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

EAGER：利用系统第一原理化学空间探索加速催化剂发现

• 批准号: 1338421
• 负责人: Ramamurthy Ramprasad
• 金额: $ 6万
• 依托单位: University of Connecticut
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2014-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1338421&HistoricalAwards=false
• 关键词: EAGER; Accelerating; catalyst; discovery; using

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.

摘要PI：Ramprasad，Ramamurthy提案编号：1338421机构：康涅狄格大学标题：EAGER：利用系统的第一性原理化学空间探索加速催化剂发现该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，以加速下一代催化剂的发现和设计。第二代氧化物催化剂，用于涉及氧化学的化学反应。PI将专注于通过掺杂元素周期表中的元素对二氧化铈进行化学改性（总共45个，包括K-As、Rb-Sb和Cs-Bi），评估二氧化铈中掺杂剂的稳定性，并询问掺杂剂改变涉及H2O、CO、CO2、O2和H2的化学反应的倾向。换句话说，其目的是快速筛选氧化铈中的掺杂剂，这些掺杂剂可以显著增强水煤气变换反应（WGS：CO + H2O-CO2 + H2）。智力优势：WGS是工业化学过程中不可或缺的单元操作，用于制造氨、甲醇、烃和氢。该反应是轻微放热的（反应焓=-41.1kJ/mol），并且平衡有利于在低温下形成产物。然而，典型催化剂上的动力学在低温下是缓慢的。目前使用的铜基氧化铈负载的WGS催化剂价格便宜。然而，它们在操作、稳定性和由于S和Cl而失活的倾向方面具有许多缺点。因此，严格的（和昂贵的）操作员培训已成为不可避免的，以延长商业WGS催化剂的寿命。相比之下，相对昂贵的贵金属催化剂，如Pt、Pd、Rh、Ru，具有高的本征活性。高成本阻碍了它们在工业规模WGS工艺中的实施。为了识别更多有前途的WGS催化剂系统，PI将使用第一原理密度泛函理论（DFT），以“高通量”的方式进行，以使他能够快速考虑在铈镧周期表中的金属掺杂元素阵列（共45个，包括K-As，Rb-Sb和Cs-Bi）。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库来解决复杂的化学相互作用，这可能导致最佳催化剂开发的突破，即使是成熟和众所周知的化学过程。从长远来看，这项调查可以帮助基本理解的信息为基础的rationalcatalytic design增强稳定性和performance. The PI的工业经验将加强学生的工程教育和willaid在拓宽学生的接触学术环境之外。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。