| Silica-supported titanium materials are widely used for thermocatalytic applications such as hydroxylation of alkanes and aromatics, oxidation of alcohols and ethers, ammoximation of carbonyls, and sulfoxidations, while Ti-based materials are widely studied for photocatalytic applications such as photo-oxidation of organic substrates and photo-reduction of CO 2. However, the underlying phenomena of how to synthesize, identify, and control the active structures in these materials is not well understood because of the narrow scope of previous work. Studies of titanium-based catalysts typically focus on materials where the metal is present as either highly-dispersed Ti cations or in bulk crystalline TiO2 form, neglecting the numerous and potentially useful intermediate structures. Furthermore, these works typically focus on a single synthesis technique and rely upon bulk characterization techniques to understand the materials.;Here rigorous titanium-silica synthesis-structure-function relationships are established by examining several different synthetic method and utilizing characterization techniques that enable an atomic-level understanding of the materials. The materials studied span the range from isolated Ti cations to clustered TiOx domains, polymeric TiO x domains, anatase-like 2D TiO2 domains, and 3D crystalline TiO2. Tools to quantify accessible TiO x and tetrahedral Ti sites are developed, utilizing the selective titration of titanium with phenylphosphonic acid (PPA). Catalytic properties are probed with the photocatalytic oxidation of benzyl alcohol and the thermocatalytic epoxidation of cis-cyclooctene with H2O2 . PPA titration data indicate that the rate of benzyl alcohol photo-oxidation is independent of titanium coordination, while the rate of alkene epoxidation with H2O2 is proportional to the number of tetrahedral titanium sites on the catalyst. PPA titration data also enables the estimation of TiO2 particle size and reveals an important distinction between particle and crystal size, as obtained from XRD. In the course of establishing these relationships we've gained the knowledge of how to control TiO x structure, which enables the design of new and better catalysts.;Understanding the synthesis-structure-function relationships allow for the design of a tandem photo/thermocatalytic reaction system for producing and consuming H2O2. By partially overcoating a TiO 2 photocatalyst with a ∼2 nm silica layer we observe a 56-fold rate improvement compared to bare-TiO2 for H2O2 synthesis from the proton-assisted reduction of O2. Addition of metal-SiO2 thermocatalysts (metal=Ti, Nb, or Ta) with sites needed for H2O2 activation creates a tandem system wherein the H2O2 produced in situ is utilized for alkene epoxidation. Compared to a thermocatalytic-only system, the tandem system accelerates epoxidation for cis-cyclooctene(11x faster), styrene(20x) and 1-octene(30x). This approach demonstrates a means for epoxidation with O2 that avoids H2O2 purification and transport, simplifies the total process, provides new opportunities for control by independent H2O2 production and consumption in the same reactor, and enhances rates relative to thermocatalytic-only epoxidation by intimately coupling H2O2 generation and consumption. Critically, establishment of titanium-silica synthesis-structure-function relationships enables the design of new catalysts and systems that are less energy- and material-intensive, leading towards more sustainable chemistry. |
