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

摘要项目负责人：Ramprasad， ramamurthy提案编号：1338421机构：University of connecticut标题：EAGER：利用系统第一性原理化学空间探索加速催化剂的发现本项目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集成范式，以加速发现和设计涉及氧化学化学反应的下一代氧化物催化剂。该项目将重点关注通过掺杂元素周期表中的元素（总共45种，包括K-As、Rb-Sb和Cs-Bi）对铈进行化学修饰，评估铈中掺杂剂的稳定性，并研究掺杂剂改变H2O、CO、CO2、O2和H2等化学反应的倾向。换句话说，目的是快速筛选能显著增强水气转换反应（WGS: CO + H2O - CO2 + H2）的铈中掺杂剂。知识优势：WGS是工业化学过程中生产氨、甲醇、碳氢化合物和氢的整体单元操作。该反应为轻度放热反应（反应焓为-41.1 kJ/mol），反应平衡有利于在低温下生成产物。然而，在低温下，典型催化剂的反应动力学是缓慢的。目前使用的铜基铈负载的WGS催化剂价格低廉。然而，它们在操作、稳定性和由于S和Cl导致的失活倾向方面存在许多缺点。因此，为了延长商用wgs催化剂的使用寿命，必须对操作人员进行严格（且昂贵）的培训。相比之下，相对昂贵的贵金属催化剂，如Pt、Pd、Rh、Ru，具有较高的本构活性。高成本阻碍了它们在工业规模ewgs工艺中的实施。为了确定许多更有前途的WGS催化剂系统，PI将使用第一性原理密度泛函数理论（DFT），以“高通量”的方式进行，使他能够快速考虑在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）。这是一系列筛查程序的第一步，然后才能对选定的少数病例进行详细评估。更广泛的影响：除了加强对WGS的基本理解外，该项目还将提供一个知识基础，以解决复杂的化学相互作用，从而在最佳催化剂开发方面取得突破，即使是对于已经建立和熟知的化学过程也是如此。从长远来看，这项研究有助于从根本上理解基于信息学的合理催化剂设计，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视野。PI将把量子力学建模技术及其在催化中的应用整合到多个课程中。

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.