Robert L. Thompson

Size-dependent photocatalytic reduction of CO2 with PbS quantum dot sensitized TiO2 heterostructured photocatalysts

The photocatalytic reduction of CO2 to value-added chemicals, such as CH4, is a promising carbon management approach which can generate revenue from chemical sales to offset the cost of implementing CO2 capture technologies. To make photocatalytic conversion approaches efficient, economically practical, and industrially scalable, catalysts capable of utilizing visible and near infrared (IR) photons need to be developed. Here we investigate the sensitization of TiO2 catalysts using PbS quantum dots (QDs) which lead to the size dependent photocatalytic reduction of CO2 at frequencies ranging from the violet to the orange-red edge of the electromagnetic spectrum (λ ∼ 420 to 610 nm). Under broad band illumination (UV- NIR), the PbS QDs enhance CO2 photoreduction rates with TiO2 by a factor of ∼5 in comparison to unsensitized photocatalysts. X-ray photoelectron spectroscopy (XPS) is used to investigate the deactivation mechanism of the QD sensitizers after prolonged photoexcitation. The synthesis, characterization, and catalytic testing of these PbS sensitized TiO2 heterostructures will aid the development of more robust, visible light active photocatalysts for carbon management applications.

Contribution of the Acetate Anion to CO2 Solubility in Ionic Liquids: Theoretical Method Development and Experimental Study

A new theoretical method was developed to compute the Henrys law constant for gas absorption in a solvent through strong nonphysical interactions. The new method was created by expanding the test particle insertion method typically applied to physisorbing systems to account for the strong intermolecular interactions present in chemisorbing systems. By using an ab initio (AI)-based Boltzmann-averaged potential to model the interaction between CO2 and the tetra-n-butylphosphonium acetate ([P4444][CH3COO]) ionic liquid, the total Henryss law constant at 298 K was computed to be 0.011 to 0.039 bar, reasonably comparable to the experimental value of 0.18 bar measured in this work. Three different AI potentials were used to verify the applicability of this approach. In contrast, when a classical force field (FF) was used to describe the interaction between CO2 and [P4444][CH3COO], the Henrys law constant was computed to be 27 bar, significantly larger than the experimental value. The classical FF underestimates the CO2-[P4444][CH3COO] interaction compared with the AI calculations, which in turn leads to the smaller simulated CO2 solubility. Simulations further indicate that the CO2 interaction with the [CH3COO](-) anion is much stronger than with the [P4444](+) cation. This result strongly suggests that the large CO2 solubility in [P4444][CH3COO] is due to the strong CO2-[CH3COO](-) interaction.

Probing the effect of electron donation on CO2 absorbing 1,2,3-triazolide ionic liquids

Development of the next generation materials for effective separation of gases is required to address various issues in energy and environmental applications. Ionic liquids (ILs) are among the most promising material types. To overcome the many hurdles in making a new class of materials technologically applicable, it is necessary to identify, access, and scale up a range of representative substances. In this work, CO2 reactive triazolide ILs were synthesized and characterized with the aim of developing a deeper understanding of how structural changes affect the overall properties of these substances. It was found that substituents on the anion play a crucial role in dictating the physical properties for CO2 capture. Depending upon the anion substituent, CO2 capacities between 0.07 and 0.4 mol CO2 per mol IL were observed. It was found that less sterically-hindered anions and anions containing electron donating groups were more reactive towards CO2. Detailed spectroscopic, CO2 absorption, rheological, and simulation studies were carried out to understand the nature and influence of these substituents. The effect of water content was also evaluated, and it was found that water had an unexpected impact on the properties of these materials, resulting in an increased viscosity, but little change in the CO2 reactivity.