Catalytic Nanodiode

催化纳米二极管

• 批准号: 0854324
• 负责人: Eduardo Wolf
• 金额: $ 37.19万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-01-15 至 2013-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0854324&HistoricalAwards=false
• 关键词: Catalytic; Nanodiode

0854324 Wolf, Eduardo E. The objective of the proposed work is to nanofabricate a catalytic diode as a model of a metal-oxide supported catalyst with the added capability to alter the electronic properties at the metal-support interface by application of an external potential. We propose to use IR spectroscopy to probe the effect of the electric field on the CO-metal surface bond. Depending on the IR results, we propose to measure the activity and selectivity as a function of applied voltage for one of two probe reactions: CO oxidation and hydrogenation of 1,3-butadiene. The catalytic nanodiode will be characterized with solid and surface analysis techniques to determine a correlation between electronic properties and catalytic activity. The novelty of the catalytic diode as a model catalyst is that it enables to study the effect of an external electrical field that has not been investigated in catalysis before. This will permit to elucidate separately the effect of electronic properties at the metal semiconductor boundary from compositional and crystallite size effects. We also propose to perform first principles molecular simulations of an analog of the junction to further understand the effect of the external field on electronic properties. The intellectual merit of this project is the investigation of a new concept of a model catalyst in which the activity of a metal-oxide interface will be altered by an external voltage. The results obtained will be the first investigation of this effect in catalysis and they will improve our understanding of the electronic effect in catalytic activity at metal-support interfaces, which although known for many years, had eluded a correlation with catalytic activity. The proposed studies will be transformative and of fundamental nature, since the model catalyst is costly to fabricate and has limited surface area. Nonetheless, we expect that the knowledge gained in these studies will permit design new improved metal catalysts supported on oxides. The results could also be relevant to other technologies involving junctions such as solar cells and solid state sensors. The broader impact of the proposed research rests upon its multi-disciplinary character including electrical engineering, advanced nanofabrication techniques, kinetics and catalysis, as well as computational chemistry. To further aid the professional growth and diverse learning experience for students of underrepresented groups, support is given for the Minority Engineering Program at Notre Dame (www.nd.edu/-mepnd) for participation in hands-on experiments. The research results will be disseminated through presentations in national meetings and publications in scientific journals in the area of catalysis, nanofabrication and computational catalysis. In addition to the existing Web pages of each investigator, a web page is under construction to publicize the work under the direction of the lead PI and collaborators in combustion synthesis in catalysis, and the work proposed here once definitive results are obtained. In addition, we propose to extrapolate what we learn about electronic effects in the nanodiode and apply it in the preparation of real metal-oxide supported catalyst. We expect that these results will bring transformative knowledge to the design of more active and selective catalysts. The fundamental insights gained in the proposed work from the combined expertise of the PI's in catalysis and co-PIs in nanofabrication and computational chemistry will benefit society in its potential use in critical technologies impacted by catalysis such as energy and in the chemical industry.

0854324 Wolf，Eduardo E。拟议工作的目标是纳米制造催化二极管作为金属氧化物负载催化剂的模型，并具有通过施加外部电势来改变金属-载体界面处的电子特性的附加能力。我们建议使用红外光谱来探测电场对CO-金属表面键合的影响。根据红外结果，我们建议测量两个探针反应之一的活性和选择性作为施加电压的函数：CO 氧化和 1,3-丁二烯氢化。催化纳米二极管将通过固体和表面分析技术进行表征，以确定电子特性和催化活性之间的相关性。催化二极管作为模型催化剂的新颖之处在于，它能够研究以前在催化中未研究过的外部电场的影响。这将允许分别阐明金属半导体边界处的电子特性与成分和微晶尺寸效应的影响。我们还建议对结的模拟进行第一原理分子模拟，以进一步了解外部场对电子特性的影响。该项目的智力优点是对模型催化剂新概念的研究，其中金属-氧化物界面的活性将通过外部电压改变。所获得的结果将是对催化中这种效应的首次研究，它们将提高我们对金属-载体界面催化活性中电子效应的理解，尽管这种效应多年来一直为人所知，但一直未能与催化活性相关。所提出的研究将具有变革性和基础性，因为模型催化剂的制造成本昂贵且表面积有限。尽管如此，我们预计在这些研究中获得的知识将允许设计新的改进的氧化物负载金属催化剂。研究结果也可能与涉及太阳能电池和固态传感器等结点的其他技术相关。拟议研究的更广泛影响取决于其多学科特征，包括电气工程、先进纳米制造技术、动力学和催化以及计算化学。为了进一步帮助弱势群体的学生获得专业发展和多样化的学习体验，圣母大学少数族裔工程项目 (www.nd.edu/-mepnd) 获得支持，以参与实践实验。 研究成果将通过在催化、纳米制造和计算催化领域的国家会议上的演讲和科学期刊上的出版物来传播。除了每个研究者现有的网页外，还在建设一个网页，以宣传在催化燃烧合成领域的主要 PI 和合作者的指导下的工作，以及一旦获得明确结果就在此提出的工作。此外，我们建议推断我们对纳米二极管中电子效应的了解，并将其应用于真正的金属氧化物负载催化剂的制备中。我们期望这些结果将为更具活性和选择性的催化剂的设计带来变革性的知识。从催化领域的 PI 和纳米制造和计算化学领域的联合 PI 的综合专业知识中获得的基本见解将有利于社会在受催化影响的关键技术（如能源和化学工业）中的潜在应用。