Download or read book Mechanistic Studies of First row Transition Metal Catalyzed Homogeneous CO2 Reduction Via H2 Using Density Functional Theory written by Linbin Yao and published by . This book was released on 2020 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Mechanistic Studies of First row Homogeneous Transition Metal Catalysts written by Bas Venderbosch and published by . This book was released on 2020 with total page 230 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Homogeneous Photocatalysis written by M. Chanon and published by John Wiley & Sons. This book was released on 1997-03-06 with total page 440 pages. Available in PDF, EPUB and Kindle. Book excerpt: Photocatalysis and related processes occupy a strategic position for the future of photochemistry. This volume provides an introduction to basic concepts and explains how applications work at the molecular level.

Download or read book Understanding Electrocatalytic CO2 Reduction and H2O Oxidation on Transition Metal Catalysts from Density Functional Theory Study written by Zaheer Masood and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: A major contribution to global warming is CO2 emitted from the combustion of fossil fuels. Electrochemical processes can help to mitigate the elevated CO2 emissions through either the conversion of CO2 into value-added chemicals or the replacement of fossil fuels with clean fuels such as hydrogen produced from water oxidation. The present dissertation focuses on the mechanistic aspects of electrochemical processes. Electrochemical water oxidation is hindered by the low efficiency of oxygen evolution reaction (OER) at the anode whereas electrochemical reduction of CO2 (ERCO2) is hampered by high overpotentials and poor product selectivity. In this dissertation, we studied the catalytic activity of transition metal-based catalysts, including FeNi spinels, metal-oxide/copper, and d metal cyclam complexes, for both OER and ERCO2 using the density functional theory (DFT) computational approach. We report a combined effort of fabricating FeNi oxide catalysts and identifying the active component of the catalyst for OER. Our collaborators at the University of California, Santa Cruze fabricated a series of FeNi spinels-based materials including Ni(OH)Fe2O4(Cl), Ni(OH)Fe2O4, Fe(OH)Fe2O4(Cl), Fe(OH)Fe2O4, Ni(OH)O(Cl), Ni(OH)O and some show exceptional activity for OER. Combined experimental characterization and computational mechanistic study based on the computational hydrogen electrode (CHE) model revealed that Ni(OH)Fe2O4(Cl) is the active ensemble for exceptional OER performance. We also investigated CO2 reduction to C1 products at the metal-oxide/copper interfaces ((MO)4/Cu(100), M = Fe, Co and Ni) based on the CHE model. The effect of tuning metal-oxide/copper interfaces on product selectivity and limiting potential was clearly demonstrated. This study showed that the catalyst/electrode interface and solvent can be regulated to optimize product selectivity and lower the limiting potential for ERCO2. Applied potential affects the stability of species on the surface of the electrode. The proton-coupled electron transfer (PCET) equilibrium assumed in the CHE model does not capture the change in free energy under the influence of the applied potential. In contrast, the constant electrode potential (CEP) model captures changes in free energy due to applied potential, we applied the CEP model to ERCO2 and OER on (MO)4/Cu(100) and compared the results with those from the CHE model. The results demonstrate that the CHE and the CEP models predict different limiting potentials and product selectivity for ERCO2, but they predict similar limiting potentials for OER. The results demonstrate the importance of accounting for the applied potential effect in the study of more complex multi-step electrochemical processes. We also studied transition metal-based homogeneous catalysts for ERCO2. We examined the performance of transition metal(M)--cyclam(L) complexes as molecular catalysts for the reduction of CO2 to HCOO- and CO, focusing on the effect of changing the metal ions in cyclam on product selectivity (either HCOO- or CO), limiting potential and competitive hydrogen evolution reaction. Our results show that among the complexes, [LNi]2+ and [LPd]2+ can catalyze CO2 reduction to CO, and [LMo]2+ and [LW]3+ can reduce CO2 to HCOO-. Notably, [LMo]2+, [LW]3+, [LW]2+ and [LCo]2+ have a limiting potential less negative than -1.6 V and are based on earth-abundant elements, making them attractive for practical application. In summary, the dissertation demonstrates high-performance catalysts can be designed from earth-abundant transition metals for electrochemical processes that would alleviate the high CO2 level in the environment. On the other hand, completely reversing the increasing trend of CO2 level in the atmosphere requires a collective human effort.

Download or read book Celebrating the Work of Prof Sourav Pal Computational Approaches in Catalysis written by Soumyajit Roy and published by Frontiers Media SA. This book was released on 2022-05-25 with total page 160 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Homogeneous Catalytic Oxygen Reduction by Monomeric Cobalt Complexes written by Yu-Heng Wang (Ph.D.) and published by . This book was released on 2018 with total page 407 pages. Available in PDF, EPUB and Kindle. Book excerpt: The oxygen reduction reaction (ORR) plays an important role in various life processes such as respiration and in energy conversion systems such as fuel cells and metal-air batteries. Achieving a selective and efficient ORR remains a significant challenge in energy conversion, where the sluggish kinetics of the ORR has also restricted its practical application. Platinum group metal (PGM) catalysts are currently the best-performing candidates for efficient reduction of O2 with overpotential less than 300 mV. However, scientists are exploring non-PGM ORR catalysts, due to their high abundance and low cost. Molecular first row transition-metal complexes, such as those macrocyclic ligands containing cobalt are the main representatives of non-precious ORR catalysts. This thesis details the comprehensive investigation of the selectivity, overpotential, mechanistic studies, and linear free energy relationship (LFER) analysis of homogeneous O2 reduction to H2O2 and H2O catalyzed by a series of monomeric cobalt complexes. Chapters 2-4 of this thesis depicts the homogeneous 2e[-]/2H+ O2 reduction catalyzed by a series of cobalt complexes bearing tetradentate N2O2-based ligands (Co(N2O2)). These studies show that H2O2 is directly produced from molecular O2 with an effective overpotential as low as 90 mV. A linear dependence of logarithm of turnover frequency (log(TOF)) is observed with respect to effective overpotential suggesting there exists a trade-off between the rate and overpotential for ORR with these Co(N2O2) complexes. However, the dependence is weaker compared with that of iron porphyrin (Fe(por)) complexes, which is rationalized by the different influence of effective overpotential on their turnover-limiting step. The subsequent mechanistic studies reveal that the protonation on the proximal oxygen atom of the CoIII(OOH) intermediate is the rate-limiting step in the ORR. Density functional theory (DFT) studies, in combination with kinetic and electrochemical studies, provide deeper mechanistic insights into the O2 reduction catalyzed by Co(N2O2) complexes. The small Brønsted coefficient and O2-independent rate law imply that the low-overpotential O2 reduction is achievable because the ORR rate is relatively insusceptible to the effective overpotential. The performance of monomeric cobalt ORR catalysts bearing N4-macrocyclic ligands reported in the literature is evaluated on the basis of their TOF and effective overpotential. It is shown for the first time that they all fall in the linear relationships between log(TOF) and effective overpotential. Chapters 5-7 of this thesis highlight the exploration of the homogeneous 4e[-]/4H+ reduction of O2 to H2O catalyzed by a series of cobalt porphyrin (Co(por)) complexes. The catalysis-initiating potential of the Co(por) complexes (half-wave potential, E1/2(CoIII/II)) is found to be independent of the pKa values of the acids, but the potential shift for O2/H2O redox couples is nearly 59 mV/pKa in organic media. This outcome suggests that the effective overpotential is correlated with the acid strength following Nernstian behavior of 59 mV/pKa unit. Thus, selective homogeneous 4e[-]/4H+ O2 reduction to H2O with effective overpotentials as low as 50 mV is achieved by using high-potential Co(por) complexes and modulating the O2/H2O redox couple with different acids. A second effect of this modulation is that the selective reduction of O2 to H2O is observed when the E1/2(CoIII/II) of the monomeric cobalt complexes are above the O2/H2O2 redox couple, implying that the ORR selectivity is tunable based on thermodynamic constraints. A crossover in the LFER of the O2 reduction mediated by the same Co(por) complex exhibits that the susceptibility of the log(TOF) to effective overpotential changes with the ORR selectivity (H2O vs. H2O2). The different slopes of the relationship between log(TOF) and effective overpotential for O2/H2O and O2/H2O2 is elucidated by their distinctive rate laws and catalytic mechanisms. Finally, the different LFERs for the O2 reduction catalyzed by monomeric cobalt and iron complexes between the log(TOF) and effective overpotential are attributed to their different Brønsted coefficients, rate laws, and catalytic mechanisms, and the performance of molecular cobalt and iron ORR catalysts are quantitatively evaluated with LFER analyses. Collectively, this thesis delineates the opportunities for the utilization of molecular cobalt catalysts for achieving selective 2e-/2H+ and 4e[-]/4H+ reduction of O2 with low overpotentials. The overpotential can be tuned using different cobalt catalysts and reaction media under homogeneous conditions, and this feature serves as the basis for switching the selectivity from H2O2 to H2O or vice versa based on thermodynamic restraints.

Download or read book Transition metal free Reduction of Carbon Dioxide written by Marc-André Courtemanche and published by . This book was released on 2015 with total page 228 pages. Available in PDF, EPUB and Kindle. Book excerpt: Only nine years have passed since the seminal discovery that Frustrated Lewis Pairs (FLPs) could split dihydrogen and yet, more than a thousand research papers have already been published on the subject. As the work presented herein commenced, metal-free systems capable of catalytically transforming CO2 could be counted on a single hand while transition-metal based systems were almost as scarce. As such, the present thesis deals with the development of novel transition-metal-free systems for the catalytic reduction of CO2 to energy rich materials, most notably methanol. Firstly, the preparation of a new FLP system bearing three pendant phosphine groups Al(C6H4(o-PPh2))3 and its ability to activate carbon dioxide in a reversible fashion are presented. In the presence of catecholborane, CO2 is catalytically reduced to methoxyboranes, species which are readily hydrolyzed to methanol. Interestingly, a decomposition product is shown to be responsible for the catalytic activity Indeed, species 1-Bcat-2-PPh2-C6H4 is the first report of a catalyst for the metal-free hydroboration of carbon dioxide. The activity of this excessively simple catalyst surpasses that of the best transition metal systems while using the cheap and high hydrogen content borane BH3.SMe2. In-depth mechanistic studies reveals that simultaneous activation of both the borane and CO2 molecules is of critical importance. Further investigation reveals that the formation of an adduct between the catalyst and formaldehyde affords an even more potent organocatalyst. It is also shown that phosphazene superbases are very active organocatalysts for the transformation of CO2 to either formate or methanol derivatives. Unexpectedly, N,N-dimethylformamide (DMF) can promote the reductive hydrosilylation of CO2 in the absence of any catalyst. Finally, the challenging task of developing a metal-free system for the hydrogenation of CO2 was undertaken. A novel strategy was developed by studying the fundamental aspects of FLP mediated hydrogenations, allowing us to achieve CO2 reduction under ambient conditions. While an unexpected decomposition pathway hampered catalysis, optimisation of the catalyst design is expected to yield the first metal-free catalyst for the hydrogenation of CO2.

Download or read book CO2 Hydrogenation Catalysis written by Yuichiro Himeda and published by John Wiley & Sons. This book was released on 2021-06-28 with total page 322 pages. Available in PDF, EPUB and Kindle. Book excerpt: A guide to the effective catalysts and latest advances in CO2 conversion in chemicals and fuels Carbon dioxide hydrogenation is one of the most promising and economic techniques to utilize CO2 emissions to produce value-added chemicals. With contributions from an international team of experts on the topic, CO2 Hydrogenation Catalysis offers a comprehensive review of the most recent developments in the catalytic hydrogenation of carbon dioxide to formic acid/formate, methanol, methane, and C2+ products. The book explores the electroreduction of carbon dioxide and contains an overview on hydrogen production from formic acid and methanol. With a practical review of the advances and challenges in future CO2 hydrogenation research, the book provides an important guide for researchers in academia and industry working in the field of catalysis, organometallic chemistry, green and sustainable chemistry, as well as energy conversion and storage. This important book: Offers a unique review of effective catalysts and the latest advances in CO2 conversion Explores how to utilize CO2 emissions to produce value-added chemicals and fuels such as methanol, olefins, gasoline, aromatics Includes the latest research in homogeneous and heterogeneous catalysis as well as electrocatalysis Highlights advances and challenges for future investigation Written for chemists, catalytic chemists, electrochemists, chemists in industry, and chemical engineers, CO2 Hydrogenation Catalysis offers a comprehensive resource to understanding how CO2 emissions can create value-added chemicals.

Download or read book Fundamental Mechanistic Studies of Formic Acid Decomposition on Transition Metals written by Sha Li and published by . This book was released on 2015 with total page 382 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Mechanistic Studies Related to the Metal Catalyzed Reduction of Carbon Monoxide to Hydrocarbons Progress Report April 1 1979 March 31 1980 written by and published by . This book was released on 1980 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The stoichiometric reactions of metal complexes which parallel probable steps in the metal catalyzed reduction of CO are being investigated. It is hoped that the study of these model reactions will lead to an understanding of the structural factors influencing these individual reaction steps. The information obtained should be useful in the design and discovery of homogeneous catalysts for the reduction of CO to hydrocarbons. We have studied metal formyl complexes which may be involved in the initiation step in CO reduction and have compared metal formyl compounds with metal acetyl compounds. We have found that the structure and kinetic stability of metal formyl compounds are very similar to metal acetyl compounds. However, metal formyl compounds are thermodynamically much less stable than metal acetyl compounds towards decarbonylation. Hydride donation reactions of metal formyl compounds have been discovered. A neutral metal formyl compound has been discovered and its reactions have been investigated. Preparation of (C5H5)Re(CO)(NO)(CH2OH), the first authentic example of a hydroxymethyl metal compound, was accomplished and studies of its reactions with acid, with base, with CO, and with H2 were begun.

Download or read book Earth Abundant Transition Metal Catalyzed Reactions written by and published by Elsevier. This book was released on 2024-09-18 with total page 270 pages. Available in PDF, EPUB and Kindle. Book excerpt: Earth-Abundant Transition Metal Catalyzed Reactions, Volume 74 in the Advances in Catalysis series, highlights new advances in the field, with this new volume presenting interesting chapters. Each chapter is written by an international board of authors. Chapters in this new release include in Chiral Iron Complexes for Asymmetric Catalysis, Recent advances in Ni-catalyzed Functionalization of Strong C-O and C-H Bonds, Low-valent Molecular Cobalt Complexes for Reductive Chemistry, Iron-catalyzed group-transfer reactions with hypervalent iodine reagents, and Iron Porphyrins for Mediating Atom Efficient C–C Bond Formations. Provides the authority and expertise of leading contributors from an international board of authors Presents the latest release in Advances in Catalysis serials Updated release includes the latest information in the field

Download or read book Mechanistic Studies for Catalytic Transformation of Small Oxygenates on Transition Metals written by Suyash Singh and published by . This book was released on 2014 with total page 178 pages. Available in PDF, EPUB and Kindle. Book excerpt: Over the past century, heterogeneous catalysis has played a central role in the development of efficient chemical processes for the conversion of fossil resources to fuels and chemicals, and identification of new, sustainable routes to upgrade renewable carbon sources that minimize the ecological footprint. More recently, unprecedented advances in electronic structure theory and related computational methods have provided a major thrust to the efforts that utilize density function theory (DFT) calculations for developing fundamental atomic-level understanding of these processes, and subsequently designing new and improved catalysts. In this dissertation, a combined theoretical and experimental approach is presented to study the reaction mechanisms for the catalytic conversion of formic acid (FA) and propylene oxide on transition metals. An iterative methodology comprising of DFT calculations, reaction kinetics measurements, and mean-field microkinetic modeling is employed to determine the nature of active sites on supported catalysts, explain the experimentally observed trends, and obtain predictions for the surface environment under reaction conditions. A detailed analysis of the DFT derived thermochemistry and kinetics parameters over a wide range of transition metal surfaces is performed to identify the key reactivity descriptors for FA decomposition on transition metal catalysts, and develop semi-empirical linear correlations that are then used to develop a microkinetic modeling based framework for the identification and design of improved (active and selective) bimetallic alloy catalysts. Finally, the possible utilization and applications of these methods and ideas in other key chemical transformations are proposed, and suggestions for future work are included.

Download or read book Mechanistic Studies of Water Oxidation and Carbon Dioxide Reduction Using Transition Metal Catalysts with Protic Ligands written by Dalton Bodine Burks and published by . This book was released on 2019 with total page 292 pages. Available in PDF, EPUB and Kindle. Book excerpt: The majority of energy produced in the world is derived from fossil fuels which are finite and have deleterious environmental effects. For a sustainable and environmentally-friendly energy future, alternative, renewable energy sources are desired. Two reactions that could have applications towards developing renewable energy sources are water oxidation to produce hydrogen and carbon dioxide reduction to form various products (e.g. formic acid or carbon monoxide); however, these reactions require catalysts to efficiently produce the desired products. Efforts to synthesize, characterize, and study catalysts for these reactions are discussed in this dissertation. The first chapter serves as an introduction to energy-related catalytic reactions. In Chapter 2, 6,6ʹ-dihydroxybipyridine (6,6ʹ-dhbp)-a protic ligand used with several metals to produce catalysts for energy-related reactions-is studied to determine its thermodynamic acidity. In the following chapter, 6,6ʹ-dhbp is used as a ligand with copper to form complexes that are water oxidation catalysts. Chapters 4 and 5 focus on iridium and ruthenium complexes containing new bidentate ligands composed of pyridinol and N-heterocyclic carbenes (NHCs). These complexes, along with an iridium complex of 6,6ʹ-dhbp, were used as catalysts for the hydrogenation of carbon dioxide to formate and the reverse dehydrogenation of formic acid to carbon dioxide and hydrogen. However, the complexes containing the new bidentate pyridinol-NHC ligands were found to be precatalysts as they undergo transformations and decomposition during the course of the reaction. A nickel-pincer complex with a protic CNC-pincer derived of pyridinol and NHCs was used as a photocatalyst for carbon dioxide reduction in Chapter 6. The protic state of the hydroxy group in the 4-position of the pyridine ring was determined to be important for catalysis, as the deprotonated hydroxy group results in 10 times the catalytic ability as the protonated form. In the penultimate chapter, ruthenium-pincer complexes that are active carbon dioxide photoreduction catalysts are studied mechanistically by UV/vis and IR spectroscopies. The most active catalyst was studied in greater detail with real-time IR spectroscopy to help elucidate potential reaction pathways. The final chapter serves as a conclusion to summarize the results discussed in the dissertation.

Download or read book Computational Mechanistic Studies on the Transition Metal Catalyzed Activation of Carbon Dioxide written by Rositha Kuniyil and published by . This book was released on 2017 with total page 168 pages. Available in PDF, EPUB and Kindle. Book excerpt: El mecanisme d'exemples representatius de reaccions involucrant diòxid de carboni i complexos amb metalls de transició han estat caracteritzats amb l'ajuda d'una varietat de mètodes computacionals: DFT (Teoria del funcional de la densitat) i models micro-cinètics. Tres procesos diferents han estat analitzats. La carboxilació d'al·lens, catalitzada per pal·ladi i assistida per alumini, s'ha trobat que té lloc mitjançant un mecanisma complex que pot explicar totes les dades experimentals aportades per reaccions estequiomètriques de passos específics per part de Hazari i col·laboradors. S'ha trobat que l'additiu tri(etil)alumini juga un rol clau en tant l'activació d'al·lens com del diòxid de carboni. La reacció de diòxid de carboni amb siloxi silans assistida per fluorur s'ha trobat que està significativament afectada per la naturalesa del contraió que acompany l'anió fluorur, el qual participa en les dues etapes d'abstracció del silil. El mecanisme de la conversió de carbonats cíclics a amines al·líliques i aldehids al·lílics catalitzat per pal·ladi ha estat examinada en col·laboració amb el grup experimental del Professor Kleij, del nostre mateix institut. Hem el·lucidat un mecanisme amb un intermedi cilometal·lat clau que explica l'elevada selectivitat del procés. Esperem que aquests estudis computacionals contribueixin a la comprensió de detalls importants de les reaccions esmentades, i també a dissenyar estratègies més eficients per aconseguir una química més sostenible basada en l'activació del diòxid de carboni.

Download or read book Homogeneous Solution Electrocatalysts for CO2 Reduction written by and published by . This book was released on 1991 with total page 6 pages. Available in PDF, EPUB and Kindle. Book excerpt: The goal of the research funded by this grant was to develop new electrocatalysts for CO2 reduction, and to probe the fundamental mechanisms of the steps that lead to the reduction of CO2. As the title suggests, this initially involved the synthesis of soluble transition metal complexes. More recently, the inability of the homogeneous catalysts to reduce CO2 past the two- electron stage, and the results of mechanistic studies, led us to investigate heterogeneous systems that could access more than two electron equivalents. Our initial investigations led to the preparation of polypyridyl complexes of ruthenium, osmium, rhenium, iridium, and rhodium.

Download or read book Studies of Electrocatalytic Carbon Dioxide Reduction by Biomimetic Bipyridyl based Rhenium Tricarbonyl Complexes written by Steven Adrian Chabolla II and published by . This book was released on 2017 with total page 125 pages. Available in PDF, EPUB and Kindle. Book excerpt: The use of CO2 as a chemical feedstock has been the focus of much research in recent years due to the promise for carbon neutral fuel storage in chemical bonds. Specifically, complexes of the type Re(bpy)(CO)3Cl (bpy = 2,2'-bipyridine and analogues thereof) have been studied for their ability to electrocatalytically reduce CO2 to CO. These catalysts are among the most active, selective, and robust homogeneous catalysts for CO2 reduction in the literature. Previous work has focused on mechanistic studies and determining the inductive effect of bipyridine functional groups on catalysis. The work presented in this dissertation focuses on the structural and biomimetic modification of these catalysts. In order to determine the optimal point of modification, the CO2 reduction capabilities of a series of Re(n,n'-dimethyl-bpy)(CO)3Cl (n = 3, 4, and 5) catalysts with a bpy modified at the 3, 4, and 5 positions with methyl substituents were assessed. A decreased catalytic current response in the n = 3 case can be explained by steric hindrance in the 3,3'- substituted catalyst disfavoring optimal charge transfer in the catalytic cycle. A series of rhenium catalysts were synthesized with bpy substituents amenable to common surface- and bio-conjugation techniques. Specifically, aminomethyl, groups were found to contribute to competent catalysts and were interrogated further. Interestingly, before the complex was coupled to amino acids, simple acylated amines (mimicking peptide bonds) on the 4- and 4,4'- positions of the bpy ligand were found to alter the mechanism by the rhenium catalyst operated electrochemically. Instead of a single metal site catalyzing the proton-dependent reduction of CO2 to CO and H2O, the bimetallic site, templated by hydrogen-bonding of the peptide bonds, reduces CO2 to CO and CO32- at potentials up to 240 mV more positive than previously studied catalysts of this type. The catalysts were then incorporated into amino acids and short peptides to investigate the advantageous effects of adding proton sources (tyrosine) and readily modifiable platform (peptides) on catalysis. In addition to proton sources, Lewis-acids can serve to increase the rates of catalysis; however insoluble carbonates prevent the reaction from being catalytic with respect to the Lewis acid. Macromolecules were used to bind the metal Lewis acids to prevent metal-carbonate formation over the course of the reaction. Furthermore, hydrogen-bonding could be utilized to template these heterobimetallic interactions and the preliminary work is presented.

Download or read book On Tuning and Understanding Electrocatalysts for Hydrogen and Carbon based Energy Storage written by Michael T Tang and published by . This book was released on 2020 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The following thesis is a composition of published and soon-to-be published works. All works use density functional theory (DFT) calculations and descriptor-based mechanistic models to tune and screen catalytic materials for the hydrogen evolution reaction (HER) and the CO2 reduction reaction (CO2RR). In several works, experiments are included to substantiate predictions. The early sections focus on elucidating the role of key descriptors in the HER and CO2RR, specifically the H* and CO* adsorption state. It was found that nickel-gallium intermetallic systems can alter the CO* adsorption energy to achieve an early onset potential for C1 and C2 product distributions. With regards to system stability, CO* adsorption was found to induce surface refaceting towards stepped motifs on three commonly used metal catalysts, Cu, Ni, and Pt. In the latter sections, the thesis builds upon past mechanistic models to develop a multi-descriptor model that suggests new strategies to screen for better catalysts for CO2RR. It is found that not all steps may be necessarily electrochemical steps; some key intermediate steps may be surface driven, which dramatically simplifies the selectivity picture of products formed in CO2RR. As such, OH* and C* are noted as possible descriptors to use in conjunction with CO* to build potential-dependent selectivity maps that describe how the competition from the HER may affects product selectivity in CO2RR. Finally, the thesis dives into the mechanistic trends of HER, where kinetic scaling relations are calculated explicitly with a metal-water interface across multiple transition metals. It was found that the Volmer-Heyrovsky route can produce an optimal peak at ∆G_H* = ~0eV, where ∆G_H* is the free binding energy of hydrogen. The active species of H* has also been elucidated to be any adsorbed hydrogen, and not strictly H* adsorbed on weaker binding, atop sites. Tafel plots indicate that although electrochemical barriers vary with potential, the overall HER rate stays governed by the surface coverage of hydrogen. Lastly, we find that CO* and OH* adsorbate-adsorbate interactions can either hinder or promote HER by leaving only weaker binding sites to H*. Prior to presenting the findings, this thesis attempt at a short primer on the physical chemistry concepts behind computational catalysis, as well as the conceptual tools used in computational catalysis. The section is aimed at theoretical or experimental researchers with an interest in computational science and catalysis. This is in part because the technical jargon used herein may seem vague or less familiar to those not in the field of computational catalysis, such as the term 'free energetics', 'atomic orbitals', 'descriptor', 'scaling relations'. The reader is welcomed to bring themselves up to speed in the background and concepts section.