Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Cong Liu Project Name: Hetero_Catalysis Division: CSE Project title: Development of Novel Heterogeneous Catalysts for Effective CO2 Conversion to Fuels Associated funding: Catalysis group fundings Other Systems: Science: The conversion of CO2 to fuels is of use for renewables in carbon-neutral technologies and for developing approaches to mitigate global warming. The high thermodynamic stability of the CO2 molecule requires substantial input of energy for its reduction and conversion. Although a number of recent studies have helped to better understand CO2 activation/reduction using catalysts, the catalytic conversion of CO2 to hydrocarbon fuels (e.g., CH3OH, CH4) is still a challenging problem. For instance, although CO2 has been shown to be reduced directly on metal surfaces, the surfaces become quickly poisoned and deactivated by the reduction products (e.g., CO).[1] Studies have achieved the reduction of CO2 to CO and formate. However, further transformation of CO and formate to more useful products such as methane or methanol requires multiple hydrogenation steps, and has only been demonstrated with low efficiency. Our work in this area will be focused on using computational methods to understand the chemical insights of the reductive conversion of CO2 to hydrocarbons on supported transition metal nanomaterials. Materials including subnanometer metal clusters and 2-dimensional transition metal dichalcogenide (TMDC) nanoflakes are taken into account. The computational studies provided not only the molecular understanding and explanations for the experimental results, but also predicted critical trends of the catalytic properties of different materials, where were confirmed by the experimental studies. Project description: Previously, we have developed highly active transition metal dichalcogenide (TMDC) nanoflakes, i.e., WSe2, for CO2 electrochemical reduction to CO (Science, 2016, 353(6298); ACS Nano, 2017, 11, 453−460) In the following year, we are going to focus on more detailed studies and predictions of the catalytic properties of transition metal dichalcogenide nanoflakes for electrochemical CO2 reduction: 1. Electrochemical reduction of CO2 to hydrocarbons on TMDC nanoflakes. Previously, the computational and experimental efforts were only focused on CO2 reduction to CO. In our experimental device, the products are a mixture of CO and H2 (syn-gas), which can be used for the synthesis of hydrocarbon fuels. It would be a significant improvement of the catalytic system if CO2 can be converted directly to hydrocarbon fuels. Future computational studies will be focused on understanding the electrochemical reduction of CO2 to hydrocarbon fuels on TMDC nanomaterials, and predict effective catalytic systems prior to experiment. Reaction mechanisms and energetics will be investigated systematically for a series of TMDC materials, and the most promising catalyst system will be identified for further experimental studies. 2. Functions of ionic liquids and other electrolytes in the electrocatalysis of CO2 reduction. In our previous studies, we discovered that utilizing ionic liquids in the electrolyte system promotes the catalytic performance of the TMDC nanomaterials for CO2 reduction. However, the exact role of the ionic liquid is still unknown. In addition, carbonate and hydroxide electrolytes are also of great interest. In the future studies, we are going to carry out detailed computational studies to investigate the interactions between ionic liquid ions and the electrode (catalyst) active site, and the electronic effects of the ionic liquid in the electocatalytic process. Furthermore, the effect of using carbonate and hydroxide electrolytes will also be explored. Calculations will be focused on the distribution of different electrolyte ions near the catalyst surface and participation of these ions in the catalytic reactions. Both explicit and inexplicit solvent effects will be taken into account, and the effect of external potential will be studied. 3. Catalytic reaction pathways at different pH values will be investigated. Previously, our studies mainly were focused on acidic solutions, where protons are abundant in the electrolyte and act as proton donors during the electrocatalysis. However, our experimental collaborators have discovered that these TMDC materials work very well under pH neutral conditions. In this condition, H2O will likely act as the proton donor. Therefore, we will carry out calculations to investigate the reaction mechanisms of CO2 electrochemical reduction at pH neutral conditions and how pH affects the properties of the catalysts. A regular calculation will require 64 processors of about 10 hours of running time. Approximately 700 calculations will be carried out, and totally about 450000 cpu hours will be necessary. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 480000 Q1: 120000 Q2: 120000 Q3: 120000 Q4: 120000 Justification: Storage requirements: Thank You, The LCRC Accounts System