A Computational Study of 2 Electron Oxygen Reduction Reaction for Direct H2O2 Electrosynthesis

Journal Title
Journal ISSN
Volume Title
Hydrogen peroxide has been identified as one of the 100 most important chemicals for global industry. This environmentally friendly oxidizing agent has many uses in several industrial sectors, including textiles, chemical synthesis, water treatment, and disinfection. The current industrial method for mass production of H2O2 is the anthraquinone process, which is energy-intensive. Additionally, environmental and transportation concerns involving the anthraquinone process make it an unsustainable method for H2O2 production. Therefore, direct electrochemical synthesis of H2O2 via 2e− oxygen reduction reaction (ORR) has gained attention from researchers in this field. This thesis is focused on developing selective electrocatalytic materials for 2e−ORR. This research employed computational chemistry theories and methods, namely Density Functional Theory (DFT), to study the electrochemical synthesis of H2O2 on carbon-based and metal electrocatalysts. DFT-based calculations have been carried out to estimate adsorption energy and formation energy, as well as Bader charge analysis and Density of States (DoS) calculations to gain insight into the thermodynamics of the reaction and the nature of the active sites. In Chapter 3, partially oxidized Pd carbon nanotubes have been investigated as a potential electrocatalyst for 2e− ORR. The results suggest the interaction between certain Pd clusters and the nearby oxygen-containing functional groups is key to reach high selectivity and low overpotential for 2e− ORR. Chapter 4 investigates an oxygen-functionalized ”holey graphene” structure as a low-cost and highly selective ORR catalyst. DFT calculations identified the presence of a mixture of functional groups that makes the neighboring carbons a suitable active site for selective H2O2 electrosynthesis. In the final section (chapter 5), we investigated a Au-based catalyst with a Pd surface layer. The thermodynamic analysis directly connected the number of Pd atoms and H2O2 selectivity. This thesis aims to support efforts to make the direct synthesis of H2O2 a more feasible process.
Mostaghimi, A. H. B. (2024). A computational study of 2 electron oxygen reduction reaction for direct H2O2 electrosynthesis (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.