Adsorption/desorption behaviors of three volatile organic compounds (VOCs) emitted from the optoelectronics industry by Y-type and ZSM-5 zeolites were studied in this work. Target VOCs include acetone, isopropyl alcohol (IPA), and propylene glycol monomethyl ether acetate (PGMEA). Adsorption/desorption experiments were conducted in a fixed-bed column using various operating conditions to mimic the commercial ones. Also studied include the adsorption kinetics for single-component, two-component, and three-component cases. Experimental results of the single-adsorbate case by both model zeolites have shown that the amount of VOC adsorbed follows the order of PGMEA > IPA > Acetone. This is ascribed to the greatest molecular weight of PGMEA among three VOCs tested. The adsorption capacity of each zeolite for each target VOC was found to increase with its increasing initial concentration. Freundlich isotherm and Langmuir isotherm were found to be suitable for describing the adsorption behaviors for the single-adsorbate case. Results of the desorption experiments also showed that most of the target VOCs could be desorbed at 180¢J in 100 minutes. The adsorption capacities of the regenerated model zeolites were found to be decreasing as the regeneration times increased. As compared with the fresh ones, the regenerated zeolites had reduced specific surface areas, but increased pore sizes. In addition, the Yoon and Nelson equation was employed to study the kinetic behaviors of adsorbing the target VOCs by the model zeolites. A good agreement of the experimental results and predictions by the Yoon & Nelson model was obtained for the single-adsorbate case. However, the Yoon and Nelson model was found to be incompetent to simulate and predict all the multi-adsorbate cases including two-component adsorption and three-component adsorption in this work. Again, it is speculated that the displacement of lower-molecular-weight adsorbates (i.e., acetone and IPA) by PGMEA (an adsorbate of a much greater molecular weight) would be responsible for this finding. For the two-adsorbate case, nevertheless, the Yoon and Nelson equation was found to be capable of describing the adsorption behavior under the circumstance of C/C0 < 1.

In this work, zeolite Beta was synthesized experimentally in order to be used as filler in fuel cell membranes in order to assess the proton conductivity of composite membranes. Effects of the Si/Al ratio, and synthesis time on yield, relative crystallinity, crystal size, and proton conductivity were investigated. Zeolite Beta with Si/Al ratio between 10 and 30 was synthesized with a batch formulation of 2.2Na2O:1Al2O3:ySiO2:4.6(TEA)2O:tH2O (where TEA&amp / #8801 / tetraethylammonium) at 150&deg / C for 5-15 days of synthesis time. Sodium aluminate, tetraethylammonium hydroxide (TEAOH) solution, sodium hydroxide pellets (NaOH), and deionized water were used for the preparation of the batch solution. Zeolite Na-Beta was calcined and treated with sulfuric acid solution at different concentrations in order to have zeolite H-Beta. Polyetherether ketone (PEEK) was sulfonated in order to have a proton conductive membrane and than zeolite H-Beta was incorporated resulting in a composite or nanocomposite membrane. X-ray diffraction (XRD) analysis helped to understand whether the synthesized material was zeolite Beta or not. The morphology and the crystal size of the crystals were observed as a result of the scanning electron microscopy (SEM) analysis. In order to see the effect of sulfuric acid treatment on the sodium (Na) content of the zeolite Beta, inductively coupled plasma (ICP) analysis was performed. Synthesis results indicate that as Si/Al ratio and synthesis time increased the yield of zeolite Beta increased. It was observed that Si/Al ratio from 10 to 30, and synthesis time between 5 to 15 days did not affect the crystal size significantly. For the sulfonation of PEEK, sulfuric acid was used. Sulfonated polyetherether ketone (SPEEK) was dissolved in a solvent that was dimethyl acetamide (DMAC), incorporated with zeolite Beta, and then solvent was removed in the vacuum oven. The proton conductivity was measured with a 2-probe impedance spectrometer. Initial results indicate that zeolite Beta at 10 and 20 wt % loadings did not affect the proton conductivity of the SPEEK membrane at 100 % relative humidity and room temperature.

Zeolite membrane synthesis is conventionally carried out in batch systems. Recently, several attempts have been performed to synthesize zeolite membranes in flow systems which can allow preparation of membranes with large specific surface areas. Membranes synthesized in the recirculating flow system had comparable N2/SF6 and n- C4H10/i-C4H10 ideal selectivities with the membranes prepared in the batch system, indicating that good quality membranes can be produced by this method. The objective of this study is to separate organic/water mixtures by pervaporation by using MFI type membranes synthesized in the flow system. Effect of number of synthesis steps and synthesis method on the separation factor and flux was investigated. Membranes were synthesized from clear solutions with a molar composition of 80SiO2:16TPAOH:1536H2O at 95oC and atmospheric pressure. The synthesis solution was recirculated through the tubular alumina support with a flow rate of 6 ml/min for 72 h. The membranes were characterized by X-ray diffraction for phase identification and scanning electron microscopy for morphology determination. Single gas permeances of N2, H2, CH4, CO2, n-C4H10 and i-C4H10 were measured between 25 and 200oC. Mixtures of 5 wt% ethanol/water, 2-propanol/water and acetone/water were separated by pervaporation at different temperatures. The single gas permeances decreased with increasing temperature for weakly adsorbed gases. For n-C4H10 the permeance passed through a maximum and i-C4H10 permeance was nearly constant. For a membrane synthesized by two consecutive synthesis steps, the ideal selectivity for n-C4H10/i-C4H10 was 132 at 200oC. The selectivity in the pervaporation separation of ethanol-water mixture was 43 with a permeate flux of 0.2 kg/m2h at 25oC. With increasing temperature, selectivity decreased but the flux increased, the selectivity was 23 and the flux was 1.9 kg/m2h at 85oC. 2-propanol/water and acetone/water separation factors were 36 and 1024 with 0.2 and 0.1 kg/m2h fluxes, respectively. The separation factors and fluxes for membranes synthesized in the flow system were comparable with membranes synthesized in the batch system.

The extent of the benefits provided by use of SCMs in cementitious systems increases as their percentage amounts in total binder increases. However, the proportion of SCMs in cementitious systems is limited, especially for natural pozzolans, by some factors such as increase in water requirement and decrease in rate of strength development. Therefore investigations are needed to increase the amount of natural pozzolans in blended cements or in concrete as much as possible without decreasing their performance. This aim requires studies on cementitious systems with more reactive natural pozzolans than widely-used ones. The objective of the study was to investigate the pozzolanic activity of natural zeolites (clinoptilolite) from two localities in Turkey, and properties of cementitious systems containing low (15%), moderate (35%) and high (55%) amount of them. The study covers characterization of the natural zeolites used, evaluation of their pozzolanic activity in comparison with some popular mineral admixtures, and properties of pastes, mortars, and concrete mixtures containing low, moderate, and high amounts of natural zeolites. Reactivity of the natural zeolites with Ca(OH)2 was found to be higher than those of the fly ash and the non-zeolitic pozzolan, but lower than that of the silica fume. Natural zeolite blended cements were characterized with the following highlighted properties / faster setting than portland cement, low amounts of Ca(OH)2 and capillary pores larger than 50 nm in hardened pastes, relatively dense microstructure of hardened paste than portland cement, more compatibility with melamine-based superplasticizer than being with naphthalene-based one, and excellent compressive strength performance. Concrete mixtures containing natural zeolites as partial replacement for portland cement were characterized with the following properties / 7-day compressive strength of ~25 MPa and 28-day strength of 45-50 MPa with only 180 kg/m3 portland cement and 220 kg/m3 zeolite dosages (55% replacement), comparable modulus of elasticity with plain portland cement concrete, &ldquo / low&rdquo / and &ldquo / very low&rdquo / chloride-ion penetrability for low and large levels of replacement, respectively.

Ion exchange of heavy metals with zeolites is important in terms of different application areas. Industrial wastewater treatment and antibacterial applications are two essential areas that have taken great attention. While silver, zinc and copper are well known for their toxicity, they are also used as antibacterial agents in zeolites. The objective of this study is to investigate the single and multicomponent ion exchange behavior of zeolite 4A for silver, zinc, copper and sodium ions. For this purpose Ag+-Na+, Zn2+-Na+, Cu2+-Na+ binary systems and Ag+-Zn2+-Na+, Ag+-Cu2+-Na+, Cu2+-Zn2+-Na+ ternary systems were investigated in batch systems at 25&deg / C and 0.1 N. Binary ion exchange isotherms indicate that zeolite 4A has high selectivity for silver, zinc and copper with respect to sodium. All exchange isotherms lie above the diagonal over the whole range. Using the equilibrium data, the thermodynamic analysis of the binary systems were carried out. The thermodynamic equilibrium constants and the standard free energies of exchange were calculated as 340.9 and -14.5 kJ/mol for silver-sodium system, 40.5 and -4.6 kJ/mol for zinc-sodium system, and 161.2 and -6.3 kJ/mol for copper-sodium system, respectively. From these values, selectivity sequence of zeolite 4A was determined as Ag+ &gt / Cu2+ &gt / Zn2+. This selectivity sequence was also verified by the results of ternary ion exchange experiments. The experimental data were compared with the Langmuir and Freundlich isotherms. While Freundlich model gives a better correlation for Ag+-Na+ and Zn2+-Na+ exchange, Langmuir model represents a better fit to the experimental data of Cu2+-Na+ exchange.

Zeolite membranes are attractive materials to separate gas and liquid mixtures. MFI is a widely studied zeolite type due to its ease of preparation and comparable pore size with the molecular size of many substances. In this study MFI type membranes were synthesized over porous &amp / #945 / -Al2O3 supports and characterized with XRD, SEM and gas permeation measurements. In the first part of this study the effect of soda concentration of the synthesis solution on the membrane morphology and crystal orientation was investigated. The synthesis was carried out from solutions with a molar composition of (0- 6.5)Na2O:25SiO2:6.9TPABr:1136H2O at 150oC. At soda concentrations between 0.45 and 1.8 the membrane layers with (h0h)/c-directed orientation were obtained. At lower and higher soda concentrations membrane layer formed from randomly oriented crystals. The (h0h)/c-oriented membranes showed H2/n-C4H10 ideal selectivities of 478 and 36 at 25&deg / C and 150&deg / C, respectively.In the second part, MFI membranes were synthesized from mixtures with different concentrations of template molecules. Tetrapropylammonium hydroxide, tetrapropylammonium bromide or mixture of both types were used as template. The nucleation period, the size of MFI crystals, membrane thickness decreased as the tetrapropylammonium hydroxide concentration increased. Besides conversion of SiO2 in the synthesis solution to MFI passed through a maximum with increasing concentration of tetrapropylammonium hydroxide in the synthesis solution. When tetrapropylammonium bromide was used as template thicker membranes were obtained. In the third part MFI type membranes with a thickness of 1.5-2 &amp / #956 / m were synthesized by mid-synthesis addition of silica to the synthesis medium. The membranes synthesized with and without mid-synthesis addition of silica have n-C4H10/i-C4H10 ideal selectivities of 47 and 8 at 100oC, respectively. The change of composition during the synthesis increases the crystal growth rate and the size of the crystals forming the membrane, thus better quality membranes can be obtained by mid-synthesis addition of silica to the synthesis medium. In the last part of this study, thin MFI type zeolite membranes were synthesized in a recirculating flow system at 95&deg / C on the inner side of the tubular &amp / #945 / - alumina supports. A membrane synthesized by two consecutive synthesis steps had a separation selectivity of 38 and 86 for equimolar mixtures of n- C4H10/CH4 and n-C4H10/N2 at 25oC, respectively. The membrane selectively permeated large n-C4H10 over small CH4 and N2, suggesting that the separation is essentially adsorption-based and the membrane has few nonselective intercrystalline pores.

Expansive soils are a worldwide problem that poses several challenges for civil engineers. Such soils swell when given an access to water and shrink when they dry out. The most common and economical method for stabilizing these soils is using admixtures that prevent volume changes. In this study the effect of using Bigadic zeolite (boron by-product) in reducing the swelling potential is examined. The expansive soil is prepared in the laboratory by mixturing kaolinite and bentonite. Bigadic zeolite (boron by-product) is added to the soil at 0 to 25 percent by weight. Grain size distribution, Atterberg limits and swell percent and rate of swell of the mixtures are determined. Specimens are cured for 7 and 28 days. As a result of the experimental study, it was seen that addition of Bigadic zeolite (boronby-product) decreased swelling potential and rate of swell of the artificially prepared expansive soil specimen at laboratory conditions. The swell percentage and rate of swell of the stabilized specimens are affected positively by curing.

The use of microporous materials with ordered porous structures as the hosts to stabilize metal nanoclusters has attracted particular interest in the catalysis because the pore size restriction could confine the growth of nanoclusters and lead to an increase in the percentage of catalytically active surface atoms. In this dissertation we report the preparation, characterization and the investigation of the catalytic performance of zeolite framework stabilized ruthenium(0) nanoclusters in the hydrolysis of sodium borohydride and the hydrogenation of aromatics. The zeolite framework stabilized ruthenium(0) nanoclusters were prepared by borohydride reduction of ruthenium(III)-exchanged zeolite-Y in aqueous solution at room temperature and isolated as black powders. Their characterization by using ICP-OES, XRD, TEM, ZC-TEM, HR-TEM, TEM-EDX, SEM, XPS, DR-UV-vis, far-IR, mid-IR, Raman spectroscopy, N2 adsorption-desorption technique and (P(C6H11)3)/(PC6H11O3) poisoning experiments reveal the formation of ruthenium(0) nanoclusters within the zeolite cages as well as on the external surface of zeolite without causing alteration in the framework lattice or loss in the crystallinity. The catalytic performance of zeolite framework stabilized ruthenium(0) nanoclusters depending on the various parameters was tested in the hydrolysis of sodium borohydride and the hydrogenation of aromatics. The important results obtained from these experiments can be listed as follows: (i) the zeolite framework stabilized ruthenium(0) nanoclusters provide a record total turnover number (103200 mol H2/mol Ru) and turnover frequency (33000 mol H2/mol Ru&bull / h) in the hydrolysis of sodium borohydride at room temperature, (ii) they also catalyze the same reaction in the basic medium (in 5 wt % NaOH solution) at room temperature with the unprecedented catalytic activity (4000 mol H2/mol Ru&bull / h) and lifetime (27200 mol H2/mol Ru), (iii) the isolated and vacuum dried samples of zeolite framework stabilized ruthenium(0) nanoclusters are active catalysts in the hydrogenation of cyclohexene, benzene, toluene and o-xylene in cyclohexane, they provide TOF values of 6150, 5660, 3200, and 1550 mol H2/mol Ru&bull / h, respectively under mild conditions (at 22.0 &plusmn / 0.1 &deg / C, and 40 &plusmn / 1 psig of initial H2 pressure), (iv) more importantly, the zeolite framework stabilized ruthenium(0) nanoclusters are the lowest temperature, most active, most selective (100 % selectivity with complete conversion) and longest lifetime catalyst hitherto known for the hydrogenation of benzene to cyclohexane in the solvent-free system (TTON of 2420 and TOF of 1040 mol benzene/mol Ru&bull / h) under mild conditions (at 22.0 &plusmn / 0.1 &deg / C, and 40 &plusmn / 1 psig of initial H2 pressure), (v) moreover, the resultant ruthenium(0) nanoclusters exhibit high durability throughout their catalytic use against agglomeration and leaching. This significant property makes them reusable catalyst without appreciable loss of their inherent activity.

Among the new hydrogen storage materials, ammonia borane (AB) appears to be the most promising one as it has high hydrogen content, high stability, and being environmentally benign. Dehydrogenation of AB can be achieved via hydrolysis, thermolysis or methanolysis. Methanolysis of AB eliminates some drawbacks of other dehydrogenation reactions of AB. The use of colloidal and supported particles as more active catalyst than their bulky counterparts for the hydrolysis of AB implies that reducing the particle size can cause an increase in the catalytic activity as the fraction of the surface atoms increases by decreasing the particle size. Similarly, transition metal nanoclusters can be utilized as catalyst for the methanolysis of AB as well. For this purpose transition metal nanoclusters need to be stabilized to a certain extent. Actually in the catalytic application of transition metal nanoclusters one of the most important problems is the aggregation of nanoclusters into bulk metal, despite of using the best stabilizers. In this regards, the use of metal nanoclusters as catalysts in systems with confined void spaces such as inside mesoporous and microporous solids appears to be an efficient way of preventing aggregation. In this dissertation we report for the first time the use of intrazeolite rhodium(0) nanoclusters as a catalyst in the methanolysis of ammonia borane. Rhodium(0) nanoclusters could be generated in zeolite-Y by a two-step procedure: (i) incorporation of rhodium(III) cations into the zeolite-Y by ion-exchange, (ii) reduction of rhodium(III) ions within the zeolite cages by sodium borohydride in aqueous solution, followed by filtration and dehydration by heating to 550 &deg / C under 10-4 Torr. Zeolite confined rhodium(0) nanoclusters are stable enough to be isolated as solid materials and characterized by ICP-OES, XRD, SEM, EDX, HRTEM, XPS and N2 adsorption-desorption technique. The zeolite confined rhodium(0) nanoclusters are isolable, bottleable, redispersible and reusable. They are active catalyst in the methanolysis of ammonia-borane even at low temperatures. They provide exceptional catalytic activity with an average value of TOF = 380 h-1 and unprecedented lifetime with 74300 turnovers in the methanolysis of ammonia-borane at 25 &plusmn / 0.1 &deg / C. The work reported here also includes the full experimental details of previously unavailable kinetic data to determine the rate law, and activation parameters (Ea, &amp / #916 / H&amp / #8800 / and &amp / #916 / S&amp / #8800 / ) for the catalytic methanolysis of ammonia-borane.

Electrochemical biosensors are cost effective, fast and portable devices, which can determine the existence and amounts of chemicals in a specific medium. These devices have many potential applications in many fields such as determination of diseases, process and product control, environmental monitoring, and drug research. To realize these potentials of the devices, many studies are being carried out to increase their sensitivity, selectivity and long term stabilities. Surface modification studies with various types of particles (metal nano particles, carbon nano tubes etc.) can be count among these studies. Although zeolites and zeo-type materials are investigated for many years, they still hold interest on them due to their capabilities. By means of their chemical resistances, large surface areas, tailorable surface properties, and porous structures they can be applied in many applicational fields. In some recent studies, these properties are intended to be used in the field of biosensors. The purpose of the current study was to investigate the effect of zeolite nanoparticles on electrochemical biosensor performances. Firstly, several different procedures were investigated in order to find the best and optimum methodology to attach previously synthesized zeolites on Si wafer substrates for the first time. For this purpose, the ultrasonication, spin coating and direct attachment methods were used and their efficiencies were compared. Perfectly oriented, fully covering, zeolite monolayers are produced by direct attachment method. Successively produced zeolite thin films were then patterned with the help of Electron Beam Lithography technique to show the compatibility of coating methods to the CMOS technology. Combination of Direct Attachment and EBL techniques resulted well controlled zeolite monolayer patterns. Then zeolite modified electrochemical biosensors were tested for their performances. With these experiments it was intended to improve the selectivity, sensitivity and storage stabilities of standard electrochemical biosensors. Experiments, conducted with different types of zeolites, showed that zeolites have various effects on the performances of electrochemical biosensors. Amperometric biosensor response magnitudes have been doubled with the addition of Silicalites. Faster conductometric electrode responses were achieved with enzyme immobilization on zeolite film technique. Also it is seen that Beta type zeolites modified through different ion exchange procedures, resulted different responses in IS-FET measurements.