Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

Organic Reactions Catalysed by Modified Clays

Department of Applied Chemistry, Cochin University of Science and Technology

Modeling and Analysis of Some Heavy Tailed Time Series

The thesis has covered various aspects of modeling and analysis of finite mean time series with symmetric stable distributed innovations. Time series analysis based on Box and Jenkins methods are the most popular approaches where the models are linear and errors are Gaussian. We highlighted the limitations of classical time series analysis tools and explored some generalized tools and organized the approach parallel to the classical set up. In the present thesis we mainly studied the estimation and prediction of signal plus noise model. Here we assumed the signal and noise follow some models with symmetric stable innovations.We start the thesis with some motivating examples and application areas of alpha stable time series models. Classical time series analysis and corresponding theories based on finite variance models are extensively discussed in second chapter. We also surveyed the existing theories and methods correspond to infinite variance models in the same chapter. We present a linear filtering method for computing the filter weights assigned to the observation for estimating unobserved signal under general noisy environment in third chapter. Here we consider both the signal and the noise as stationary processes with infinite variance innovations. We derived semi infinite, double infinite and asymmetric signal extraction filters based on minimum dispersion criteria. Finite length filters based on Kalman-Levy filters are developed and identified the pattern of the filter weights. Simulation studies show that the proposed methods are competent enough in signal extraction for processes with infinite variance.Parameter estimation of autoregressive signals observed in a symmetric stable noise environment is discussed in fourth chapter. Here we used higher order Yule-Walker type estimation using auto-covariation function and exemplify the methods by simulation and application to Sea surface temperature data. We increased the number of Yule-Walker equations and proposed a ordinary least square estimate to the autoregressive parameters. Singularity problem of the auto-covariation matrix is addressed and derived a modified version of the Generalized Yule-Walker method using singular value decomposition.In fifth chapter of the thesis we introduced partial covariation function as a tool for stable time series analysis where covariance or partial covariance is ill defined. Asymptotic results of the partial auto-covariation is studied and its application in model identification of stable auto-regressive models are discussed. We generalize the Durbin-Levinson algorithm to include infinite variance models in terms of partial auto-covariation function and introduce a new information criteria for consistent order estimation of stable autoregressive model.In chapter six we explore the application of the techniques discussed in the previous chapter in signal processing. Frequency estimation of sinusoidal signal observed in symmetric stable noisy environment is discussed in this context. Here we introduced a parametric spectrum analysis and frequency estimate using power transfer function. Estimate of the power transfer function is obtained using the modified generalized Yule-Walker approach. Another important problem in statistical signal processing is to identify the number of sinusoidal components in an observed signal. We used a modified version of the proposed information criteria for this purpose.

Studies on Catalysis by Ordered Mesoporous SBA-15 Materials Modified with Transition Metals

To meet the challenges related to the chemical industry,development of efficient catalysts is necessary.The mesoporous materials like SBA-15 are considered as good catalyst candidates of 21st century.SBA-15 mesoporous materials are catalytically inactive,but allow the dispersion of catalytically active phases into the framework.So these materials can be considered as an interesting alternative for preparing catalytically active metal nanoparticles in-situ into it.In the present work various transition metals are incorporated to improve the catalytic activity of SBA-15 material.The fundamental aspects of the preparation,characterization and the activity studies are briefly viewed in this thesis. Systematic investigation of the physico-chemical properties and catalytic activity studies of the prepared materials were carried out and presented in this Study.

Studies on Photocatalysis by Nano Titania Modified with Non-Metals

The present work aims to prepare visible light responsive anion doped titania via sol-gel precipitation method.The prepared catalysts were characterized by various techniques.The photocatalytic abilities of the prepared catalysts were measured by the degradation of dyes,pesticides,hydrogen production through water splitting reaction and antibacterial study.We also compared the activities of prepared catalysts with pure titania prepared in the laboratory and one of the commercial anatase titania samples.

Effect of Improving Energy Efficiency on System Reliability

In the present scenario of energy demand overtaking energy supply top priority is given for energy conservation programs and policies. Most of the process plants are operated on continuous basis and consumes large quantities of energy. Efficient management of process system can lead to energy savings, improved process efficiency, lesser operating and maintenance cost, and greater environmental safety. Reliability and maintainability of the system are usually considered at the design stage and is dependent on the system configuration. However, with the growing need for energy conservation, most of the existing process systems are either modified or are in a state of modification with a view for improving energy efficiency. Often these modifications result in a change in system configuration there by affecting the system reliability. It is important that system modifications for improving energy efficiency should not be at the cost of reliability. Any new proposal for improving the energy efficiency of the process or equipments should prove itself to be economically feasible for gaining acceptance for implementation. In order to arrive at the economic feasibility of the new proposal, the general trend is to compare the benefits that can be derived over the lifetime as well as the operating and maintenance costs with the investment to be made. Quite often it happens that the reliability aspects (or loss due to unavailability) are not taken into consideration. Plant availability is a critical factor for the economic performance evaluation of any process plant.The focus of the present work is to study the effect of system modification for improving energy efficiency on system reliability. A generalized model for the valuation of process system incorporating reliability is developed, which is used as a tool for the analysis. It can provide an awareness of the potential performance improvements of the process system and can be used to arrive at the change in process system value resulting from system modification. The model also arrives at the pay back of the modified system by taking reliability aspects also into consideration. It is also used to study the effect of various operating parameters on system value. The concept of breakeven availability is introduced and an algorithm for allocation of component reliabilities of the modified process system based on the breakeven system availability is also developed. The model was applied to various industrial situations.

Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

Multi-objective assembly job shop scheduling using genetic algorithm and tabu search

Assembly job shop scheduling problem (AJSP) is one of the most complicated combinatorial optimization problem that involves simultaneously scheduling the processing and assembly operations of complex structured products. The problem becomes even more complicated if a combination of two or more optimization criteria is considered. This thesis addresses an assembly job shop scheduling problem with multiple objectives. The objectives considered are to simultaneously minimizing makespan and total tardiness. In this thesis, two approaches viz., weighted approach and Pareto approach are used for solving the problem. However, it is quite difficult to achieve an optimal solution to this problem with traditional optimization approaches owing to the high computational complexity. Two metaheuristic techniques namely, genetic algorithm and tabu search are investigated in this thesis for solving the multiobjective assembly job shop scheduling problems. Three algorithms based on the two metaheuristic techniques for weighted approach and Pareto approach are proposed for the multi-objective assembly job shop scheduling problem (MOAJSP). A new pairing mechanism is developed for crossover operation in genetic algorithm which leads to improved solutions and faster convergence. The performances of the proposed algorithms are evaluated through a set of test problems and the results are reported. The results reveal that the proposed algorithms based on weighted approach are feasible and effective for solving MOAJSP instances according to the weight assigned to each objective criterion and the proposed algorithms based on Pareto approach are capable of producing a number of good Pareto optimal scheduling plans for MOAJSP instances.

“Reconstruction of Gene Regulatory Network from Expression Profile of Plasma RNA Data of Colorectal Cancer Patients using Soft Computing Techniques”

Microarray data analysis is one of data mining tool which is used to extract meaningful information hidden in biological data. One of the major focuses on microarray data analysis is the reconstruction of gene regulatory network that may be used to provide a broader understanding on the functioning of complex cellular systems. Since cancer is a genetic disease arising from the abnormal gene function, the identification of cancerous genes and the regulatory pathways they control will provide a better platform for understanding the tumor formation and development. The major focus of this thesis is to understand the regulation of genes responsible for the development of cancer, particularly colorectal cancer by analyzing the microarray expression data. In this thesis, four computational algorithms namely fuzzy logic algorithm, modified genetic algorithm, dynamic neural fuzzy network and Takagi Sugeno Kang-type recurrent neural fuzzy network are used to extract cancer specific gene regulatory network from plasma RNA dataset of colorectal cancer patients. Plasma RNA is highly attractive for cancer analysis since it requires a collection of small amount of blood and it can be obtained at any time in repetitive fashion allowing the analysis of disease progression and treatment response.

“Catalysis by Nanocrystalline Ceria Modified with Transition Metals”

The objective of the present work is to improve the textural and structural properties of cerium oxide by the incorporation of transition metals as well as sulphate ions. We have incorporated tungsten, molybdenum and chromium oxide into pure as well as sulphated cerium oxide and the catalytic systems thus prepared were characterised using various techniques. lndustrially important reactions such as acetalization and deacetalization, oxidative dehydrogenation of ethylbenzene, MTBE synthesis and Beckmann rearrangement of cinnamaldoxime and salicylaldoxime have been selected for the measurement of the catalytic activity of the systems. The work is presented in eight chapters

Chemically Modified Glassy Carbon Electrode as Sensors for Various Pharmaceuticals

Voltammetric methods are applicable for the determination of a wide variety of both organic and inorganic species. Its features are compact equipment, simple sample preparation, short analysis time, high accuracy and sensitivity. Voltammetry is especially suitable for laboratories in which only a few parameters have to be monitored with a moderate sample throughput. Of various electrode materials, glassy carbon electrode is particularly useful because of its high electrical conductivity, impermeability to gases, high chemical resistance, reasonable mechanical and dimensional stability and widest potential range of all carbonaceous electrodes. Electrode modification is a vigorous research area by which the electrochemical determination of various analyte species is facilitated. The scope of pharmaceutical analysis includes the analytical investigation of pure drug, drug formulations, impurities and degradation products of drugs, biological samples containing the drugs and their metabolites with the aim of obtaining data that can contribute to the maximal efficacy and maximal safety of drug therapy. This thesis presents the modification of glassy carbon electrode using metalloporphyrin and dyes and subsequently using these modified electrodes for the determination of various pharmaceuticals. The thesis consists of 9 chapters.

‘‘catalysis by nano sulfated titania modified by transition metals"

in the present study, we have prepared and evaluated the physical and chemical properties and catalytic activities of transition metal loaded sulfated titania via the sol-gel route. Sol-gel method is widely used for preparing porous materials having controlled properties and leads to the formation of oxide particles in nano range, which are spherical or interconnected to each other. Characterization using various physico-chemical techniques and a detailed study of acidic properties are also carried out. Some reactions of industrial importance such as Friedel-Crafts reaction, fen-butylation of phenol,Beckmann rearrangement of cyclohexanone oxime, nitration of phenol and photochemical degradation of methylene blue have been selected for catalytic activity study in the present venture. The work is organized into eight chapters

Fixed Point Decimal Multiplication Using RPS Algorithm

Decimal multiplication is an integral part of financial, commercial, and internet-based computations. A novel design for single digit decimal multiplication that reduces the critical path delay and area for an iterative multiplier is proposed in this research. The partial products are generated using single digit multipliers, and are accumulated based on a novel RPS algorithm. This design uses n single digit multipliers for an n × n multiplication. The latency for the multiplication of two n-digit Binary Coded Decimal (BCD) operands is (n + 1) cycles and a new multiplication can begin every n cycle. The accumulation of final partial products and the first iteration of partial product generation for next set of inputs are done simultaneously. This iterative decimal multiplier offers low latency and high throughput, and can be extended for decimal floating-point multiplication.

Synthesis, Characterization and Catalytic Activity of Nanocrystalline Ceria Modified With Zirconia

The use of catalysts in chemical and refining processes has increased rapidly since 1945, when oil began to replace coal as the most important industrial raw material. Catalysis has a major impact on the quality of human life as well as economic development. The demand for catalysts is still increasing since catalysis is looked up as a solution to eliminate or replace polluting processes. Metal oxides represent one of the most important and widely employed classes of solid catalysts. Much effort has been spent in the preparation, characterization and application of metal oxides. Recently, great interest has been devoted to the cerium dioxide (CeO2) containing materials due to their broad range of applications in various fields, ranging from catalysis to ceramics, fuel cell technologies, gas sensors, solid state electrolytes, ceramic biomaterials, etc., in addition to the classical application of CeO2 as an additive in the so-called three way catalysts (TWC) for automotive exhaust treatment. Moreover, it can promote water gas shift and steam reforming reactions, favours catalytic activity at the interfacial metal-support sites. The solid solutions of ceria with Group IV transitional-metals deserve particular attention for their applicability in various technologically important catalytic processes. Mesoporous CeO2−ZrO2 solid solutions have been reported to be employed in various reactions which include CO oxidation, soot oxidation, water-gas shift reaction, and so on. Inspired by the unique and promising characteristics of ceria based mixed oxides and solid solutions for various applications, we have selected ceria-zirconia oxides for our studies. The focus of the work is the synthesis and investigation of the structural and catalytic properties of modified and pure ceria-zirconia mixed oxide.

A Data Mining Approach for the Identification of Adverse Drug Events (ADE) resulting from Drug-Drug Interactions (DDI) to improve pharmacovigilance

In the current study, epidemiology study is done by means of literature survey in groups identified to be at higher potential for DDIs as well as in other cases to explore patterns of DDIs and the factors affecting them. The structure of the FDA Adverse Event Reporting System (FAERS) database is studied and analyzed in detail to identify issues and challenges in data mining the drug-drug interactions. The necessary pre-processing algorithms are developed based on the analysis and the Apriori algorithm is modified to suit the process. Finally, the modules are integrated into a tool to identify DDIs. The results are compared using standard drug interaction database for validation. 31% of the associations obtained were identified to be new and the match with existing interactions was 69%. This match clearly indicates the validity of the methodology and its applicability to similar databases. Formulation of the results using the generic names expanded the relevance of the results to a global scale. The global applicability helps the health care professionals worldwide to observe caution during various stages of drug administration thus considerably enhancing pharmacovigilance