Chemical and Structural Consequences of High Oxygen Coverages and Subsurface Oxygen in Catalytically Active Metals

催化活性金属中高氧覆盖率和地下氧的化学和结构后果

• 批准号: 1800291
• 负责人: Daniel Killelea
• 金额: $ 46.96万
• 依托单位: Loyola University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2022-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800291&HistoricalAwards=false
• 关键词: Chemical; Structural; Consequences; Oxygen; Coverages

Catalysis is essential to technological advances, especially in the chemical industry. Partial oxidation of organic chemicals on metal surfaces (catalysts) is an extensively used catalytic reaction. However, the atomic-level details of these seemingly straightforward oxidation reactions have remained elusive. Many aspects of the metal surface factor in to its reactivity. Among them, the arrangements of metal atoms, and the abundance of various oxygen-containing species, play key roles. In this project, Dr. Dan Killelea of Loyola University Chicago (LUC) and his research group are studying how the surface structures and reactivity of these metal catalysts change under reaction conditions. Significantly, this project also examines subsurface oxygen, which are oxygen atoms dissolved into the near-surface layers of the solid catalysts. Although subsurface oxygen atoms may not be reactants themselves, they may affect the reactivity and properties of the surface in important ways. While surface chemistry research is central to this proposal, this project broadens participation in science outreach efforts to the Chicago Public Schools (CPS). One goal of this project is to support students of under-represented socioeconomic status to develop their interest in scientific careers. Through this project, LUC students engage CPS students in several contexts: the high school lab, tours of LUC facilities, and a Summer Internship Program. Additional engagement and outreach efforts include hosting CPS student meetings with admissions counselors from local universities, and trips to Argonne National Laboratory. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Dan Killelea of Loyola University Chicago is advancing the understanding of the behavior of subsurface oxygen in metals by investigating its formation, and physical and chemical effects in three catalytic metals: rhodium, palladium, and platinum. In each, subsurface oxygen is thought to contribute to the selectivity of catalytic processes, but the origins of their activity remain unclear. The reactivity of the metals with various oxygen abundances is measured and the formation of subsurface oxygen is quantified with a combination of surface science techniques. The changes in the surface structures of the oxidized metals are directly observed using Scanning Tunneling Microscopy (STM). In addition to the STM images, density functional theory (DFT) is used to identify stable structures of surface and subsurface oxygen atoms on these metals and their effects. The data obtained with STM is complemented with other surface science measurements. In concert, these provide a detailed picture of the ensemble-averaged physical and chemical properties of metal surfaces with subsurface oxygen. The results of this project advance surface catalysis by providing much needed fundamental information about subsurface oxygen and reveal the importance of it in industrially relevant heterogeneously catalyzed reactions. Additionally, support from the NSF strengthens active collaborations with researchers in The Netherlands, Tulsa, and Chicago, as well as outreach efforts to local Chicago Public High Schools.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

催化对技术进步至关重要，特别是在化学工业中。 有机化学品在金属表面（催化剂）上的部分氧化是广泛使用的催化反应。然而，这些看似简单的氧化反应的原子级细节仍然难以捉摸。 金属表面的许多方面影响其反应性。 其中，金属原子的排列和各种含氧物种的丰度起着关键作用。 在这个项目中，Loyola大学芝加哥（LUC）的Dan Killelea博士和他的研究小组正在研究这些金属催化剂的表面结构和反应性在反应条件下如何变化。 值得注意的是，该项目还研究了次表面氧，即溶解在固体催化剂近表面层中的氧原子。 虽然表面下的氧原子本身可能不是反应物，但它们可能以重要的方式影响表面的反应性和性质。 虽然表面化学研究是这个建议的核心，这个项目扩大了参与科学推广工作的芝加哥公立学校（CPS）。 该项目的一个目标是支持社会经济地位低下的学生发展他们对科学事业的兴趣。 通过这个项目，LUC学生从事CPS学生在几个方面：高中实验室，LUC设施的图尔斯之旅，和暑期实习计划。 其他的参与和推广工作包括与当地大学的招生顾问举行CPS学生会议，以及前往阿贡国家实验室。在化学部化学催化计划的资助下，芝加哥洛约拉大学的Dan Killelea博士正在通过研究其形成以及三种催化金属（铑，钯和铂）的物理和化学效应来推进对金属中表面下氧行为的理解。 在每一种情况下，表面下的氧被认为有助于催化过程的选择性，但其活性的起源仍不清楚。 测量了金属与各种氧丰度的反应性，并结合表面科学技术对地下氧的形成进行了量化。 利用扫描隧道显微镜（STM）直接观察到氧化金属表面结构的变化。 除了STM图像，密度泛函理论（DFT）被用来确定这些金属表面和亚表面氧原子的稳定结构及其影响。 用STM获得的数据与其他表面科学测量相补充。 在音乐会上，这些提供了一个详细的整体平均的物理和化学性质的金属表面与表面下的氧。 该项目的结果通过提供关于表面下氧的急需的基本信息来推进表面催化，并揭示了它在工业相关的非均相催化反应中的重要性。 此外，NSF的支持加强了与荷兰、塔尔萨和芝加哥研究人员的积极合作，以及与当地芝加哥公立高中的外联工作。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Oxygen-induced surface reconstructions on curved Ag(111)

弯曲 Ag(111) 上的氧诱导表面重建

• DOI: 10.1116/6.0001167
• 发表时间: 2021
• 期刊: Journal of Vacuum Science & Technology A
• 影响因子: 2.9
• 作者: Turano, Marie E.;Juurlink, Ludo B. F.;Gillum, Maxwell Z.;Jamka, Elizabeth A.;Hildebrandt, George;Lewis, Faith;Killelea, Daniel R.
• 通讯作者: Killelea, Daniel R.

Emergence of Subsurface Oxygen on Rh(111)

Rh(111) 上地下氧的出现

• DOI: 10.1021/acs.jpclett.1c01820
• 发表时间: 2021
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Turano, Marie E.;Jamka, Elizabeth A.;Gillum, Maxwell Z.;Gibson, K. D.;Farber, Rachael G.;Walkosz, Weronika;Sibener, S. J.;Rosenberg, Richard A.;Killelea, Daniel R.
• 通讯作者: Killelea, Daniel R.

Temperature-resolved surface infrared spectroscopy of CO on Rh(111) and (2 × 1)-O/Rh(111)

CO 在 Rh(111) 和 (2→→1)-O/Rh(111) 上的温度分辨表面红外光谱

• DOI: 10.1116/6.0001932
• 发表时间: 2022
• 期刊: Journal of Vacuum Science & Technology A
• 影响因子: 2.9
• 作者: Jamka, Elizabeth A.;Gillum, Maxwell Z.;Grytsyshyn-Giger, Christina N.;Lewis, Faith J.;Killelea, Daniel R.
• 通讯作者: Killelea, Daniel R.

Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen

• DOI: 10.1021/acs.jpcc.9b09131
• 发表时间: 2020-01
• 期刊: Journal of Physical Chemistry C
• 影响因子: 3.7
• 作者: Marie E. Turano;R. G. Farber;E. C. Oskorep;R. Rosenberg;D. R. Killelea

Structural Inhibition of Silver Surface Oxidation

银表面氧化的结构抑制

• DOI: 10.1021/acs.jpcc.1c04368
• 发表时间: 2021
• 期刊: The Journal of Physical Chemistry C
• 作者: Turano, Marie E.;Juurlink, Ludo B.;Gillum, Maxwell Z.;Jamka, Elizabeth A.;Killelea, Daniel R.
• 通讯作者: Killelea, Daniel R.