dc.contributor.author	Mou, Tianyou	en
dc.contributor.committeechair	Xin, Hongliang	en
dc.contributor.committeemember	Achenie, Luke E.	en
dc.contributor.committeemember	Zhu, Huiyuan	en
dc.contributor.committeemember	Valeyev, Eduard Faritovich	en
dc.contributor.department	Chemical Engineering	en
dc.date.accessioned	2023-07-20T08:00:16Z	en
dc.date.available	2023-07-20T08:00:16Z	en
dc.date.issued	2023-07-19	en
dc.description.abstract	Carbon dioxide (CO2), as a greenhouse gas, has shown to achieve the highest level in history, causes the global warming issue, leading to a 1.2 ℃ increase of the global average temperature. The consumption of fossil fuels is one of the main reasons that cause CO2 emission. Current industrial production of chemicals accounts for 29% of total fossil fuels consumption, which can be the feedstock or raw materials for carbon source, or act as the fuel to generate heat and power. CO2 conversion technologies, e.g., thermo-catalytic reaction and electrochemical reduction, have drawn researchers' attention, since they have the potential to resolve the feedstock and fuel consumption sectors of chemical production at the same time. CO2 conversion technologies use CO2 as the direct carbon source of chemicals and store the intermittent renewable energies as the energy source, which can ultimately achieve a net-zero CO2 emission and produce value-added chemical products. However, there are challenges for a practical application of CO2 conversion technologies. For instance, electrochemical CO2 reduction reaction (ECO2RR) suffers from the low activity and selectivity, while thermocatalytic CO2 conversion, or the CO2 hydrogenation reaction, usually requires harsh reaction conditions and has a low selectivity. Nonetheless, the improvement of developing new promising catalysts remains limited, due to the lack of insights of the reactions. The complex reaction networks and kinetics lead to an elusive reaction mechanism, and various effects, e.g., solvation, potential, structure, and coverage, hinder our fundamental understanding of catalytic processes. Herein, we report the efforts that we have been put in to gain insights of reaction mechanism of CO2 reduction reactions. Bi has shown to reduce CO2 to formic acid (HCOOH), while we have found that, by constituting a Bi-Cu2S heterostructure catalyst, a better catalytic performance was achieved, due to the structural effect of the interface (Chapter 2). However, it is shown that the CO2 electrochemical reduction mechanism on Bi has changed when switching the electrolyte from water to aprotic media, e.g., ionic liquids, and CO was obtained as the main product instead of HCOOH, showing a shift of reaction pathway due to the electrolyte effect (Chapter 3). However, the fundamental understanding of reaction mechanism requires not only the reaction pathways, but the reaction kinetics under reaction conditions, where the lateral or adsorbate-adsorbate interactions play an important role. In this case, we summarized recent advances of applications of machine learning (ML) algorithms for adsorbate-adsorbate interaction model developments to deal with the realistic reaction kinetics (Chapter 4). The lattice based Kinetic Monte Carlo (KMC) has shown promising performances for considering the lateral interactions of surface reactions. We report the mechanistic and KMC kinetic study of CO2 hydrogenation on Cesium promoted Au(111) surface, to gain insights of alkali metal promoting effects under reaction conditions (Chapter 5). To expand the scope, the integration of CO2 reduction with the C-N bond formation provides a promising strategy to produce more value-added product such as urea. Recent studies show that urea can be produced by reducing CO2 and nitrate (NO3-) from wastewater, which mitigate both global warming and nitrate pollution issue. However, the reaction mechanism remains elusive due to the complicated reaction network. Therefore, we employed the first-principles molecular dynamics to reveal the reaction mechanism of C-N coupling and the effect of different reaction conditions including applied potential and electrolyte (Chapter 6). Although recent advances in the computational catalysis field have significantly push forward the understanding of the chemistry nature of heterogeneous catalysis, the gap between theory and experiment remains far beyond bridged due to the complexity nature of the problem in a wide range of time and length scales, hinders the development and discovery of active catalytic materials. Recent advances of narrowing and bridging the complexity gap between theory and experiment with machine learning have been summarized to emphasize the importance of utilizing machine learning for rational catalyst design (Chapter 7).	en
dc.description.abstractgeneral	Global warming issue is a rising topic in recent years which has severe impacts on environments. One of the main reasons is the increase level of greenhouse gases that prevent the release of heat that captured from the sun. Carbon dioxide (CO2) is achieving the highest level in history due to the human activities including the consumption of fossil fuels. Therefore, CO2 conversion technologies are needed to tackle reduce the CO2 level in the atmosphere and the emission of CO2 in industries. CO2 conversion technologies, e.g., thermo-catalytic reaction and electrochemical reduction, have drawn researchers' attention, since they have the potential to resolve the feedstock and fuel consumption sectors of chemical production at the same time. However, the complexity of the CO2 conversion processes hinders the development of new technologies. Since the nature of these technologies are heterogeneous catalytic reactions, all reactions are happening at the interface between catalysts and reactants/products, which calls for the understanding of interfacial mechanisms of CO2 reduction reactions. For this type of high degree of freedom problem where many phases including solid-solid, solid-liquid, and solid-gas phases exist, multiscale simulations turn out to be a proper approach since the wide time and length scale that can be covered. Herein, we employed different multiscale modeling methods to tackle various CO2 reduction problems. For electrochemical reduction of CO2, we designed a novel Bi-Cu2S hetero-structured catalyst, which has abundant interfacial sites between Bi and Cu2S, demonstrating the improved catalytic performance of ECO2RR toward formate production. At the same time, it has been found that in non-aqueous solution, the reaction pathway has been switched, where CO is obtained as the final product instead of formate. This effect has been investigated using constant potential calculation method to probe the reaction under reaction condition. For thermo-catalytic reactions, we studied the CO2 hydrogenation on Cesium promoted Au(111) surface using quantum mechanics and kinetic Monte Carlo (KMC) calculations, to gain insights of alkali metal promoting effects under reaction conditions. To expand the scope, the integration of CO2 electroreduction with C-N coupling is a promising strategy for global warming and pollution control, which utilizes the nitrate (NO3-) from wastewater and CO2 to produce high value-added product such as urea. The fundamental investigation of reaction mechanism of C-N coupling has been studied using first principles molecular dynamics.	en
dc.description.degree	Doctor of Philosophy	en
dc.format.medium	ETD	en
dc.identifier.other	vt_gsexam:37762	en
dc.identifier.uri	http://hdl.handle.net/10919/115796	en
dc.language.iso	en	en
dc.publisher	Virginia Tech	en
dc.rights	In Copyright	en
dc.rights.uri	http://rightsstatements.org/vocab/InC/1.0/	en
dc.subject	Computational catalysis	en
dc.subject	reaction kinetics	en
dc.subject	multiscale simulations	en
dc.subject	machine learning	en
dc.title	Understanding Interfacial Kinetics of Catalytic Carbon Dioxide Transformations from Multiscale Simulations	en
dc.type	Dissertation	en
thesis.degree.discipline	Chemical Engineering	en
thesis.degree.grantor	Virginia Polytechnic Institute and State University	en
thesis.degree.level	doctoral	en
thesis.degree.name	Doctor of Philosophy	en

Understanding Interfacial Kinetics of Catalytic Carbon Dioxide Transformations from Multiscale Simulations

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