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，由乙烯和丙烯等建筑物化学物质制成的对消费品的需求会增加。该项目的重点是发现节能催化剂，以从天然气中生产这些化学建筑块，并最少产生不希望的副产品，例如二氧化碳。 研究人员的初步研究表明，需要富含硼硼的催化剂的非凡希望，但是需要更深入的原子水平理解来进一步提高催化剂的性能和耐用性。 该项目将利用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的组合来获得所需的原子级理解，并利用该洞察力来设计改进的催化剂。 这项研究将通过有效地转换为我们国家的庞大的页岩气资源到增值燃料和化学物质来支持美国清洁能源安全。轻烷烃的氧化脱氢（ODH）是生产重要化学块的有希望的替代方法。然而，尽管进行了数十年的研究，但高度选择性的催化剂仍然难以捉摸，因为过度氧化是一个轻松而热力学的过程。主要研究者小组的最新研究表明，含硼的催化剂（HBN，BNNT，WB等）是轻质烷烃的高度选择性催化剂。对于丙烷ODH，可以获得高达80％的丙烯选择性高达20％的转化率，而60％的丙烯选择性在10％的丙烷转化率时可用于基于最先进的氧化钒的丙烷转化率。鉴于最近发现了这类材料作为ODH催化剂，因此，关于活动地点及其形成需要回答许多基本问题。受控合成，最先进的固态NMR（SSNMR）光谱法和计算建模将用于洞悉催化活性位点（S），并建立用于硼隆携带ODH催化剂的结构表现关系。这项工作将有助于分子级别对一个具有工业重要性的复杂问题的理解。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开发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生产成员。除了有针对性的反应之外，该研究还将对更广泛的催化群落具有价值，因为具有广义的催化见解以及用于表征异质材料的方法。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的审查审查标准来通过评估来通过评估来获得支持的。

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