Collaborative Research: Correlating Molecular Structure and Activity in Boron-containing ODH Catalysts

合作研究：含硼 ODH 催化剂的分子结构和活性的关联

• 批准号: 1916809
• 负责人: Aaron Rossini
• 金额: $ 22.46万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1916809&HistoricalAwards=false
• 关键词: Collaborative; Research; Correlating; Molecular; Structure

As the world population grows, the demand for consumer goods, which are made from building-block chemicals such as ethylene and propylene, increases. The project focuses on discovery of energy-efficient catalysts for the production of these chemical building-blocks from natural gas with minimal generation of undesired by-products such as carbon dioxide. Preliminary studies by the investigators have shown exceptional promise of boron-containing catalysts, but deeper, atomic-level understanding is needed to further improve the catalyst performance and durability. The project will utilize a combination of new catalyst synthesis protocols, state-of-the-art solid-state nuclear magnetic resonance imaging, and computational methods to obtain the needed atomic-level understanding, and use that insight to design improved catalysts. The research will support U.S. clean-energy security through its potential for the efficient conversion of our nation's vast shale gas resources to value-added fuels and chemicals. Oxidative Dehydrogenation (ODH) of light alkanes is a promising alternative for the production of important chemical building blocks. However, despite decades of research, a highly selective catalyst has remained elusive, as over-oxidation is a facile and thermodynamically favored process. Recent studies by the lead investigator's group has demonstrated that boron-containing catalysts (hBN, BNNT, WB, among others) are highly selective catalysts for the ODH of light alkanes. For propane ODH, propylene selectivity as high as 80% can be obtained up to 20% conversion, compared to 60% propylene selectivity at 10% propane conversion for the state-of-the-art vanadium oxide-based catalyst. Given the recent discovery of this class of materials as ODH catalysts, there are many fundamental questions that need to be answered regarding the active sites and their formation. Controlled synthesis, state-of-the-art solid-state NMR (SSNMR) spectroscopy, and computational modelling will be utilized to gain insights into the catalytically active site(s) and build up a structure-performance relationship for boron-containing ODH catalysts. The work will contribute to a molecular-level understanding of a complex problem that is of industrial importance. Our multidisciplinary approach comprised of synthesis, SSNMR characterization, catalytic testing, and computational modelling will train the participating students to use information from a variety of fields to develop a detailed picture of a complex system. Additionally, the collaborative nature of this work will help the students grow as productive members of a research team. Beyond the targeted reactions, the study will be of value to the broader catalysis community because of the generalized catalytic insights and the methods developed for characterization of heterogeneous materials.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.

随着世界人口的增长，对由乙烯和丙烯等基础化学品制成的消费品的需求也在增加。该项目的重点是发现节能催化剂，用于从天然气生产这些化学构件，同时尽量减少二氧化碳等不需要的副产品的产生。 研究人员的初步研究表明，含硼催化剂具有非凡的前景，但需要更深入的原子级了解来进一步提高催化剂的性能和耐用性。 该项目将结合新的催化剂合成方案、最先进的固态核磁共振成像和计算方法来获得所需的原子级理解，并利用这种见解来设计改进的催化剂。 该研究将通过其将我国庞大的页岩气资源有效转化为增值燃料和化学品的潜力，支持美国的清洁能源安全。轻质烷烃的氧化脱氢 (ODH) 是生产重要化学结构单元的一种有前景的替代方案。然而，尽管经过数十年的研究，高选择性催化剂仍然难以捉摸，因为过度氧化是一个容易且热力学有利的过程。首席研究员小组最近的研究表明，含硼催化剂（hBN、BNNT、WB 等）是轻质烷烃 ODH 的高选择性催化剂。对于丙烷 ODH，在高达 20% 的转化率下可以获得高达 80% 的丙烯选择性，而最先进的氧化钒基催化剂在 10% 丙烷转化率下的丙烯选择性为 60%。鉴于最近发现了这类材料作为 ODH 催化剂，有许多关于活性位点及其形成的基本问题需要回答。将利用受控合成、最先进的固态核磁共振 (SSNMR) 光谱和计算模型来深入了解催化活性位点并建立含硼 ODH 催化剂的结构-性能关系。这项工作将有助于从分子水平理解具有工业重要性的复杂问题。我们的多学科方法包括合成、SSNMR 表征、催化测试和计算建模，将训练参与的学生使用来自各个领域的信息来绘制复杂系统的详细图片。此外，这项工作的协作性质将帮助学生成长为研究团队的富有成效的成员。除了目标反应之外，由于广义的催化见解和为表征异质材料而开发的方法，该研究将对更广泛的催化界具有价值。该奖项反映了 NSF 的法定使命，并通过使用基金会的评估进行评估，被认为值得支持。智力价值和更广泛的影响审查标准。

项目成果

Synthesis and Characterization of Silica-Supported Boron Oxide Catalysts for the Oxidative Dehydrogenation of Propane

• DOI: 10.1021/acs.jpcc.9b07429
• 发表时间: 2019-11-07
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Love, Alyssa M.;Cendejas, Melissa C.;Hermans, Ive
• 通讯作者: Hermans, Ive

Formation of a Strong Heterogeneous Aluminum Lewis Acid on Silica

在二氧化硅上形成强非均相铝路易斯酸

• DOI: 10.1002/anie.202205745
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Samudrala, Kavyasripriya K.;Huynh, Winn;Dorn, Rick W.;Rossini, Aaron J.;Conley, Matthew P.
• 通讯作者: Conley, Matthew P.

Controlled Grafting Synthesis of Silica-Supported Boron for Oxidative Dehydrogenation Catalysis

• DOI: 10.1021/acs.jpcc.1c01899
• 发表时间: 2021-06-07
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Cendejas, Melissa C.;Dorn, Rick W.;Hermans, Ive
• 通讯作者: Hermans, Ive

Hydrogenation/Hydrodeoxygenation Selectivity Modulation by Cometal Addition to Palladium on Carbon-Coated Supports

• DOI: 10.1021/acssuschemeng.2c02399
• 发表时间: 2022-06
• 期刊: ACS Sustainable Chemistry & Engineering
• 作者: Alireza Saraeian;Geet Gupta;R. Johnson;Rick W. Dorn;Alex M. Kauffmann;H. Bateni;J. Tessonnier;Luke T. Roling;Aaron J. Rossini;B. Shanks