbon monoxide (CO), which is a common pollutant and highly toxic gas, with O2 to create CO2, a much less dangerous pollutant. Our catalyst thus makes this reaction happen much faster and thus allows us to remove CO from exhaust streams, such as car exhaust, better. A single atom catalyst is a catalyst that is primarily a single atom on a metal oxide support. A subnanometer cluster catalyst is thus a catalyst that is smaller than one nanometer (0.00000004 inches). These are typically 10-20 atoms grouped together. This size is interesting as it is bigger than a single atom, but it is still much smaller than a classical catalyst nanoparticle and is thus controlled or dominated by different properties. In this work we will look at how different characteristics of the singe atom and cluster catalysts affect how good of a catalyst it is. The first is how the amount of single atoms and nanoparticles affect the overall activity of the catalyst. This study will tell us what the best mixture of single atoms is. The second study is how small clusters of Ir/MgAl2O4 react differently than single atoms and large nanoparticles. This tells us what the best size for Ir/MgAl2O4 catalysts are. The third study tells us how Ir/TiO2 single atom catalysts react which is useful when compared to Ir/MgAl2O4 and Ir/CeO2 (Chapter 7). The combination of single atom studies then allows us to make predictions on which supports (apart from Ir/MgAl2O4, Ir/TiO2, and Ir/CeO2) will be the best for CO oxidation. The fourth study compares different single atoms (all of Ir/TiO2) and shows how they behave differently, this is another possibility to increase the effectiveness of the catalyst. The fifth study discusses how different conditions affect the size of the Ir/TiO2 catalysts. Specifically, whether they exist as single atoms, subnanometer clusters, or larger clusters. All of these different studies represent another way that we can potentially increase catalytic activity and hopefully will allow our group, or another group to create even more active catalysts.

The adrenal medulla is the inner part of adrenal glands located above each kidney, that produces catecholamines. Neuroblastoma and pheochromocytoma are the most prevalent malignancies of the adrenal medulla. Quantitative diagnosis of urinary catecholamines using HPLC-coupled Mass detectors is the current method for the diagnosis of neuroblastoma and pheochromocytoma. There are two major problems with this approach, (i) Because the catecholamines concentrations have short half-life (10-100 s), a series of urine tests must be performed throughout 24hr, detecting each catecholamine separately, is inconvenient and time-consuming; (ii) mass detectors are expensive, bulky, and require highly skilled personal. Vanillylmandelic (VMA), and homavanillic acid (HVA) are the by-products of catecholamines and are emerging alternative biomarker for catecholamines due to their high stability. Here, we developed a rapid, sensitive, miniaturized, and cheaper sensing platform for simultaneous quantifications of dopamine (DA), VMA, and HVA, with the aid of iron single-atom catalysts (Fe-SACs), based electrochemical sensor. SACs are atomically distributed metal atoms that have a maximum atomic utility rate of nearly 100%, compared to 30% for traditional metal nanoparticles. MXene sheets are employed to stabilize Fe-SACs, where, the exposed lone pairs of MXene serve as sites covalently linking high-energy single Fe atoms. MXene/Fe-SACs were synthesized by treating Ti3C2TxMXene with Iron chloride via freeze-drying followed by annealing. The successful formation of the material was verified by state-of-the-art characterizations. The MXene/Fe-SACs show superior electrocatalytic performance to the commonly used Fe- nanomaterials. Then, it was coated on the electrode surface and used to analyze DA, VMA, and HVA simultaneously via cyclic voltammetry (CV) and square-wave voltammetry (SWV). Under optimized conditions, the MXene/Fe-SACs electrochemical sensor showed detection limits as low as 1 nM and a linear range between 1 nM-100 μM for DA, LOD of 5 nM & linear range of 10 nM-100 μM VMA, and LOD of 10 nM & linear range of 20 nM-100 μM HAV. The method proved successful in detecting biomarkers in (spiked) synthetic urine and human serum. Furthermore, the method was successfully demonstrated in the determination of DA release from PC12 live cells, suggesting the wide practical use of SACs in sensing catecholamines-related metabolites.

Hydrogen is a carrier energy gas that can be utilized as a clean energy source instead of oil and natural gas. Splitting the water into hydrogen and oxygen is one of the most favorable methods to generate hydrogen. The catalytic properties of molybdenum disulfide (MoS2) could be valuable in this role, particularly due to its unique structure and ability to be chemically modified, enabling its catalytic activity to be further enhanced or made comparable to that of Pt-based materials. In general, these modification strategies may involve either structural engineering of MoS2 or enhancing the kinetics of charge transfer, including by confining to single metal atoms and clusters or integrating with a conductive substrate. We present the results of synergetic integration of MoS2 films with a Si-heterojunction solar cell for generating H2 via the photochemical water splitting approach. The results of the photochemical measurements demonstrated an efficient photocurrent of 36. 3 mA cm-2 at 0 V vs. RHE and an onset potential of 0.56 V vs. RHE. In addition to 25 hours of continuous photon conversion to H2 generation, this study points out that the integration of the Si-HJ with MoS2 is an effective strategy for enhancing the internal conductivity of MoS2 towards efficient and stable hydrogen production. Moreover, we studied the effect of doping an atomic scale of Pt on the catalytic activity of MoS2. The electrochemical results indicated that the optimum single Pt atoms loading amount demonstrated a distinct enhancement in the hydrogen generating, in which the overpotential was minimized to -0.0505 V to reach a current density of 10 mA cm−2 using only 10 ALD cycles of Pt. The Tafel slopes of the ALD Pt/ML-MoS2 electrodes were in the range of 55–120 mV/decade, which indicates a fast improvement in the HER velocity as a result of the increased potential. Stability is another important parameter for evaluating a catalyst. The same (10 ALD cycles) Pt/ML-MoS2 electrode was able to continuously generate hydrogen molecules at for 150 hours. These superior results demonstrate that the low conductivity of semiconductive MoS2 can be enhanced by anchoring the film with Pt SAs and clusters, leading to sufficient charge transport and a decrease in the overpotential.

Heterogeneous catalysis plays a significant role in the chemical industry and the global economy. Most heterogeneous catalysts in the chemical industry and laboratory consist of supported metal nanoparticles, clusters and isolated (single) atoms. Understanding structure sensitivity and identifying the active site or sites are crucially essential for designing efficient catalysts. To determine the active sites of a catalyst for a particular chemical reaction, in-situ/operando spectroscopy, such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray absorption fine structure (XAFS) spectroscopy, is usually implemented as characterization tools. However, understanding the limitation of the characterization tools is crucial to eliminate misleading conclusions. Therefore, the main object of this work is not only to characterize the catalyst before and after the reaction but to investigate the reliability of the characterization tools as well as the stability of the metal clusters and single atoms during CO oxidation. There are four main findings that will be present in this work. First, a high-flux X-ray beam can induce structural change that leads to a reduction of the metal and agglomeration of metal clusters. This finding is very important since X-ray beam damage is uncommon for heterogeneous catalysis as for homogeneous catalysts and biological samples. In the study, the effect of high-flux X-ray on the Rh clusters and nanoparticles was highlighted along with providing mitigation strategies in order to reduce the damage caused by the high-flux X-ray beam. The second important finding is about the characterization of Rh clusters and nanoparticles during CO reduction treatment using DRIFTS. In this study, the integration of low-temperature CO oxidation kinetics as a characterization tool with DRIFTS, XAFS and scanning/transmission electron microscopy (STEM) was found to be necessary to improve the characterization of Rh single atoms. Implementing CO oxidation measurements at low temperatures can provide a rough estimation of the percentage of Rh single atoms. The third finding is related to the stability of Rh clusters upon exposure to CO, oxygen and CO oxidation at different temperatures. The study shows an unexpected dynamic structural change that the Rh cluster undergoes during exposure to oxygen even at room temperature in which the Rh clusters disperse to form Rh single atoms. This dispersion phenomenon was found to be size, gas environment and temperature dependent. For example, small clusters tend to disperse while large nanoparticles resist dispersion. additionally, increasing the temperature to ∼ 160 with CO and oxygen lead to an increase in the percentage of Rh single atoms. More importantly, the dispersed catalyst (Rh single atoms) exhibits higher CO oxidation activity than Rh nanoparticles by 350x. This finding can also be used for Rh single atoms synthesis for different oxide supports such as MgAl2O4, TiO2, and CeO2. Finally, the fourth finding is about investigating the CO oxidation kinetics and mechanism. The kinetics of Rh single atoms differ from Rh nanoparticles. Implementing in-situ spectroscopy helps to identify the resting state of the Rh complex during CO oxidation which is Rh(CO)2. By combining CO oxidation kinetics and in-situ spectroscopy, the plausible mechanism was suggested to be Eley-Rideal/Mars Van Krevelen mechanism. / Doctor of Philosophy / Heterogeneous catalysts are solid materials that scientists and chemical engineers use to convert undesirable raw reactants (liquid or gas) to other products (liquid or gas). One example of a heterogeneous catalyst is a catalytic converter used in most cars around the world. One goal of the catalytic converter is to convert CO (toxic gas) to CO2 (less toxic). The catalyst in a catalytic converter contains precious metals as nanoparticles such as Platinum (Pt), Palladium (Pd) and Rhodium (Rh) deposits on oxide supports (inert materials) such as Al2O3. These Pt, Pd and Rh nanoparticles help to accelerate the chemical reaction (e.g.CO oxidation) in which converting the toxic gas CO to CO2 at a relatively low temperature compared to if the reaction proceeds without those metal nanoparticles. In order to improve the performance of the catalyst, scientists and engineers implement characterization techniques to identify the active site based on the shape and size of the nanoparticles. One method to improve the catalyst performance is to decrease the particle size below 2 nm or even to reach isolated atoms. Unfortunately, synthesizing isolated (single) atoms supported on oxide support is very challenging. One main discovery presented in this work is that Rh single atoms can be synthesized using a simple but effective method. More importantly, Rh single atoms show higher performance than Rh nanoparticles by 350 times which helps to convert CO the toxic gas to CO2 at room temperature. This finding is important in which that the synthesis presented here can be used for different chemical reactions such as methane oxidation and methanol carbonylation.

Les acides carboxyliques aliphatiques sont utilisés dans de nombreux secteurs industriels et leur importance économique augmente. Ils sont actuellement produits en grande quantité, grâce à des procédés utilisant le C0 qui est principalement non- renouvelable. L'anhydride carbonique est une molécule potentiellement écologique, renouvelable et abondante. Cette thèse décrit l'étude et l'optimisation d'un système catalytique homogène de Rh, utilisé pour produire des acides carboxyliques aliphatiques à partir de substrats oxygénés, C02 et H2. Le système consiste en un précurseur de Rh, un additif à base d'iodure et un ligand PPh3, fonctionnant dans un réacteur discontinu sous une pression de C02 et de H2. Les conditions de réaction ont été optimisées pour chaque classe de substrats étudiés: alcools primaires et secondaires, cétones, aldéhydes et époxydes. 30 molécules différentes ont été converties en acides carboxyliques, conduisant à des rendements jusqu'à 80%. En plus, le système a été étudié avec une approche de « Design of Experiment », ce qui a permis d'obtenir des informations supplémentaires concernant les paramètres étudiés. Le mécanisme de réaction et les espèces catalytiques actives ont été étudiés par différentes manipulations comme des réactions compétitives, des expériences de RMN et l'utilisation de molécules marquées. La réaction est composée de transformations non catalytiques et de deux étapes catalytiques. La réaction se déroule à travers une réaction de reverse Water Gas Shift (rWGSR) transformant le C02 et l'H2 en C0 et H20, qui sont consommés dans l'hydrocarboxylation suivante de l'alcène formé in situ pour livrer l'acide carboxylique. Le système catalytique est similaire aux catalyseurs traditionnels à base du Rh pour les réactions de carbonylation et de Water Gas Shift. Le PPh3 est nécessaire pour fournir des ligands supplémentaires, permettant au catalyseur de fonctionner avec une quantité minimale de ligand toxique de C0. En plus, un système catalytique hétérogène a été étudié pour la même réaction. « Single Atom Catalysts » (SACs) reçoit beaucoup plus d'attention que les solutions catalytiques, car il présente à la fois les avantages des catalyseurs homogènes (sélectivité, haute activité) et des catalyseurs hétérogènes (séparation et recyclage faciles). Des atomes de rhodium simples dispersés sur du graphène dopé avec l'N ont été synthétisés et caractérisés, obtenant des informations concernant la structure chimique et physique du matériau. Finalement, ils ont été testés ainsi que les catalyseurs pour l'activation du C02, la production d'acides carboxyliques, les réactions d'hydrogénation et d'hydrogénolyse / Aliphatic carboxylic acids are used in many industrial sectors and their importance from an economical point of view is increasing. They are currently produced in large quantities, through processes exploiting the mostly non-renewable C0 as C1 synthon. Carbon dioxide is a potential environmentally friendly, renewable and abundant C1 building block. The aim of this work is to provide a catalytic protocol converting C02, H2 and oxygenated substrates to obtain useful chemicals, like carboxylic acids.To this end a homogeneous catalytic Rh system, used to produce aliphatic carboxylic acids starting from oxygenated substrates, C02 and H2 was investigated and optimized. The system consists of a Rh precursor, iodide additive and PPh3 ligand working in a batch reactor under C02 and H2 pressure. The reaction conditions were optimized for each class of investigated substrates: primary alcohols, secondary alcohols, ketones, aldehydes and epoxides. The reaction scope was investigated and 30 different molecules were converted into carboxylic acids, leading to yields of up to 80%. ln addition, the system was studied using a Design of Experiment approach, obtaining additional information regarding the studied parameters.The reaction mechanism and the catalytically active species were studied, by different experiments like competitive reactions, NMR and labelling experiments. This investigation resulted in a deeper knowledge of the reaction pathway, composed of some non-catalytic transformations and two catalytic steps. The reaction proceeds through a reverse Water Gas Shift Reaction (rWGSR) transforming C02 and H2 into C0 and H20, which are consumed in the following hydrocarboxylation of the in-situ formed alkene to give the final carboxylic acid product. The catalytic system is similar to traditional Rh carbonylation and Water Gas Shift catalysts. The PPh3 is needed to supply additional ligands allowing the catalyst to work in reaction conditions with a minimal amount of toxic C0 ligand. ln addition, a heterogeneous catalytic system was investigated for the same reaction. Single atom catalysts (SACs) are receiving much attention as catalytic solution, since they have both the advantages of homogeneous (selectivity, high activity) and heterogeneous (easy separation and recycling) catalysts. Single Rh atoms dispersed on N-doped graphene were synthesized and characterized, obtaining information regarding the chemical and physical structure of the material. Eventually, they were tested as catalysts for C02 activation, carboxylic acid production, hydrogenation and hydrogenolysis reactions / Aliphatische Carbonsauren werden in vielen industriellen Bereichen verwendet und ihre wirtschaftliche Bedeutung nimmt zu. Sie werden derzeit in gror.en Mengen hergestellt, indem das meistens nicht erneuerbare Kohlenmonoxid als C1-Synthon genutzt wird. Kohlendioxid ist ein potenziell umweltfreundlicher, erneuerbarer und abundanter C1-Baustein. Das Ziel dieser Arbeit ist die Entwicklung eines Protokolls zur katalytischen Umwandlung von C02, H2 und sauerstoffhaltigen Substraten, um nützliche Chemikalien, wie Carbonsauren zu erhalten. Zu diesem Zweck wird ein homogenes Rh-Katalysatorsystems zur Herstellung aliphatischer Carbonsauren aus sauerstoffhaltigen Substraten, C02 und H2 untersucht und optimiert. Das System besteht aus Rh-Prakursor, lodid-Additiv und PPh3 als Ligand, die in einem Batchreaktor unter C02 und H2 eingesetzt werden. Die Reaktionsbedingungen wurden für folgende Substratklassen optimiert: primare Alkohole, sekundare Alkohole, Ketone, Aldehyde und Epoxide. Es wurden insgesamt 30 verschiedene Substrate mit Ausbeuten bis zu 80% zu Carbonsauren umgesetzt. Darüber hinaus wurde das System mit einem ,,Statistische Versuchsplanung"-Ansatz untersucht, um zusatzliche lnformationen zu den untersuchten Parametern zu erhalten. Mechanismus und katalytisch aktive Spezies wurden durch verschiedene Experimente wie Konkurrenzreaktionen, NMR- und Markierungsexperimenten untersucht. Dies erschloss den Reaktionsweg, der aus mehreren nicht-katalytischen Transformationen und zwei katalytischen Schritten besteht. Die Reaktion verlauft durch eine ,,reverse Wassergas-Shift-Reaktion" (rWGSR), die C02 und H2 in C0 und H20 umwandelt. Diese werden wiederum bei der nachfolgenden Hydrocarboxylierung des in-situ gebildeten Alkens unter Bildung der Carbonsaure verbraucht. Das katalytische System ahnelt herkômmlichen Rh-Carbonylierungs- und WGSR-Katalysatoren. PPh3 fungiert als zusatzlicher Ligand, der es dem Katalysator ermôglicht unter den gleichen Reaktionsbedingungen mit minimaler Menge toxischen C0 als Liganden zu arbeiten. Zusatzlich wurde ein heterogenes katalytisches System für die gleiche Reaktion untersucht. ,,Single atom catalysts" (SACs) erhalten gror.e Aufmerksamkeit als neue Katalysatorklasse. Sie kombinieren die Selektivitat und hohe Aktivitat homogener und die einfache Abtrennung und Recycling heterogener Katalysatoren Verschiedene Katalysatoren aus auf N-dotiertem Graphen dispergierten Rh-Atomen, wurden synthetisiert und charakterisiert. Dadurch wurden lnformationen über die chemische und physikalische Struktur des Materials gewonnen und als Katalysatoren für C02-Aktivierung, Carbonsauresythese, Hydrierung und Hydrogenolyse getestet

Single atoms are promising candidates for physically implementing quantum bits, the fundamental unit of quantum information. We have built an apparatus for cooling, trapping and imaging single rubidium atoms in microscopic optical tweezers. The traps are formed from a tightly focused off-resonant laser beam, which traps atoms using the optical dipole force. The traps have a diameter of ~1 μm and a depth of ~1 mK. The novelty of our approach is the use a digital mirror device (DMD) to generate multiple independently movable tweezers from a single laser beam. The DMD consists of an array of micro-mirrors that can be switched on and off, thus acting as a binary amplitude modulator. We use the DMD to imprint a computer-generated hologram on the laser beam, which is converted in to the desired arrangement of traps in the focal plane of a lens. We have developed fast algorithms for calculating binary holograms suitable for the DMD. In addition, we use this method to measure and correct for errors in the phase of the wavefront caused by optical aberrations, which is necessary for producing diffraction-limited focal spots. Using this apparatus, we have trapped arrays of up to 20 atoms with arbitrary geometrical arrangements. We exploit light-assisted collisions between atoms to ensure there is at most one atom per trapping site. We measure the temperature of the atoms in the traps to be 12 μK, and their lifetime to be 1.4 s. Finally, we demonstrate the ability to select individual atoms from an array and transport them over a distance of 14μm with laser cooling, and 5 μm without.

Ultracold neutral atoms confined in optical dipole traps have important applications in quantum computation and information processing, quantum simulators of interacting-many-body systems and atomic frequency metrology. While optical dipole traps are powerful tools for cold atom experiments, the energy level structures of the trapped atoms are shifted by the trapping field, and it is important to characterize these shifts in order to accurately manipulate and control the quantum state of the system. In order to measure the light shifts, we have designed a system that allows us to reliably trap individual 87Rb atoms. A non-destructive detection technique is employed so that the trapped atoms can be continuously observed for over 100 seconds. Single atom spectroscopy, trap frequency measurements, and temperature measurements are performed on single atoms in a single focus trap and small number of atoms in a 1D optical lattice in order to characterize the trapping environment, the perturbed energy level structures, and the probe-induced heating. In the second part of the thesis, we demonstrate deterministic delivery of an array of individual atoms to an optical cavity and selective addressability of individual atoms in a 1D optical conveyor, which serves as a potential candidate for scalable quantum information processing. The experiment is extended to a dual lattice system coupled to a single cavity with the capability of independent lattice control and addressability. The mutual interactions of atoms in different lattices mediated by a common cavity field are demonstrated. A semi-classical model in the many-atom regime based on the Jaynes-Cummings model is developed to describe the system that is in good qualitative agreement with the data. This work provides a foundation for developing multi-qubit quantum information experiments with a dual lattice cavity system.

Copper-based materials are one of the most promising catalysts for performing transformations of important organic compounds in both academic and industrial operations. However, it is challenging to consistently synthesize highly active and stable copper species as heterogeneous catalysts due to their relatively high surface energy. As a result, agglomeration usually occurs, which limits the catalytic activities of the copper species. The work presented in this dissertation shows different synthetic strategies for obtaining active and stable copper-based materials by modifying chemical/physical properties of copper nanoparticles (NPs). Emphasis is placed on discussing specific catalytic systems, including carbon-supported catalysts (monometallic and bimetallic copper-based heterogeneous catalysts) and titania-supported catalysts, and their advantages in terms of catalytic performance. In recent years, there has been increasing interest in using metal-organic frameworks (MOFs) as a sacrificial template to obtain carbon-supported NPs via a thermolysis process. The advantages of using MOFs to prepare carbon supported nanomaterials are a fine distribution of active particles on carbon matrix without post-synthesis treatments and corresponding increased catalytic activity and stability in many reaction conditions. To better understand the potential of this synthetic approach, MOF pyrolyzed products have been characterized. Then, they were applied as heterogeneous catalysts for several chemical reactions. In particular, the high energy copper-based MOF, CuNbO-1, was decomposed to obtain an amorphous copper species supported on carbon (a-Cu@C). This catalyst was found to be highly active for reduction, oxidation, and N-arylation reactions without further tuning or optimization. Higher catalyst turnover numbers for each of these transformations were obtained when comparing a-Cu@C activity to that of similar Cu-based materials. To improve catalyst performance, a secondary metal can be introduced to create synergistic effects with the parent copper species. In order to gain insights into the role of the second metal, a well-known Cu-MOF, HKUST-1, was doped with nickel, cobalt, and silver solutions, followed by a decomposition process with 2,4,6-trinitrotoluene (TNT) as additive. This additive was used to enhance the rapid thermolysis of the bimetallic MOFs. In these bimetallic systems, the addition of a second metal was found to help in dispersing both metals over the carbon composite support and in influencing the particle size and oxidation state of the metals. Catalytic performance showed that even <1% of a secondary metal increased the rate for nitrophenol reduction. Optimal catalytic performance was achieved using a Ni-CuO@C bimetallic catalyst. Another synthetic strategy for Cu-catalyst preparation involves using the deposition-precipitation method, in which a copper catalyst anchored on a titania support was synthesized at low weight % in order to obtain a single atom catalyst (1-Cu/TiO2). The higher copper loading catalyst, 5-Cu/TiO2, was synthesized as a benchmark catalyst for comparison. The copper structure in the synthesized catalysts was investigated by powder X-ray diffraction (PXRD), Raman, scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX), X-ray photoelectron spectroscopy (XPS), N2 physisorption and inductively coupled plasma mass spectrometry (ICP-MS) in order to characterize physical and chemical properties. STEM-EDX observations showed single atom copper species less than 0.75 nm in size, as well as nanoparticles with an average diameter of ~1.31 nm. This catalyst was highly active in the reduction of nitro-aromatic compounds with NaBH4 at room temperature. The small to atomic level sizes of the Cu species and multiple oxidation states of Ti species were found to play a crucial role in the catalytic activity.