GOALI: Atomic Tailoring of Catalyst Surfaces for High Selectivity: Partial Oxidation of Propane

建议标题：GALI：用于高选择性的催化剂表面的原子剪裁：丙烷部分氧化建议编号：CTS-0432593主要研究人员：约翰·T·格里夫斯机构：华盛顿大学混合金属氧化物(MMO)被广泛用作石油、化工、环境和制药行业的催化剂。催化剂性能的一个控制因素是MMO表面的氧和金属物种的浓度。工业MMO催化剂是通过块体技术制备的，这种技术提供了对表面性质的有限控制。具有相同大块晶体结构和组成的样品在不同的制备方法下可以表现出不同的性能。这种差异可以归因于一个或多个催化剂组分的表面浓度的变化。这一目标研究项目将建立一种新的方法，在保持本体组成不变的情况下，向块状催化材料的表面添加原子，并绘制出表面受热或暴露在反应物混合物中时催化性能的变化。这种被称为“原子剪裁”的新工艺将被用来开发高选择性和高活性的丙烷部分氧化制丙烯酸催化剂。原子束沉积，一种用于表面科学的技术，已经被采用，以便金属原子(包括那些高熔点的)可以直接沉积在颗粒上。沉积后，将使用特殊的真空瞬变响应实验(称为TAP实验)来监测改性材料受热并暴露在反应物气氛中的催化性能。改进的丙烷转化为丙烯酸的催化剂将允许丙烷取代丙烯作为原料。丙烷的原料成本较低，加上直接法而不是两步法所提供的资本减少，将使生产成本降低20%-25%。制备活性更高、选择性更好的丙烷部分氧化催化剂所获得的知识将适用于其他选择性氧化反应，特别是其他烷烃的反应。从美国经济和环境的角度来看，开发用于烷烃活化和选择性氧化为商业有用产品的新催化剂将带来高达37万亿BTU/年的能源节约，并将显著减少温室气体的产生。这项研究发表的结果也将对其他正在设计实验以探测复杂催化表面上的分子水平过程的研究人员有用。这一目标课程将向研究生和本科生介绍令人兴奋的现实世界问题，这些问题一旦得到解决，将会对经济、社会和环境产生重大影响。学生将作为不同团队的一部分工作，他们将获得设计、构建和运行定义最先进水平的复杂实验的实践经验。该计划大力鼓励少数民族和女性学生参与研究，同时仍然鼓励所有本科生攻读更高的学位。研究生和本科生将在工业实验室与工业研究人员合作，并将有机会在学术-工业小组会议和国家科学会议上展示他们的工作。

AbstractProposal Title: GOALI: Atomic Tailoring of Catalyst Surfaces for High Selectivity: Partial Oxidation of Propane Proposal Number: CTS-0432593Principal Investigator: John T. GleavesInstitution: Washington University Mixed metal oxides (MMO) are widely used as catalysts in the petroleum, chemical, environmental, and pharmaceutical industries. A controlling factor in catalyst performance is the concentration of oxygen and metal species in the MMO surface. Industrial MMO catalysts are prepared by bulk techniques, which provide limited control of surface properties. Samples with the same bulk crystal structure and composition can exhibit different performance when prepared by different routes. This difference may be attributed to a change in the surface concentration of one or more of the catalyst constituents. This GOALI research project will establish a new method of adding atoms to the surface of bulk catalytic materials while maintaining the same bulk composition, and charting the change in catalytic properties as the surface is heated or exposed to a reactant mixture. This new process, dubbed "atomic tailoring", will be used to develop highly selective and active catalysts for the partial oxidation of propane to acrylic acid. Atomic beam deposition, a technique used in surface science, has been adapted so that metal atoms (including those with high melting points) can be directly deposited on particles. After deposition, special vacuum transient response experiments (called TAP experiments) will be used to monitor catalytic properties as the modified material is heated and exposed to a reactant atmosphere.Improved catalysts for propane conversion to acrylic acid will allow propane to replace propene as a feedstock. The lower feedstock cost for propane, coupled with reduced capital afforded by a direct rather than two-step process, will lower production costs by 20-25%. The knowledge gained from fabricating more active and selective partial oxidation catalysts for propane will be applicable to other selective oxidation reactions, especially reactions of other alkanes. From a U.S. economic and environmental perspective, the development of new catalysts for alkane activation and selective oxidation to commercially useful products will deliver energy savings of up to 37 trillion BTUs/yr and will significantly reduce the generation of green-house gases. Published results from this study will also be useful to other researchers who are designing experiments to probe molecular level processes on complex catalytic surfaces. This GOALI program will introduce graduate and undergraduate students to exciting real-world problems that when solved will have a significant economic, social, and environmental impact. Students will work as part of a diverse team, and they will gain hands-on experience designing, building, and running complex experiments that define the state of the art. The program strongly encourages minority and female students to become involved in research while still encouraging all undergraduates to pursue advanced degrees. Graduate and undergraduate students will work with industrial researchers at an industrial laboratory and will have the opportunity to present their work at academic-industrial group meetings and at national scientific meetings.