Poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) triblock copolymer with di-hydroxyl terminated groups (HO-PEO-PS-PEO-OH) was conjugated with nitrilotriacetic acid (NTA) via esterification reaction using N,N'-Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and Dimethylformamide (DMF) as a solvent at 80 ○C. The poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with NTA end groups (NTA-PEO-PS-PEO-NTA) was characterized and structure confirmed by 1H NMR, 13C NMR, and FT-IR spectroscopies. Thermogravimetric analysis (TGA) was carried out to investigate the thermal stability of the starting triblock copolymer poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with di-hydroxyl terminated groups (HO-PEO-PS-PEO-OH) and the conjugated poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) functional polymer (NTA-PEO-PS-PEO-NTA). Surface morphologies of the (HO-PEO-PS-PEO-OH) and (NTA-PEO-PS-PEO-NTA) were studied by atomic force microscopy. In addition, the size distributions were determined using dynamic light scattering. The thermal behavior of the (HO-PEO-PS-PEO-OH) and (NTA-PEO-PS-PEO-NTA) were examined by differential scanning calorimetry (DSC). DSC thermograms indicate the formation of a two phase polymer matrix. The poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with NTA functionalized end groups (NTA-PEO-PS-PEO-NTA) was bound or chelated with Ni(II) metal ion. The binding studies were carried out by ultraviolet-visible (UV-Vis) spectroscopy. The electronic behaviors of PEO-b-PS-b-PEO/ PS/ NTA-PEO-b-PS-b-PEO-NTA with ratio (1/5/1) and PEO-b-PS-b-PEO/ PS/ NTA-PEO-b-PS-b-PEO-NTA-Ni containing 1% of oxidized single-walled carbon nanotubes (SWCNTs) were investigated by I–V plots from Kelvin sensing. The I–V plots before sensitizing with protein varied from the I–V plots after binding with protein indicating that the composites may be used as active components in biosensors.

<p>There are still technique hurdles that needed to be overcome in the commercialization of electrochromic devices (ECDs) for energy-saving smart windows. Among them, the long-term stability of ECDs and the high fabrication cost are <a>the critical issues</a>. The pricey ECDs can only be paid off through saving the energy for years, and their price will be dramatically lower if they can be solution-processed. Here, we studied the ions behaviors in the open-circuit state of electrochromic conjugated polymers (ECPs) which is important to the stability of ECDs during the operation. Moreover, we investigated the solution-processable ion storage layers and paired them with p-type ECPs and demonstrated the possibility of using them in the highly efficient roll-to-roll fabrication of ECD.</p> <p>The crosslinkable non-color changing nitroxy radical-based polymer was investigated as the ion storage layer. With the applied of crosslinking strategy, the dissolution problems of radical polymers-based counter electrode in the electrolyte was suppressed, resulting in the enhancement of both performance and cycling stability of ECDs. Although p-type ion storage materials are widely studied as the ion storage layers for ECPs, they need to go through complicated pretreatment processes, including pre-oxidation, washing, and drying, before they can be paired with ECPs in an ECD. This complicated process greatly increases the fabrication cost. </p> <p>In our last work, we applied the UV ozone (UVO) pretreatment to the solution-processed n-type niobium oxide and evaluated its potentials to be used as the ion storage layer for p-type ECPs. The UVO pretreatment generates strong oxidants like ozone or atomic oxygen which induce the photolysis of organic residues of ligands and organic solvent trapped in the solution-processed metal oxide layer led to the formation of free radical species. These highly reactive species promoted the formation of the amorphous metal−oxygen network. Following by low-temperature annealing (< 150 ^oC), the ion-storage properties of niobium oxide is comparable with the high temperature annealed (300 ^oC) niobium oxide. The method is successfully applied to fabricate niobium oxide on a flexible conductive substrate and demonstrate the capability to pair with p-type ECPs and fabricate high-performance ECDs without the need of any pretreatments. The low-temperature solution processing of both layers will significantly reduce the fabrication cost of ECDs. </p>

Metal-organic frameworks (MOFs) have been extensively studied because of their amazing applications in gas storage, purification, photocatalysis, chemical sensing, and imaging techniques. Ruthenium polypyridyl complexes have been broadly considered as photosensitizers for the conversion of solar energy and photoelectronic materials. With this aspect, we have synthesized three new ruthenium polypyridyl based MOFs ([Ru(H2bpc)Cu(bpc)(Hbpc)2(H2O)]·5H2O (1), [Ru(H2bpc)(Fe(bpc)(Hbpc)2(H2O)2]·6H2O (2) and [Ru(H2bpc)Ni(bpc)(Hbpc)2(H2O)2]·6H2O (3)) from ruthenium(III) chloride, bpc (2,2’- bipyridine-4,4’-dicarboxylic acid) ligand, and 3d M(II) metal ions (M(II)= Cu(II), Fe(II), Ni(II)). These MOFs were synthesized under hydro or solvothermal conditions by using water, ethanol or methanol as solvents. The crystal structures of the new compounds contains zigzag chains of [Ru(bpc)3]n- complex ions linked by Cu, Fe or Ni complex ions individually. Above synthesized crystal structures were characterizing by single-crystal Xray and powder X-ray diffraction strategies, UV-vis and IR spectroscopy. Thermal properties were determining by thermogravimetric analysis. Magnetic properties were also studied.

Supercapacitors, as promising energy storage devices, have been of interest for their long lifespan compared to secondary batteries, high capacitance and excellent reliability compared to conventional dielectric capacitors. Transition metal oxides can be applied as the electrode materials for pseudocapacitors and offer a much higher specific capacitance. Co3O4 is one of the most investigated transition metal oxides for supercapacitor. Besides simple monometallic oxides, bimetallic transition oxides have recently drawn growing attention in electrochemical energy storage. They present many unique properties such as achievable oxidation states, high electrical conductivities because of the coexistence of two different cations in a single crystal structure. This study focuses on the bimetallic iron cobalt oxide based materials for the application of energy storage. We selected iron as the substituent in spinel Co3O4, by virtue of its abundant and harmless character. Four types of iron cobalt oxides based electrode materials with different morphologies and components have been synthesized for the first time. The hydrothermal method was the main strategy for the synthesis of iron cobalt based materials, which achieved the control of morphology and ratio of components. Multiple characterization methods, including SEM, TEM, XRD, XPS, TGA, BET, have been applied to study the morphologies and nano/submicron structures. The electrochemical properties of as-fabricated samples were performed by electrochemical workstation. In addition, in order to investigate the practical application of electrode materials, asymmetric supercapacitors have been assembled by using as-prepared samples as the positive electrodes and activated carbon as the negative electrodes.

To discover the potential of IR spectroscopy and explore the details of FTIR instrumentation, a FTIR was built from most basic parts to provide access to every aspect of a IR spectrometer including the hardware and software. The optical system followed the most widely used double-interferometer design. The software control system was developed with LabVIEW to perform data acquisition of the detectors, data processing and controls of the actuators. The FTIR built will be able to provide a full optical IR spectroscopy platform which has a complete control and data acquisition system and can be continuously improved in accuracy and resolution to reach high lab experiment class as the research keep going. The availability of the hardware setup and software source code allows updating of this system for many advanced IR spectroscopy like spatially resolved and time resolved applications. To achieve in-situ material characterization with multiple measurements, some instruments can be modified and integrated with experiments. This thesis provides a practical and useful example of measuring IR spectra and mass of the sample simultaneously during thermal reactions. This instrument was designed and build with a Fourier transform infrared spectrometer (FTIR) and a thermogravimetric analyzer (TGA). Diffuse reflectance Fourier transform (DRIFT) was equipped to a commercial FTIR to acquire the IR spectra. A micro-balance was taken from a TGA was refitted to this system to measure the sample mass. A series of LabVIEW applications was developed for the FTIR control and communication, TGA communication and temperature control. The system was successfully built and tested with calcium oxalate decomposition experiments. The data showed that the instrument has good accuracy and repeatability of both the IR and mass measurement. The analysis of the calcium oxalate data demonstrated good correlation between the IR, mass and temperature parameters.

Gold monolayer-protected nanoclusters (MPCs) with average diameters of 1-5 nm protected by alkane- and arenethiolates were synthesized. Mixed-monolayer protected nanoparticles (MMPCs) were prepared by functionalizing hexanethiolate-protected MPCs with either 11-mercaptoundecanoic acid (MUA-MMPC), 11-mercaptoundecanol (MUO-MMPC), or 4-aminothiophenol (ATP-MMPC) using ligand place exchange. Presentation of various chemical reagents such as nucleophile, acid, or base and change in physical environment through ultrasonic and thermal irradiation resulted in changes to particles and their physical properties. Thermogravimetric analysis (TGA) was used to measure maximum temperature of the derivated thermogravimetric peaks (Tmax,DTG) as a means of comparing temperature dependence of mass loss. The absorption spectrum within the surface plasmon resonance (SPR) band was monitored over time throughout chemical and ultrasonic treatments to assess stability of these particles in solution. MUA-MMPCs and ATP-MMPCs were self-assembled with Cu2+, poly(sodium 4- styrenesufonate), poly(allylamine hydrochloride), generation 2 polyamidoamine dendrimer, and C60 fullerene as linking molecules on functionalized glass substrates using a layer-by-layer approach resulting in nanoparticle multi-layer films. The thin films were characterized using UV-vis spectroscopy during deposition, and then before and after chemical treatment, and thermal and ultrasonic irradiation to assess stability of nanocomposites. Finally, an in-situ cross-linking approach was used to deposit gold MPC-C60 thin film nanocomposite on functionalized glass substrate. UV-vis spectroscopy was used to monitor deposition rates of the resulting film in comparison with the MPC-C60 multilayer film assembled layer-by-layer. These MPC-C60 nanocomposites were also characterized using conductive atomic force microscopy (C-AFM).

To investigate the interaction between nanoparticles and electromagnetic waves, a numerical simulation model based on FEM was built in this thesis. Numerical simulation is an important auxiliary research method besides experiments. The optical properties of nanoparticles consist of scattering, absorption, and extinction, and in the case of nanoparticle suspension, the transmission is also involved. This thesis addressed two typical applications based on the established model, one was regarding the nanofluids for solar energy harvesting, and the other was regarding the optical properties of atmospheric soot. In the case of the nanofluids solar energy harvesting, the established model provided a convenient and rapid screening of potential nanoparticles and nanofluids candidates for solar energy harvesting. A core-shell structure nanoparticle, using Cu as the core material in a diameter of 90 nm coated with 5 nm thickness graphene, exhibited a better photothermal property under the solar radiation. In the second case regarding atmospheric soot, the established model provided an efficient method for understandings on the optical properties and warming effects of realistic soot particles. It was found that the sizes and material characteristics of soot, would greatly affect their scattering and absorption of light. Moreover, two submodels were introduced and integrated, which can better predict behaviors of real atmospheric soot involving their core-shell structures (moisture or organic condensates) and their fractal agglomerate structures. In conclusion, the established model helps to understand the interaction between nanoparticles and electromagnetic waves, which shows great potentials of wide applications.

The focus of this dissertation is on the interactions of compounds containing group 12 and 16 elements. This work is presented in three major parts. First, the interaction of the synthetic dithiol N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH2, with selenite. Second, the interaction of cysteine with Cd(II) and the biologically relevant Cd-Cysteine crystal structure. Third, the green synthesis of CdSe quantum dots (QDs). The interaction of BDTH2 with selenite is different from the interactions with other metals and metalloids previously studied. Under ambient conditions, BDTH2 is oxidized to the disulfide, BDT(S-S), while selenite is reduced to elemental selenium. However, under carefully controlled conditions, the reaction of BDTH2 with selenite produces a mixture of BDT(S-S) and the covalently bound Se(II) species, BDT(S-Se-S). While the mixture could not be separated, experimental 77Se NMR combined with computational analysis confirmed the presence of BDT(S-Se-S). The interaction of the amino acid cysteine with Cd(II) was studied as a means to sequester, and potentially recycle, Cd(II) from bulk CdS waste. Single crystals of Cd(Cys)Cl·H2O were grown, and the crystal structure determined. Surprisingly, this is only the second structure to be determined by X-ray crystallography of a compound containing the Cd-Cysteine unit. Not only does this structure have biological relevance, but it also corrects a structure proposed in 1965. Using the knowledge gained from studying the interaction of BDTH2 with selenite, a green synthesis of water-soluble CdSe QDs by the reaction of selenite with Cd(Cys)Cl·H2O in water at room temperature was developed. This green method for the synthesis of CdSe QDs was extended to ZnSe and HgSe QDs. The mechanism of CdSe formation was investigated using Cd(II) combined with various thiols.

Control of solid state ordering in conjugated small molecules is paramount to the continued development and implementation of organic materials in electronic devices. However, there exists no reliable method on which to predicatively determine how a change to the molecular structure will impact the solid-state packing. As such, the molecule must be synthesized before its solid-state packing can be definitively evaluated. However, once the packing structure of a material is known there exist both qualitative structure- function relationships derived from the literature, as well as quantitative computational methods that can be employed to suggest if a material will perform well in a given device. This type of bottom-up strategy is used in Chapter 2 to design and synthesize a high performance material for organic field effect transistors. A core molecule is synthesized, and through rigorous optimization of pendant and solubilizing groups a material with exceptional solid-state packing is developed and its performance in an organic field effect transistor is discussed. Chapter 3 discusses the use of conjugated organic molecules in conjunction with inorganic materials to develop hybrid organic/inorganic materials. A scalable synthesis is developed so derivatives can be rapidly synthesized and their properties evaluated. Two classes of materials are developed and synthesized: tetracene-based ligands for quantum dots and diammonium-substituted anthracene and tetracene derivatives for 2D-perovskites. Initial results for both classes of materials are presented. Chapter 4 discusses the topochemical photopolymerization of heptacene [4+4] dimers. Multiple derivatives were synthesized in order to give the ideal alignment of molecules in the crystal, followed by irradiation of crystals to give crystal templated polymerization. In Chapter 5, triarylmethane derivatives are synthesized and their performance as radiochromic sensors is evaluated. Chapter 6 involves the development of a robust synthetic scheme toward a difficult to attain π- extended regioisomer of pyrene. Photophysical characterization reveals that the direction of π-extension from the pyrene core has a profound effect on electron delocalization.

Over the past few years, energy storage devices have received tremendous interest due to the increasing demand for sustainable and renewable energy in modern society. Supercapacitors are considered as one of the most promising energy storage devices because of their high power density and long cycle life. However, low energy density remains as the main shortcoming for supercapacitors. The overall performance of supercapacitors is predominantly determined by the characteristics of the electrodes. Specifically, constructing nanostructured electrode material has been proven as an efficient way to improve the performance by providing large surface area and short ionic and electronic diffusion paths. Another approach to improve the performance of supercapacitors is the rational design of the asymmetric supercapacitor (ASC), which can extend the operation voltage. In this regard, we have focused on the synthesis and utilization of several nanomaterials, in particular, pseudocapacitance materials such as metal oxides and metal phosphides, on both positive and negative electrodes, as well as the ASC design and fabrication. First, three-dimensional TiO2 nanorod arrays have been synthesized on Ti substrate by a facile one-step hydrothermal method and demonstrated as an ideal supercapacitor positive electrode, which exhibited good areal capacitance and excellent cycling stability. Owing to the novel “dissolve and grow” mechanism, this method provides a simple and low-cost technique for flexible supercapacitor application. Second, using cobalt phosphide and iron phosphide as examples, we have demonstrated metal phosphides as high-performance supercapacitor negative electrodes for the first time. Cobalt phosphide nanowire arrays have been synthesized and presented a high capacitance of 571.3 mF/cm2. To improve the cycling stability, gel electrolyte was used to suppress the irreversible electrochemical reaction. The flexible solid-state asymmetric MnO2//CoP supercapacitor exhibited good electrochemical performance, such as a high energy density of 0.69 mWh/cm3 and a high power density of 114.2 mW/cm3. Furthermore, a PEDOT coating has been adapted to further enhance the cycling stability as well as capacitance performance of FeP nanorod arrays. The FeP/PEDOT electrode represents an outstanding capacitance of 790.59 mF/cm2 and a good stability of 82.12% retention after 5000 cycles. In addition, a MnO2//FeP/PEDOT ASC was fabricated with an excellent volumetric capacitance of 4.53 F/cm3 and an energy density of 1.61 mWh/cm3.