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. 所提出的工作的目的是nanofabricate的催化二极管作为一个模型的金属氧化物负载的催化剂与附加的能力，通过施加外部电位改变在金属载体界面的电子性能。我们建议使用红外光谱来探测电场对CO-金属表面键的影响。根据红外光谱的结果，我们建议测量的活性和选择性作为一个功能的两个探针反应：CO氧化和氢化的1，3-丁二烯的施加电压。催化纳米二极管的特征在于与固体和表面分析技术，以确定电子性能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奇在于，它能够研究之前在催化中没有研究过的外部电场的影响。这将允许分别阐明在金属半导体边界处的电子性质的影响，从组成和微晶尺寸的影响。我们还建议进行第一性原理分子模拟的模拟结，以进一步了解的电子性质的外部场的影响。该项目的智力价值是研究一种新概念的模型催化剂，其中金属氧化物界面的活性将被外部电压改变。所获得的结果将是第一次调查这种影响在催化，他们将提高我们的理解，在催化活性的电子效应在金属载体界面，虽然已知多年，已经回避了与催化活性的相关性。拟议的研究将是变革性的和基本的性质，因为模型催化剂是昂贵的制造和有限的表面积。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金属催化剂负载在氧化物上。这些结果也可能与其他涉及结的技术有关，如太阳能电池和固态传感器。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，先进的纳米纤维技术，动力学和催化，以及计算化学。为了进一步帮助代表性不足群体的学生的专业成长和多样化的学习经验，为圣母大学的少数民族工程方案（www.nd.edu/-mepnd）提供了参与实践实验的支持。 研究成果将通过在催化、纳米纤维和计算催化领域的国家会议上的介绍和科学期刊上的出版物传播。除了现有的网页，每个研究者，一个网页正在建设中公布的工作的指导下，主要PI和合作者在燃烧合成催化，并在这里提出的工作，一旦获得明确的结果。此外，我们建议外推我们所了解的纳米二极管中的电子效应，并将其应用于制备真实的金属氧化物负载催化剂。我们希望这些结果将为设计更活性和选择性的催化剂带来变革性的知识。从PI在催化方面的综合专业知识和纳米纤维和计算化学中的co-PI中获得的基本见解将使社会受益于其在受催化影响的关键技术（如能源和化学工业）中的潜在用途。