Understanding Grafted Cations in Controlled Environments for Heterogeneous Catalysis

Catalytic processes occurring on the surfaces of heterogeneous catalysts are controlled by the molecular structures of active sites where these reactions occur. These active sites can be broadly thought to consist of an active center, where bond making and breaking events occur, surrounding by the surface of the support. These are the inner-sphere (i.e. active center) and outer-sphere (i.e. surface) environments of the active site. Catalyst design typically focuses on the choice of the optimal inner-sphere environment, while surfaces are often regarded as inert oxide supports onto which active sites are dispersed to facilitate catalyst recovery. In this thesis, I demonstrate that the outer-sphere surface environment is, in fact, an essential element for controlling the structure and reactivity of active sites supported on silicates.The theoretical concepts, silicate supports, and synthetic approaches that are used in this thesis are introduced in Chapter 1. Given the importance of silanol groups as grafting sites in synthetic approaches used in this thesis, I begin by providing a detailed study of silanol speciation across zeotypes and amorphous supports, in Chapter 2. Subsequently, I provide an example of how silanol environments control grafting processes and how crystalline silicates provide stable support environments for FeIII cations, in Chapter 3. I then introduce an approach to synthesizing well-defined active sites by controlling the structure of a grafted cation using an organic ligand, applied to calix[4]arene-TiIV complexes grafted on amorphous SiO2 as epoxidation catalysts, in Chapter 4. Having established the structure of silicates and approaches to synthesize well-defined active sites on their surface, I present three studies where this enables the study of structure and catalytic properties. In Chapter 5, I demonstrate how this approach enables the unambiguous deconvolution of the effect of support outer-sphere on epoxidation catalysis. In Chapter 6, I investigate how the support outer-sphere can also control the conformation and structure of grafted complexes, while providing insight into adsorption processes occurring on surfaces. Finally, in Chapter 7, I provide a detailed mechanistic study of how partially confining outer-sphere environments impact catalytic reactivity for olefin epoxidation. Taken together, this work provides fresh insights into the structure of silicate supports and their ability to control catalysis, providing an additional and important avenue to the design of heterogeneous catalysts