EAGER: Accelerating catalyst discovery using systematic first principles chemical space explorations

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AbstractPI: Ramprasad, RamamurthyProposal number: 1338421Institution: University of ConnecticutTitle: EAGER: Accelerating catalyst discovery using systematic first principles chemical space explorationsThe vision underlying this project is to create an integrated paradigm based on high throughputfirst principles density functional theory computations to accelerate the discovery and designof next-generation oxide catalysts for chemical reactions involving oxygen chemistry.The PI will focus on chemical modifications of ceria through doping with elements across the Periodic Table(45 in all, including K-As, Rb-Sb, and Cs-Bi), assess the stability of the dopants in ceria,and interrogate the propensity of the dopant to alter chemical reactions involving H2O, CO,CO2, O2 and H2. In other words, the intent is to rapidly screen for dopants in ceria thatcan significantly enhance the water-gas shift reaction (WGS: CO + H2O - CO2 + H2).Intellectual Merit :WGS is an integral unit operation in industrial chemical processes to manufacture ammonia,methanol, hydrocarbons, and hydrogen. The reaction is slightly exothermic (enthalpy of reaction= -41.1 kJ/mol) and the equilibrium favors product formation at low temperature. However,the kinetics on typical catalysts are slow at low temperature. The currently employed Cu-basedceria-supported WGS catalysts are cheap. However, they have a number of disadvantages in termsof operation, stability and propensity for deactivation due to S and Cl. As a result, rigorous(and expensive) operator training has become inevitable to prolong the life of the commercialWGS catalysts. In contrast, the relatively expensive noble metal catalysts, such as Pt, Pd,Rh, Ru, have high intrinsic activity. High cost has hindered their implementation in industrial-scaleWGS processes.In an attempt to identify many more promising WGS catalyst systems,the PI will use first principles density functional theory (DFT), performed in a "high-throughput"manner to allow him to rapidly consider an array of metallic dopant elements in ceriaspanning the Periotic Table (45 in all, including K-As, Rb-Sb, and Cs-Bi). This is the firststep in a hierarchy of screening procedures before a detailed assessment can be made on a few selected cases.Broader Impacts :Aside from enhancing the fundamental understanding of WGS, the project will provide a knowledge baseto tackle complex chemistry interactions that could lead to breakthroughs in optimum catalystdevelopment, even for well-established and well-known chemical processes. In the long-term,this investigation could aid in the fundamental understanding of informatics-based rationalcatalyst design for enhanced stability and performance.Industrial experience of the PI will enhance the engineering education of students and willaid in broadening student exposure beyond the academic environment. The PI will integratequantum mechanical modeling techniques, and their applications in catalysis, into multiple courses.