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

University Of Connecticut, Storrs CT

Investigators

Abstract

Abstract PI: Ramprasad, Ramamurthy Proposal number: 1338421 Institution: University of Connecticut Title: EAGER: Accelerating catalyst discovery using systematic first principles chemical space explorations The vision underlying this project is to create an integrated paradigm based on high throughput first principles density functional theory computations to accelerate the discovery and design of 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 that can 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-based ceria-supported WGS catalysts are cheap. However, they have a number of disadvantages in terms of 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 commercial WGS 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-scale WGS 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 ceria spanning the Periotic Table (45 in all, including K-As, Rb-Sb, and Cs-Bi). This is the first step 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 base to tackle complex chemistry interactions that could lead to breakthroughs in optimum catalyst development, even for well-established and well-known chemical processes. In the long-term, this investigation could aid in the fundamental understanding of informatics-based rational catalyst design for enhanced stability and performance. Industrial experience of the PI will enhance the engineering education of students and will aid in broadening student exposure beyond the academic environment. The PI will integrate quantum mechanical modeling techniques, and their applications in catalysis, into multiple courses.