Exploring Catalytic Properties of Polyoxometalates in Aerobic Decontamination and Water Oxidation 公开

Song, Jie (2011)

Permanent URL: https://etd.library.emory.edu/concern/etds/5x21tf88b?locale=zh
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Abstract

Abstract Exploring Catalytic Properties of Polyoxometalates in Aerobic Oxidation and Water Oxidation By Jie Song The focus of this thesis is to explore the catalytic properties of POMs either in degradation of toxic industrial chemicals via aerobic oxidation or splitting water via water oxidation. In chapter 2, new types of covalently-linked organic-hexavanadate hybrids are synthesized through solvothermal method or postsynthesis techniques and demonstrate their catalytic capability in aerobic oxidation of toxic organic chemicals such as propanethiol, hydrogen sulfide, and aldehyde, under ambient condition. In chapter 3, two novel inorganic-organic hybrid clusters with one or two covalently linked pyrene fluorescent probes are employed as synthons for the controlled assembly of large vesicle nanostructure in solution and exhibit interesting pH-dependent fluorescence and interactions between hybrid clusters and their counterions. In chapter 4, a polyoxometalate-metal organic framework material was documented as a new type of catalyst that exhibits the attractive features of both its components (POM and MOF) and mutual enhancement of stability by each unit. This catalyst can effectively catalyze detoxification of various sulfur-containing compounds including H2S using only ambient air. In chapter 5, two photosensitizer-POM hybrids were studied by both spectroscopic techniques and computational methods. This research provides detailed structural information in understanding the electron transfer character between cationic photosensitizers commonly-employed in dye-sensitized solar cells and catalytic polyanions studied in the water splitting process. In chapter 6, a multicobalt substituted polyoxometalate was discovered to be a new efficient all-inorganic molecular water oxidation catalyst. The extremely high turnover number (TON ≈1500) and turnover frequency (TOF >10 s-1) under the optimal conditions set a new record in this area to date. Multiple physicochemical techniques and catalytic kinetics studies provide the evidences that the POM-based catalysts remain intact during turnovers.


Exploring Catalytic Properties of Polyoxometalates in Aerobic Oxidation and Water Oxidation By Jie Song B.S.,Shandong University, China, 1997 M.S., Lanzhou University, China, 2001 Advisor: Craig L. Hill , pH. D. A dissertation submitted to the Faculty of the James T. Laney School of Graduate Studies of Emory University in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry 20 11

Table of Contents

Table of Contents

Chapter One:

Introduction: Structures and Features of Isopolyanions and Heteropolyanions 1

Chapter Two:

Covalently-linked organic-POM hybrids: synthesis, characterization, and catalytic removal of toxic chemicals 42

Chapter Three:

Inorganic-Organic Hybrid Vesicles with Counterion- and pH-Controlled Fluorescent Properties 86


Chapter Four:

A Multi-unit Catalyst with Synergistic Stability and Reactivity: A Polyoxometalate-Metal Organic Framework for Aerobic Decontamination 124

Chapter Five:

Synthesis, structure, and characterization of two polyoxometalate-photosensitizer hybrid materials 155

Chapter Six:

An Efficient Homogeneous Carbon-free Multi-cobalt Water Oxidation Catalyst: New Structure and High Activity 182


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