Hello, A new project on the LCRC cluster has been requested. Please forward the information on to the LCRC Allocation sub-committee. Applicant's name: Badri Narayanan Applicant's institution: ANL Applicant's division: MSD Project Name: BioFuel Project title: Metal carbide catalysts for upgrading bio-fuels Associated funding: EERE Other Systems: Science: Biomass holds tremendous promise as a sustainable source of carbon for synthesizing fuels, chemicals, and other carbon-based materials. In particular, the ubiquitous presence of oxygenate hydrocarbons in bio-mass derivatives has made the removal of O a critical research direction towards bio-fuel upgrading in the recent times. Two promising routes to reduce O content of bio-mass derivatives are (a) hydrodeoxygenation, involving C-O/C=O bond cleavage, and (b) decarbonylation or decarboxylation via C-C bond scission. Among these, the former (hydroxylation) has garnered lot of interest since it involves selective dissociation of C-O bonds while retaining the C-C chains; additionally, it produces H2O as by-product, which is more environment friendly than decarbonylation/decarboxylation that leads to CO2. Recently, metal carbides, e.g., Mo2C have been reported to be very effective in selectively catalyzing scission of C-O/C=O bonds without influencing the C-C bonds. Introduction of suitable dopants, e.g., Ni have been found to enhance selectivity, activity, and stability of these catalysts. Although experimental works on Ni-doped Mo2C indicate great promise of these catalysts for bio-fuel upgrading, a fundamental understanding of the role of dopants, including the type of dopants and their concentration in enhancing catalytic properties of Mo2C are not well known. Such knowledge is crucial to design new catalysts with exceptional selectivity, catalytic activity, and stability. In this project, we will employ total energy calculations, nudged elastic band barrier calculations, and charge distribution analysis in the framework of density functional theory (DFT) to understand the role of Ni, and its concentration on the catalytic activity of Mo2C catalysts. An important descriptor of the catalytic activity of Mo2C is the O* removal at Mo2C, since strong binding of O* on Mo2C can cause slow desorption of adsorbed atomic O and lead to catalyst poisoning. Hence, we will focus on binding energies of reaction intermediates during O* removal, namely O*, OH*, H2O*, and H * at different levels of Ni doping. This study will not only advance the fundamental knowledge of metal-carbide chemistry, but also enable computation-aided accelerated discovery of catalysts for bio-fuel upgrading. Project description: Our efforts will be focused on one commonly employed Mo2C surface, namely (001). We will employ density functional theory (DFT) calculations to compute the adsorption energies, as well as atomic charges for 4 adsorbents: (a) O*, (b) OH*, (c) H2O*, and (d) H* on Mo2C (001) doped with Ni at 5 different concentrations in the range 0--8% by weight. All the calculations will be performed on a Ni-Mo2C (001) slab using plane-wave DFT package VASP; the Brillouin zone will be sampled with 4 x 4 x1 Monkhorst-Pack grid, and plane wave energy cutoff of 400 eV will be used. The Perdew-Burke-Ernzerhof pseudopotentials will be employed for exchange correlations within the generalized gradient approximation. The atomic positions for the dopant Ni atoms, as well as the adsorbents are known from our recent computational work. Each of these simulations is expected to take 150 hours on 96 cores (i.e., 3 nodes on Bebop). So, we need 5 (concentrations) x (4 (adsorbents) + 1(bare slab)) x 96 (cores) x 150 (hours) = 360,000 core hours. Next, we will compute the energy barriers for 3 different reactions (a) O* + H* ↔ OH* +*, (b) OH* + H* ↔ H2O* +*, and (c) OH* + OH* ↔ H2O* +O* at each dopant concentration using climbing image nudged elastic band approach. Each of these calculations is expected to take about 96 hours on 96 cores. So, we require 5 (concentrations) x 3 (reactions) x 96 (cores) x 96 (hours) = 138,240 core hours. In all, we require a total of 498,240 core hours Industry partnership: Project URL: Requested allocation: 498240 Q1: 124560 Q2: 124560 Q3: 124560 Q4: 124560 Justification: Storage requirements: 1 TB The requester has used undetermined amount hours of their initial startup project. In addition to approving an initial amount, please specify a Category and Subcategory for this project. For a list of the current selection of approved categories, please see: https://wiki.lcrc.anl.gov/wiki/Processes/Categories Once the Allocation committee has approved the project, please go to the Project Management page to create it: https://accounts.lcrc.anl.gov/projects.php Thank You, The LCRC Accounts System