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

PI：Ramprasad，Ramamurty Proposal编号：1338421机构：康涅狄格大学标题：HEARGER：使用系统的第一性原理化学空间探索加速催化剂发现这个项目背后的愿景是创建一个基于高通量第一性原理密度泛函理论计算的综合范式，以加速发现和设计涉及氧气化学的化学反应的下一代氧化物催化剂。PI将专注于通过在元素周期表(总共45个元素，包括K-As、Rb-Sb和Cs-Bi)中掺杂对CeO2进行化学修饰，评估CeO2中掺杂物的稳定性，并询问掺杂物改变涉及H2O、CO、CO2、O2和H2的化学反应的倾向。换句话说，目的是快速筛选CeO2中可以显著增强水-气变换反应(WGS：CO+H2O-CO2+H2)的掺杂物。智力优势：WGS是工业化学过程中生产氨、甲醇、碳氢化合物和氢气的整体单元操作。该反应为轻微放热反应(反应热焓为-41.1kJ/mol)，在低温下平衡有利于产物的生成。然而，典型催化剂在低温下的反应动力学较慢。目前使用的铜基CeO_2负载的WGS催化剂价格低廉。然而，它们在操作、稳定性和因S和氯离子引起的失活倾向方面都有一些缺点。因此，严格的(且昂贵的)操作员培训已成为延长商用WGS催化剂寿命的必然。相比之下，价格相对较高的贵金属催化剂，如铂、钯、Rh、Ru，具有较高的本征活性。高昂的成本阻碍了它们在工业规模的WGS工艺中的实施。为了寻找更有前途的WGS催化剂体系，PI将使用第一性原理密度泛函理论(DFT)，以高通量的方式执行，使他能够快速考虑元素周期表中的一系列金属掺杂元素(总共45种，包括K-As、Rb-Sb和Cs-Bi)。这是筛选程序分级的第一步，然后才能对选定的几个案例进行详细评估。广泛的影响：除了加强对WGS的基本了解外，该项目还将提供一个知识库，以处理复杂的化学相互作用，这些相互作用可能导致最佳催化剂开发方面的突破，即使是成熟和众所周知的化学过程也是如此。从长远来看，这项调查将有助于对基于信息学的合理催化剂设计的基本了解，以提高稳定性和性能。PI的工业经验将加强学生的工程教育，并有助于拓宽学生在学术环境之外的接触。PI将把量子力学建模技术及其在催化中的应用整合到多门课程中。

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.