<p>U&nbsp; ovoj&nbsp; doktorskoj&nbsp; disertaciji&nbsp; ispitivani&nbsp; su&nbsp; elektroliti&nbsp; na&nbsp; bazi binarnih&nbsp; sme&scaron;a&nbsp; imidazolijumovih&nbsp; jonskih&nbsp; tečnosti&nbsp; i&nbsp; laktona&nbsp; koji su&nbsp; pogodni&nbsp; za&nbsp; primenu&nbsp; u&nbsp; litijum-jonskim&nbsp; baterijama.&nbsp; Fizičkohemijska&nbsp; svojstva&nbsp; binarnih&nbsp; sme&scaron;a&nbsp; jonskih&nbsp; tečnosti&nbsp; na&nbsp; bazi imidazolijum katjona i <em>bis </em>(trifluorometilsulfonil)imidnog anjona i laktona ispitana su u celom opsegu molskih udela i na različitim temperaturama.&nbsp; Na&nbsp; osnovu&nbsp; izmerenih&nbsp; gustina,&nbsp; viskoznosti&nbsp; i električne&nbsp; provodljivosti&nbsp; izračunati&nbsp; su&nbsp; različiti&nbsp; fizičko-hemijski parametri i diskutovane&nbsp; interakcije između komponenata sme&scaron;a. Ispitana&nbsp; je&nbsp; termička&nbsp; i&nbsp; elektrohemijska&nbsp; stabilnost&nbsp; odabranih elektrolita.&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata,&nbsp; prvo&nbsp; je&nbsp; odabran odgovarajući&nbsp; lakton&nbsp; koji&nbsp; je&nbsp; kasnije&nbsp; kombinovan&nbsp; sa&nbsp; jonskim<br />tečnostima&nbsp; na&nbsp; bazi&nbsp; imidazola,&nbsp; koje&nbsp; se&nbsp; međusobno&nbsp; razlikuju&nbsp; u dužini&nbsp; bočnog&nbsp; niza&nbsp; katjona.&nbsp; Na&nbsp; osnovu&nbsp; fizičko-hemijskih svojstava&nbsp; na&nbsp; različitim&nbsp; temperaturama&nbsp; i&nbsp; pri&nbsp; različitim&nbsp; sastavima binarnih&nbsp; sme&scaron;a&nbsp; diskutovan&nbsp; je&nbsp; način&nbsp; organizacije&nbsp; njihovih<br />komponenata.&nbsp; U&nbsp; binarne&nbsp; sme&scaron;e&nbsp; koje&nbsp; su&nbsp; se&nbsp; pokazale&nbsp; kao najperspektivnije&nbsp; sa&nbsp; stanovi&scaron;ta&nbsp; električne&nbsp; provodljivosti, viskoznosti,&nbsp; elektrohemijske&nbsp; stabilnosti&nbsp; i&nbsp; (ne)zapaljivosti&nbsp; dodata je litijumova so. Tako dobijeni ternarni sistemi su okarakterisani<br />u zavisnosti od koncentracije litijumove soli. Odabrani elektroliti upotrebljeni su za ispitivanje performansi litijum-jonske ćelije sa elektrodama&nbsp; na&nbsp; bazi&nbsp; anatas&nbsp; TiO₂&nbsp; nanocevi.&nbsp; Cikličnom voltametrijom&nbsp; i&nbsp; galvanostatskim&nbsp; cikliranjem&nbsp; ispitane&nbsp; su<br />performanse ćelije u toku 350 ciklusa punjenja i pražnjenja. Na osnovu&nbsp;&nbsp; ciklovoltametrijskih&nbsp; merenja&nbsp; izračunati&nbsp; su&nbsp; koeficijenti difuzije jona Li^{&nbsp; +}i energija aktivacije za difuziju.&nbsp; Kombinacijom jonskih&nbsp; tečnosti&nbsp; i&nbsp; laktona&nbsp; moguće&nbsp; je&nbsp; dobiti&nbsp; elektrolite&nbsp; smanjene viskoznosti,&nbsp; povećane&nbsp; električne&nbsp; provodljivosti,&nbsp; povećane<br />termičke&nbsp; stabilnosti&nbsp; usled&nbsp; međusobnog&nbsp; stabilizacionog&nbsp; efekta laktona na imidazolijumove jonske tečnosti.</p> / <p>In&nbsp; this&nbsp; doctoral&nbsp; dissertation,&nbsp; binary&nbsp; mixtures&nbsp; based&nbsp; on&nbsp; imidazolium&nbsp; ionic&nbsp; liquids&nbsp; with&nbsp; lactones&nbsp; were&nbsp; tested&nbsp; for&nbsp; use&nbsp; in lithium-ion&nbsp; batteries.&nbsp; The&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; binary&nbsp; mixtures&nbsp; of&nbsp; imidazolium&nbsp; based&nbsp; ionic&nbsp; liquids&nbsp; with&nbsp;<em> bis </em>(trifluoromethylsulfonyl)imide&nbsp; anions&nbsp; and&nbsp; lactones&nbsp; were&nbsp; examined&nbsp; throughout&nbsp; the&nbsp; whole&nbsp; composition&nbsp; range&nbsp; and&nbsp; at&nbsp; different temperatures. Based on the measured densities, viscosity&nbsp; and electrical conductivity, various physical chemical parameters&nbsp; and discrete interactions between the components of the mixture are&nbsp; calculated.&nbsp; Thermal&nbsp; and&nbsp; electrochemical&nbsp; stability&nbsp; of&nbsp; selected&nbsp; binary&nbsp; mixtures&nbsp; were&nbsp; examined.&nbsp; Based&nbsp; on&nbsp; obtained&nbsp; results&nbsp; was&nbsp; selected lactone&nbsp; which is later combined with imidazolium based&nbsp; ionic liquid,&nbsp; differing from each other in the length of the cation. Based&nbsp; on&nbsp; the&nbsp; physico-chemical&nbsp; properties&nbsp; at&nbsp; different&nbsp; temperatures and in the different compositions of binary mixtures, the way of organizing their components is discussed. Lithium salt&nbsp; is added to the binary mixtures that have been shown as the most perspective&nbsp; from&nbsp; the&nbsp; standpoint&nbsp; of&nbsp; electrical&nbsp; conductivity, viscosity,&nbsp; electrochemical&nbsp; stability&nbsp; and&nbsp; (non)flammability.&nbsp; The&nbsp; resulting&nbsp; ternary&nbsp; systems&nbsp; are&nbsp; characterized&nbsp; according&nbsp; to&nbsp; the concentration of lithium salt.&nbsp; The selected electrolytes were used to test the performance of the lithium-ion cell with anatase TiO₂ nanotubular&nbsp; electrodes.&nbsp; Cyclic&nbsp; voltammetry&nbsp; and&nbsp; galvanostatic&nbsp; cycling&nbsp; tested&nbsp; the&nbsp; cell&#39;s&nbsp; performance&nbsp; during&nbsp; the&nbsp; 350&nbsp; charge&nbsp; and discharge&nbsp; cycles.&nbsp; Based&nbsp; on&nbsp; cyclic&nbsp; voltammetric&nbsp; measurements, the&nbsp; Li ⁺ ion&nbsp; diffusion&nbsp; coefficients&nbsp; and&nbsp; activation&nbsp; energies&nbsp; for diffusion&nbsp; were&nbsp; calculated.&nbsp; Combination&nbsp; ionic&nbsp; liquid&nbsp; and&nbsp; lactone could&nbsp; be&nbsp; obtained&nbsp; electrolytes&nbsp; with&nbsp; lower&nbsp; viscosity,&nbsp; higher electrical&nbsp; conductivity,&nbsp; improved&nbsp; thermal&nbsp; stability&nbsp; due&nbsp; to stabilization effect of lactone on imidazolium based ionic liquids.</p>

O sistema peróxi-oxalato consiste na reação entre ésteres oxálicos e peróxido de hidrogênio, na presença de um catalisador básico e/ou nucleofílico e de um composto fluorescente com baixo potencial de oxidação (ACT), resultando em uma emissão eficiente de quimiluminescência. O sistema é amplamente utilizado em diversas aplicações analíticas, entretanto, sua aplicação é limitada devido às dificuldades de sua adaptação em meios aquosos. Nesse trabalho foram realizados estudos cinéticos da reação peróxi-oxalato em uma mistura binária de 1,2-dimetóxietano/água (1/1) em tampão fosfato (pH 6, 7 e 8), utilizado-se os ésteres oxalato bis(2,4,6-triclorofenila) (TCPO), oxalato de bis(4- metilfenila) (BMePO) e oxalato de bis(4-nitrofenila) (BNPO). A partir da dependência da constante de velocidade de decaimento da intensidade de emissão (kobs) com a concentração de peróxido de hidrogênio e do tampão fosfato obteve-se evidências da ação do fosfato como catalisador básico específico na reação de TCPO. Porém, os resultados indicam também que na reação de BMePO o fosfato age principalmente como catalisador ácido. A reação peróxi-oxalato (TCPO, H2O2, ACT e imidazol) foi realizada também em meio de 80% de líquidos iônicos. Três líquidos iônicos contendo o cátion 1-butil- 3-metilimidazólio (bmim) com os contra-íons tetrafluroborato, hexafluorofosfato e hexafluoroantimonato foram utilizados obtendo-se valores de kobs maiores em bmimPF6, seguida do meio em bmimBF4e por fim em bmimSbF6. Os rendimentos quânticos determinados alcançaram valores de quase 20% em meio de bmimSbF6, além disso, foram obtidas evidências experimentais de que o mecanismo CIEEL esteja envolvido no passo de quimi-excitação da reação peróxi-oxalato nestes meios / The peroxyoxalate system consists in the reaction of oxalic esters with hydrogen peroxide in the presence of basic and/or nucleofilic catalysts and a fluorescent compound with low oxidation potential (ACT), resulting in efficient chemiluminescence emission. This system is widely utilized in various analytical applications; however, its use is limited due to the difficulties to adapt it to aqueous media. In this work, kinetic studies of the peroxyoxalate reaction were performed in phosphate buffered (pH 6, 7 and 8) binary 1,2-dimethoxyethane/water mixtures (1/1), using the oxalate esters bis(2,4,6-trichlorophenyl) oxalate (TCPO), bis(4- methylphenyl) oxalate (BMePO) and bis(4-nitrophenyl) oxalate (BNPO). Evidence for the action of the phosphate as a specific base catalyst in the reaction of TCPO was obtained from the dependence of the emission decay rate constant (kobs) on the hydrogen peroxide and phosphate buffer concentration. However, the results also indicate that phosphate acts mainly as an acid catalyst in the reaction of BMePO. The peroxyoxalate reaction (TCPO, H2O2, ACT and imidazole) was also performed in 80 % of ionic liquids. Three ionic liquids containing the cation 1-butyl- 3-methylimidazolium (bmim) with contra-ions tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate were used obtaining higher rate constant values for bmimPF6, followed by bmimBF4 media and finally bmimSbF6. The quantum yields determined reached almost 20% in the medium bmimSbF6, additionally, experimental evidence was obtained for the occurrence of the CIEEL mechanism in the chemiexcitation step of the peroxyoxalate reaction in these media

Este trabalho consiste em estudar o comportamento eletroquímico de biomoléculas imobilizadas sobre o eletrodo de carbono vítreo, utilizando materiais biocompatíveis como meios imobilizadores para detecções em meios aquosos. Foram utilizados inicialmente compósitos de hidrogéis capazes de auxiliar a permanência da enzima sobre a superfície do eletrodo e beneficiar a transferência de carga entre a enzima e o eletrodo de trabalho. Para melhorar a resposta eletroquímica do biossensor, também foram estudados métodos que utilizam líquidos iônicos no processo de imobilização da enzima. Deste modo a eletroatividade da enzima foi inicialmente estudada por voltametria cíclica, a fim de evidenciar tal eletroatividade no meio totalmente iônico, como também avaliar o melhor método de imobilização, para futuras aplicações em detecções de analitos. Os líquidos iônicos utilizados são compostos por cátions alquil-imidazol com ânions de natureza orgânica ou inorgânica. Como se sabe os íons que compõem o líquido iônico podem distinguir sua funcionalidade, pois é o tamanho desses íons que influencia na maioria das suas propriedades físico-químicas, tais como hidrofobicidade e viscosidade. / The aim of this work is to study the electrochemical behavior of biomolecules immobilized on a glassy carbon electrode, using biocompatible materials as a way for immobilizing detection in aqueous media. Initially, hydrogels composite were used because they are able to assist the permanence of the enzyme on the electrode surface and they are benefit to the charge transfer between enzyme and electrode surface. To improve the electrochemical response of the biosensor, methods using ionic liquids in the process of immobilization of the enzyme were also studied. Thus the electroactivity of the enzyme was initially analyzed by cyclic voltammetry in order to show that the electroactivity remains in an entirely ionic media, as well as evaluating the best method of immobilization, for future applications in biosensors. The ionic liquids used are composed of imidazole-alkyl cations with anions of organic or inorganic nature. As it is well known, the ions in the ionic liquid can distinguish its functionality, due to the fact that it is the size of these ions that influences most on their physicochemical properties such as hydrophobicity and viscosity.

Uma reação relativamente simples vem auxiliando cada vez mais uma variedade de aplicações analíticas na determinação de diversos compostos. A reação peroxioxalato, que produz o fenômeno de quimiluminescência, pode identificar compostos como peróxido de hidrogênio e compostos orgânicos fluorescentes presentes em diferentes meios. O estudo dessa reação em líquidos iônicos utilizados como solvente se torna cada vez mais interessante, por se tratar de solventes verdes, beneficiando assim o meio ambiente. Neste projeto, foi estudado a reação de oxalato de bis(2,4,6-triclorofenila) (TCPO) com peróxido de hidrogênio, em 1,2-dimetoxietano (DME), carbonato de propileno (CP) e misturas binárias de líquido iônico e DME, catalisada por imidazol. Dois líquidos iônicos (LIs) foram utilizados, sendo eles o tetrafluoroborato de 1-butil-3-metilimidazólio (BuMeImBF4) e o tetrafluoroborato de 1-decil-3-metilimidazólio (DecMeImBF4). As misturas binárias foram preparadas com até 50% de sua composição constituída de LI, definindo assim diferentes condições experimentais no estudo da reação, podendo ser aproveitado em futuras aplicações analíticas. Estudos cinéticos mostraram que o imidazol age não somente como catalisador básico mas também nucleofílico, tanto nos solventes orgânicos puros quanto nos meios contendo LI. Nos solventes puros e nas misturas binárias destes com líquidos iónicos determinaram-se os valores das constantes de velocidade observadas (kobs) e os rendimentos quânticos singlete (&#934;S). Os valores de kobs se tornam maiores nas misturas contendo LI em sua composição, entretanto, os valores de &#934;S não sofrem alteração significativa, mostrando uma leve tendência de diminuição. A determinação dos parâmetros de polaridade e viscosidade das misturas binárias DME/LI mostra que ambos aumentam com o aumento da concentração do LI. A baixa sensibilidade dos rendimentos quânticos à composição dos meios DME/LI pode ser entendida por um efeito de composição da viscosidade e polaridade do meio. Enquanto o aumento da viscosidade deve aumentar a eficiência de quimiexcitação, o aumento da polaridade pode levar à diminuição do rendimento devido a separação dos íons radicais envolvidos no passo de quimiexcitação ocorrendo pelo mecanismo CIEEL (Chemically Initiated Electron Exchange Luminescence). De acordo com os estudos realizados, foi demonstrado que a reação peroxioxalato pode ser conduzida em meios contendo líquidos iônicos, favorecendo assim uma maior utilização destes solventes verdes. / A relatively simple chemical reaction has increasingly shown utility in a variety of analytical applications for the determination of various compounds. The peroxyoxalate reaction, which produces the chemiluminescence phenomenon, can be used to identify and quantify several compounds, such as hydrogen peroxide and fluorescent organic compounds in different reaction media. The study of this reaction in media containing ionic liquids is of increasing interest, because of its possible utilization as \"green\", environmental compatible, solvents in analytical assays. In this project, the kinetics of the imidazole catalyzed reaction of bis(2,4,6- trichlorophenyl) oxalate (TCPO) with hydrogen peroxide in 1,2-dimethoxyethane (DME), propylene carbonate (CP) and binary mixtures of ionic liquids and DME, is studied, using the two ionic liquids (LIs) 1-butyl-3-methylimidazolium tetrafluoroborate (BuMeImBF4) and 1- decyl-3-methylimidazolium tetrafluoroborate (DecMeImBF4). The binary mixtures were prepared with up to 50% of their composition consisting of LI, thus, defining different experimental conditions in the study of the reaction, which could be used in future analytical applications. Kinetic studies show that imidazole acts not only as base, but also studied as nucleophilic catalyst, in molecular solvents as well as in LI-containing media. In the binary mixtures studied, the values of the observed rate constants (kobs) and singlet quantum yields (&#934;S) were determined. The kobs values are higher in mixtures containing LIs in their composition, however, &#934;S values do not change significantly, showing only a slight tendency to decrease. The determination of the polarity and viscosity parameters of the binary DME / LI mixtures shows that both increase with increasing LI concentration. The low sensitivity of quantum yields to the composition of the DME / LI media can be understood by a combined medium effect of the viscosity and polarity. While increased viscosity should increase the efficiency of chemiexcitation, increased polarity may lead to decreased quantum yields due to separation of the radical ions involved in the chemiexcitation step occurring by the Chemically Initiated Electron Exchange Luminescence (CIEEL) mechanism. According to the studies, it has been demonstrated that the peroxyoxalate reaction can be conducted in media containing ionic liquids, indicating that analyical assays with the peroxyoxalate reaction migt be performed in these \"green\" solvents.

The needs for sustainable energy generation, but also a sustainable chemistry display the basic motivation of the current thesis. By different single investigated cases, which are all related to the element carbon, the work can be devided into two major topics. At first, the sustainable synthesis of “useful” carbon materials employing the process of hydrothermal carbonisation (HC) is described. In the second part, the synthesis of heteroatom - containing carbon materials for electrochemical and fuel cell applications employing ionic liquid precursors is presented. On base of a thorough review of the literature on hydrothermolysis and hydrothermal carbonisation of sugars in addition to the chemistry of hydroxymethylfurfural, mechanistic considerations of the formation of hydrothermal carbon are proposed. On the base of these reaction schemes, the mineral borax, is introduced as an additive for the hydrothermal carbonisation of glucose. It was found to be a highly active catalyst, resulting in decreased reaction times and increased carbon yields. The chemical impact of borax, in the following is exploited for the modification of the micro- and nanostructure of hydrothermal carbon. From the borax - mediated aggregation of those primary species, widely applicable, low density, pure hydrothermal carbon aerogels with high porosities and specific surface areas are produced. To conclude the first section of the thesis, a short series of experiments is carried out, for the purpose of demonstrating the applicability of the HC model to “real” biowaste i.e. watermelon waste as feedstock for the production of useful materials. In part two cyano - containing ionic liquids are employed as precursors for the synthesis of high - performance, heteroatom - containing carbon materials. By varying the ionic liquid precursor and the carbonisation conditions, it was possible to design highly active non - metal electrocatalyst for the reduction of oxygen. In the direct reduction of oxygen to water (like used in polymer electrolyte fuel cells), compared to commercial platinum catalysts, astonishing activities are observed. In another example the selective and very cost efficient electrochemical synthesis of hydrogen peroxide is presented. In a last example the synthesis of graphitic boron carbon nitrides from the ionic liquid 1 - Ethyl - 3 - methylimidazolium - tetracyanoborate is investigated in detail. Due to the employment of unreactive salts as a new tool to generate high surface area these materials were first time shown to be another class of non - precious metal oxygen reduction electrocatalyst. / Die Notwendigkeit einer nachhaltigen Energiewirtschaft, sowie der nachhaltigen Chemie stellen die Motivation der vorgelegten Arbeit. Auf Grundlage separater Untersuchungen, die jeweils in engem Bezug zum Element Kohlenstoff stehen, kann die Arbeit in zwei Themenfelder geordnet werden. Der erste Teil behandelt die nachhaltige Herstellung nützlicher Kohlenmaterialien mit Hilfe des Verfahrens der hydrothermalen Carbonisierung. Im zweiten Teil wird die Synthese von Bor und Stickstoff angereicherten Kohlen aus ionischen Flüssigkeiten für elektrochemische Anwendungen abgehandelt. Insbesondere geht es um die Anwendung in Wasserstoff-Brennstoffzellen. Als Ergebnis einer sorgfältigen Literatur¬zusammenfassung der Bereiche Hydrothermolyse, hydrothermale Carbonisierung und Chemie des Hydroxymethylfurfurals wird ein chemisch-mechanistisches Modell zur Entstehung der Hydrothemalkohle vorgestellt. Auf der Basis dieses Modells wird ein neues Additiv zur hydrothermalen Carbonisierung von Zuckern vorgestellt. Die Verwendung des einfachen Additivs, genauer Borax, erlaubt eine wesentlich verkürzte und zu niedrigeren Temperaturen hin verschobene Prozessführung mit höheren Ausbeuten. Anhand des mechanistischen Modells wird ein Einfluss auf die Reaktion von Zuckern mit der reaktiven Kohlenvorstufe (Hydroxymethylfurfural) identifiziert. Die chemische Wirkung des Minerals Borax in der hydrothermalen Carbonisierung wird im Folgenden zur Herstellung vielfältig anwendbarer, hochporöser Kohlen mit einstellbarer Partikelgröße genutzt. Zum Abschluss des ersten Teils ist in einer Serie einfacher Experimente die Anwendbarkeit des mechanischen Modells auf die Verwendung „echter“ Biomasse in Form von Wassermelonenabfall gezeigt. Im zweiten Teil werden verschiedene cyano-haltige ionische Flüssigkeiten zur ionothermalen Synthese von Hochleistungskohlen verwendet. Durch Variation der ionischen Flüssigkeiten und Verwendung unterschiedlicher Synthesebedingungen wird die Herstellung hochaktiver, metallfreier Katalysatoren für die elektrochemische Reduktion von Sauerstoff erreicht. In der direkten Reduktion von Sauerstoff zu Wasser (wie sie in Brennstoffzellen Anwendung findet) werden, verglichen zu konventionellen Platin-basierten elektrochemischen Katalysatoren, erstaunliche Aktivitäten erreicht. In einem anderen Beispiel wird die selektive Herstellung von Wasserstoffperoxid zu sehr geringen Kosten vorgestellt. Abschließend wird anhand der Verwendung der ionischen Flüssigkeit 1-Ethyl-3-methylimidazolium-tetracyanoborat eine detaillierte Betrachtung zur Herstellung von graphitischem Borcarbonitrid vorgestellt. Unter Verwendung unreaktiver Salze, als einfaches Werkzeug zur Einführung großer inneren Oberflächen wird erstmals die elektrokatalytische Aktivität eines solchen Materials in der elektrochemischen Sauerstoffreduktion gezeigt.

Nanotechnology is the science and technology of manipulating materials at atomic and molecular scale with properties different from bulk. Semiconductor QDs are important class of nanomaterials with unique physical and chemical properties owing to the quantum confinement effect. Size dependent optical properties make research on semiconductor QDs more attractive in the field of nanotechnology. Semiconductor QDs are usually composed of combination of elements from groups II–VI, III–V, or IV–VI of the periodic table. Group II-VI semiconductor QDs (ZnS, ZnSe, ZnO, CdSe, CdS) are most extensively studied systems, having bandgap which can be engineered through the variation of the material composition and size. Most common QDs are made of CdE (E=S, Se, Te) which are toxic. Recent environmental regulations restrict the use of toxic metals and therefore QDs containing nontoxic metals such as Zn are of great importance. The chemical synthesis of QDs involves different methods. Usually high temperature thermal decomposition of organometallic compounds in high boiling point organic solvents is used which needs long reaction time and involves complex synthesis procedures. New simpler and efficient synthetic routes with alternative solvents are required. Recently the synthesis of non-toxic QDs using green chemical routes is a promising approach receiving increasing attention. The aim of this Thesis is to develop novel routes for synthesis of semiconductor QDs employing green nanomaterial synthesis techniques. Therefore, in this work, we developed different green chemical routes mainly for the synthesis Zn-based QDs. Low temperature synthesis routes were developed for the synthesis of ZnS and ZnO QDs. Microwave irradiation was also used as efficient heating source which creates numerous nucleation sites in the solution, leading to the formation of homogeneous nanoparticles with small size and narrow size distribution. Different polar solvents with high MW absorption were used for synthesis of ZnS QDs. We also introduced ionic liquids as solvents in the synthesis of ZnS QDs using microwave heating. ILs are excellent reaction media for absorbing microwaves and are recognized as ‘green’ alternative to volatile and toxic organic solvents. For ZnS systems, the QDs produced by different methods were less than 5 nm in size as characterized by high-resolution transmission electron microscopy (HR-TEM). Selected area electron diffraction (SAED) patterns revealed that ZnS QDs synthesized by low temperature synthesis technique using conventional heating are of cubic crystalline phase while the QDs synthesized by using MW heating are of wurtzite phase. The optical properties were investigated by UV-Vis absorption spectrum and show a blue shift in absorption as compared to bulk due to quantum confinement effect. The photoluminescence (PL) spectra of ZnS QDs show different defect states related emission peaks and depend on different synthesis methods, high bandedge related emission is observed for ZnS QDs synthesized by using ionic liquids. ZnO QDs synthesized by low temperature route were found to be less than 4 nm in size and also show a blue shift in their absorption. The PL spectrum show bandedge related emission which is blue shifted compared with bulk with no emission originating from surface defect levels. The results show that QDs are of high crystalline quality with narrow size distribution. A comparative study of using conventional and MW heating in the synthesis of CdSe QDs was performed. The reactions involving microwave heating showed enhanced rates and higher yields. The developed methods involve all principles for green nanomaterials synthesis i.e. design of safer nanomaterials, reduced environmental impact, waste reduction, process safety, materials and energy efficiency. / <p>QC 20121115</p>

In this work, electrolytes for secondary batteries and fuel cells were investigated. Ionic liquids (ILs), for use as battery electrolytes, were formed using quaternary ammonium salts (Quats) and aluminum chloride. The room temperature (RT) carbonate fuel cell was demonstrated by modifying a commercially available anion exchange membrane, utilizing positive quaternary ammonium fixed sites, to transport carbonate. The charge density on the nitrogen and the symmetry of the Quat were demonstrated to be the dominant factors in determining the IL melting point (MP). The introduction of a benzyl ring was found to lower the MP of the ILs by increasing the size of the Quat, while disrupting its symmetry. ILs formed from asymmetric quaternary ammonium salts having three distinct groups were found to have lower melting points than those formed using Quats with two groups. Replacement of an alkyl group with a rigid ether linkage can lower the IL melting point. Assymetric alkyl substituted Quats were found to form more electrochemically stable, less viscous ILs than their benzyl substituted counterparts. The increased electrochemical stability is due to the smaller butyl chain being a worse leaving group than the benzyl group. Similarly, the smaller size of the alkyl substituted Quats results in the lower viscosities. Lithium and sodium can be reversibly deposited from neutral ILs following the addition of an additive (such as SOCl2). The additive disrupts the strong coordination between Na+, or Li+, and AlCl4-. Chlorinated compounds, such as chloroform-D and carbon tetrachloride, were demonstrated to catalyze the reversible reduction of sodium. When neutralized with lithium and sodium, reversible Li-Na alloys were deposited. The Li-Na alloy appears to suppress dendrite formation and could potentially be used as a metal based anode in a rechargeable Li battery. A novel room temperature carbonate fuel cell was constructed. The alkaline environment could eliminate the need for water in the oxidation of methanol. Cells were operated on hydrogen, 1M methanol, and pure methanol fuels. CO2 was produced at the anode and O2 and CO2 were necessary at the cathode for operation, indicating that carbonate was the conducting ion.

This work showcases the utility of switchable materials. Included are a switchable room-temperature ionic liquid, a switchable solvent, a switchable heterogeneous catalyst system, and a switchable gel. First, the switchable ionic liquid 2-butyl-1,1,3,3-tetramethylguanidium methylcarbonate is fully investigated. Its use in a complete chemical process (including reaction, separation, reformation, and recycle) is demonstrated with several reactions. Furthermore, its potential use for bitumen separation and purification and SO2 capture/isolation are discussed, and preliminary data is presented. Next, piperylene sulfone (PS), a switchable solvent, is synthesized and fully characterized. Anionic nucleophilic substitution reactions were performed in PS, the products were isolated in high yields, and then the PS was reformed for reuse. Then, we designed an immobilized fluorous microphase system that uses F-MonoPhos to induce high enantioselectivities as a switchable heterogeneous catalyst system. Finally, stable reversible polyethyleimine-CO2 gels have been synthesized with 1-octanol. Our findings indicate that PEI-1200/octanol/CO2 gels have potential as a possible drug carrier matrix for transdermal delivery applications.

We develop, characterize, and apply novel solvent systems for enhanced separations. The field of separations has long been explored by chemical engineers. One way to optimize separations is through solvent manipulation. Through molecular design, smart solvents can be created which accomplish this task. Smart solvents undergo step or gradual changes in properties when activated by a stimulus. These property changes enable unique chemistry and separations. This thesis explores the application of two different types of smart solvents: switchable and tunable solvents. First we show that a neutral liquid can react with carbon dioxide and be switched into an ionic liquid which can then be thermally reversed back to its molecular form. Each form that the solvent takes has unique properties that can be structurally tuned to span a large range. We also look at a tunable solvent system based on polyethylene glycol/dioxane that is initially homogeneous, but induced to a heterogeneous system through carbon dioxide pressurization. Finally, we look at the advantage of using carbon dioxide as a co-solvent that is easily removed post-reaction for the grafting of silanes onto polyolefin backbones.

Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on both solvent forms to serve as a tool for optimal solvent identification as well as future solvent design. A reflectance infrared spectroscopic technique is introduced to allow for the examination of CO₂ and solvent composition under high pressures and temperatures. The magnitude of solvent property changes afforded by this "switch" creates opportunities for sustainable processing; discussed are the application to coupling reactions and separations, and CO₂ capture. The switchable solvents are shown to serve as effective media for running reactions, with the switch providing facile recovery of products and catalysts for solvent recycling. Lastly, the switch itself is exploited to provide for the separation of CO₂ from low partial pressure feed streams, and structure-property relationships were successfully used to develop next generation materials with enhanced absorption capacities. The viscosity of the solvents, as a function of temperature and composition, is also presented.