Transformation of hydrocarbon feedstocks to complex molecules found in the fine chemical, agro chemical, and pharmaceutical industries require selective oxidations to impart the desired functionality. Oxidation of alcohols is commonly done employing harsh and potentially hazardous oxidants with stoichiometric amounts of byproducts being produced. The use of O2 as the terminal oxidant provides a safe and environmentally benign alternative with selectivity control being realized through the use of a catalyst. The use of a Ru(OH)x/Al2O3 catalyst for the oxidation of alcohols to aldehydes or ketones was studied for applicability and scalability in a continuous process. The catalyst was found to undergo rapid deactivation in the first 50-100 turnovers. High yields of diverse aldehydes and ketones were realized in the continuous process over the deactivated Ru(OH)x/Al2O3 catalyst. The discovery of a new heterogeneous catalyst was accomplished through rapid admixture screening and optimization using design of experiment techniques. The optimized catalyst compositions of PdBi0.47Te0.09/C (PBT-1) and PdBi0.35Te0.23/C (PBT-2) were found to be very active and selective for the aerobic oxidation of 1-octanol to methyl octanoate. These optimized catalysts show high yields of many diverse methyl esters from the oxidation of alcohols, and their stability was demonstrated in a continuous process achieving nearly 60,000 turnovers with no apparent loss in activity. The role of the Bi and Te promoters and mechanism of the PBT-2 catalyst was explored through kinetic studies and characterization of the catalyst. Through the use of kinetics and other mechanistic probes we discovered that the reaction shows saturation dependence in [substrate] and [K2CO3] and is first order in pO2, supporting a Langmuir-Hinshelwood mechanism with the reaction occurring between alkoxide and O2 adsorbed to the catalyst. The promoters are proposed to protect the Pd catalyst from over oxidation to inactive PdOx species as well as prevent side reactions (Bi) and electronically modify the Pd (Te). Oxidation of alcohols to aldehydes or nitriles was demonstrated in a continuous process using a CuI/TEMPO catalyst. The oxidation to the nitrile was accomplished through the addition of anhydrous ammonia, and excellent yields were observed from the oxidation of diverse primary benzylic alcohols.

This book deals with the search for environmentally benign procedures for the oxidation of alcohols and gives an overview of their transition-metal-catalyzed aerobic oxidation.

Safe and selective aerobic oxidation of organic substrates represents a grand challenge in catalysis. The productive utilization of oxygen is key to many, seemingly disparate, systems, for example, enzymatic catalysis, fine chemical production, and energy generation in fuel cells. This thesis describes new methods for carrying out aerobic oxidation in the latter two applications. Fuel cells are a promising technology for generating electrical energy from the energy in chemical bonds. However, the high loadings of Pt needed to catalyze oxygen reduction at the cathode have hindered broad adoption. To address this, a new fuel cell design was developed wherein oxygen reduction is executed off-electrode in an external reactor with non-Pt catalysts, using quinones as electron-proton transfer mediators. This represents the first instance of organic mediator use outside of low-power, enzymatic fuel cells. The latter part of this thesis details the development of new reactors and catalysts for general aerobic alcohol oxidations. Safe execution of aerobic oxidation in the presence of organic solvents is typically achieved by operating below the limiting oxygen concentration with inert diluents. 'Tube in shell' membrane reactors offer an intriguing alternative, permitting passage of O2 from the gas phase into a liquid-phase reaction through semi-permeable membranes. Use of a membrane reactor with inexpensive PTFE tubing enabled alcohol oxidation at rates an order of magnitude higher than previously reported. Heterogeneous catalysts, particularly noble metals such as Pt and Pd, have been extensively studied for alcohol oxidation. However, these catalysts exhibit low rates and limited substrate scopes due to poisoning by excess oxygen or various heterocycles; thus, various species were explored as catalyst 'promoters.' In the oxidative coupling of alcohols and ammonia to make nitriles, the addition of Bi to a Pt catalyst accelerated the rate of alcohol oxidation and enabled high yields with challenging heterocyclic alcohols. Furthermore, the addition of Bi and Te to a Pd catalyst increased the yield and rate for the oxidative coupling of alcohols with methanol to make methyl esters. Collectively, the above work highlights the opportunities for reaction engineering to enable the safe and selective utilization of oxygen in a range of chemistries.

Heterogeneously catalyzed selective oxidations of alcohols is a highly topical field. The first chapter of this brief describes the importance of the selective oxidation of alcohols and advantages of heterogeneous catalysts over conventional catalysts, use of environmentally benign oxidants, and the design of selective catalysts by tailoring of polyoxometalates at the molecular level. Chapter 2 describes synthesis, characterization 11-molybdophosphate based supported materials and their use as heterogeneous catalysts for oxidation of alcohols with molecular oxygen under solvent free mild reaction condition. ZrO2, Al2O3, MCM-41 and zeolite Hβ were used as supports. Chapter 3 describes synthesis, characterization of transition metals (Mn, Co, Ni, Cu)- substituted phosphomolybdates and their use as heterogeneous catalysts for oxidation of alcohols with molecular oxygen under solvent free mild reaction condition. Chapter 4 describes conclusive remarks for present catalytic systems.

This book presents a state-of-the-art review on recent advances in nanocatalysts and electrocatalysis in DOFCs.

This book offers a comprehensive overview of the most recent developments in both total oxidation and combustion and also in selective oxidation. For each topic, fundamental aspects are paralleled with industrial applications. The book covers oxidation catalysis, one of the major areas of industrial chemistry, outlining recent achievements, current challenges and future opportunities. One distinguishing feature of the book is the selection of arguments which are emblematic of current trends in the chemical industry, such as miniaturization, use of alternative, greener oxidants, and innovative systems for pollutant abatement. Topics outlined are described in terms of both catalyst and reaction chemistry, and also reactor and process technology.