Catalytic Nanodiode

[054324] Wolf, Eduardo E.本研究的目标是纳米制造一个催化二极管，作为金属氧化物负载催化剂的模型，该催化剂具有通过施加外部电位来改变金属负载界面电子特性的附加能力。我们提出利用红外光谱来探测电场对co -金属表面键的影响。根据红外结果，我们建议测量活性和选择性作为两个探针反应之一的施加电压的函数：CO氧化和1,3-丁二烯加氢。催化纳米二极管将用固体和表面分析技术来表征，以确定电子性质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，它可以研究以前在催化中没有研究过的外电场效应。这将允许从成分和晶体尺寸效应中分别阐明金属半导体边界的电子特性的影响。我们还建议对该结的模拟进行第一性原理分子模拟，以进一步了解外场对电子性质的影响。这个项目的智力价值在于研究了一种新型催化剂的概念，在这种催化剂中，金属-氧化物界面的活性将被外部电压改变。所获得的结果将是对这种催化效应的首次研究，它们将提高我们对金属支撑界面催化活性中的电子效应的理解，尽管多年来人们一直知道电子效应与催化活性的相关性。所提出的研究将是革命性的和根本性的，因为模型催化剂制造成本高，表面积有限。尽管如此，我们期望在这些研究中获得的知识将允许设计新的改进的氧化物支撑的金属催化剂。该结果也可能与其他涉及连接的技术相关，如太阳能电池和固态传感器。拟议研究的广泛影响取决于其多学科特征，包括电气工程，先进的纳米制造技术，动力学和催化，以及计算化学。为了进一步帮助弱势群体学生的专业成长和多样化的学习体验，我们为圣母大学的少数族裔工程项目（www.nd.edu/-mepnd）提供了参与动手实验的支持。研究结果将通过在催化、纳米制造和计算催化领域的国家会议和科学期刊上发表的报告和出版物来传播。除了每位研究者现有的网页外，一个网页正在建设中，以宣传在首席PI和合作者的指导下在催化燃烧合成方面的工作，一旦获得明确的结果，在这里提出的工作。此外，我们建议将我们对纳米二极管中电子效应的了解推断出来，并将其应用于实际金属氧化物负载催化剂的制备中。我们期望这些结果将为设计更具活性和选择性的催化剂带来变革性的知识。从催化方面的PI和纳米制造和计算化学方面的co-PI的综合专业知识中获得的基本见解将有益于社会，因为它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。

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.