New Strategies for Creating Single and Dual Atom Catalysts on Silica Surfaces

在二氧化硅表面制造单原子和双原子催化剂的新策略

基本信息

批准号：
1900100
负责人：
Janet Bluemel
金额：
$ 44.96万
依托单位：
Texas A&M 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：
2019-08-15 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900100&HistoricalAwards=false
关键词：
New Strategies Creating Single Dual

项目摘要

Catalysts allow reactions to proceed faster and to produce greater quantities of desirable products. Industrial chemistry would not be possible without the use of catalysts. However, big challenges remain regarding the sustainable use and recycling of catalysts. An optimal catalyst would consist of only one or two atoms that are prevented from grouping together and forming large bundles (aggregates). This separation of atoms can be achieved by arranging the atoms on a surface and retaining them at their specific surface sites. In this project, Professor Janet Bluemel of Texas A&M University is making use of two earlier discoveries to reach this goal. First, a well-defined one layer (monolayer) of metal complexes are placed on surfaces such as silica. The metal complexes are then modified to form single atoms that remain in place, dispersed on the surface. Similarly, two-atom assemblies are being prepared from metal complexes containing two different metal centers that are bound to the surface. Professor Bluemel's group is exploring the catalytic activities of these single- and dual-atom catalysts, their ability to form products selectively, and their recyclability. Different analytical approaches are being used and refined to obtain better insight into the surface processes and ultimately generate more efficient catalysts with superior characteristics. The project is enhancing the fundamental knowledge about how to create well-defined, efficient, recyclable catalysts in general and is leading to more sustainable processes. This project also provides broad, in-depth training for undergraduate and graduate students in Professor Bluemel's laboratory. In particular, the students are provided with opportunities for direct interaction with both domestic and international chemical companies, thus giving them unique and beneficial industrial experience.With funding from the Chemical Catalysis Program of the Chemistry Division, Professor Janet Bluemel of Texas A&M University is investigating dynamic processes on silica surfaces that involve supported molecular nickel, palladium, and copper complexes. The species are supported by tethering the complexes to the surface with the use of linkers. The tethered species are used as precursors to deliberately create well-defined single- and dual metal atom catalysts on surfaces such as silica. Dynamic processes do not occur only when covalently immobilized catalysts are suspended in a solvent. The Bluemel group has discovered that metal complexes adsorbed via Van der Waals interactions also display different modes of mobility on surfaces within pores, even in the absence of a solvent. At present there is a rudimentary understanding of how catalysts and their precursors diffuse in suspension or on dry surfaces. The ultimate goal of this project is to exploit the impact of specific tridentate phosphine linkers and the dry adsorption of nickelocene, which leads to well-defined monolayers, and to explore new methods for generating single- and dual atom catalysts (SACs, DACs) and well-defined nanoparticles on oxide surfaces. All approaches, which aim at stabilizing the metal particles and preventing their unrestricted growth are only feasible on surfaces. Investigating molecular immobilized and adsorbed catalyst precursors and the supported active metal catalysts generated from them, improves the understanding of their decomposition, agglomeration, and formation of metal particles. Direct insight regarding the structure and dynamics of all surface species is provided by High Resolution Transmission Electron Microscopy, dia- and paramagnetic 1H, 2H, 13C, 29Si, and 31P Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy of the dry materials and other techniques.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.

催化剂允许反应更快，并产生更多的理想产品。没有使用催化剂，工业化学将是不可能的。但是，在催化剂的可持续使用和回收方面仍然存在重大挑战。最佳催化剂将仅由一个或两个原子组成，这些原子被阻止将其分组并形成大束（聚集体）。通过将原子排列在表面上并将其保留在其特定的表面位点上，可以实现原子的这种分离。在这个项目中，得克萨斯州农工大学的珍妮特·布鲁梅尔教授正在利用两个较早的发现来实现这一目标。首先，将一层（单层）的金属配合物（单层）放在二氧化硅等表面上。然后将金属络合物修饰以形成保留在地面上的单个原子，分散在表面上。同样，正在从包含两个与表面结合的不同金属中心的金属配合物中制备两种原子组件。 Bluemel教授的小组正在探索这些单原子和双原子催化剂的催化活性，有选择性地形成产品的能力及其可回收性。正在使用不同的分析方法并进行了完善，以更好地了解表面过程，并最终产生具有较高特征的更有效的催化剂。该项目正在增强有关如何创建定义明确，高效，可回收催化剂的基本知识，并导致更可持续的过程。该项目还为Bluemel教授实验室的本科生和研究生提供了广泛的，深入的培训。特别是，为学生提供了与国内和国际化学公司直接互动的机会，从而为它们提供了独特而有益的工业经验。在化学部门的化学催化计划中，得克萨斯州A＆M大学的珍妮特·布鲁梅尔（Janet Bluemel）教授正在调查二氧化硅表面上的动态过程，涉及支持分子镍，palladium，palladium，palladium，palladium和copperess和copperes。通过使用接头将复合物绑定到表面，可以支持该物种。束缚物种被用作前体，故意在二氧化硅等表面上产生明确定义的单金属原子催化剂。仅当将共价固定的催化剂悬浮在溶剂中时，就不会发生动态过程。 Bluemel组发现，即使在没有溶剂的情况下，通过Van der Waals相互作用吸附的金属复合物在孔内也显示出不同的迁移率。目前，人们对催化剂及其前体在悬浮液或干燥表面上的扩散有基本的了解。该项目的最终目的是利用特定的三叉戟磷酸连接器的影响以及镍的干燥吸附，这会导致明确定义的单层，并探索新方法在氧化和双原子催化剂（SAC，DACS）以及在氧化范围内产生纳米植物的新方法。旨在稳定金属颗粒并防止其无限生长的所有方法仅在表面上可行。研究分子固定和吸附的催化剂前体以及从中产生的有活性金属催化剂，从而提高了对金属颗粒的分解，团聚和形成的理解。高分辨率的传输电子显微镜，透明和顺磁性1H，2H，13C，29SI和31p魔术角度旋转核磁共振光谱和其他技术的直接见解是由高分辨率传输电子显微镜，二磁和顺式磁性的，2H，2H，13C，29SI和31p的魔术角提供的。这项奖项反映了NSF的法定任务和审查的范围。

项目成果

期刊论文数量（13）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Creating Solid Solutions of Metallocenes: Migration of Nickelocene into the Ferrocene Crystal Lattice in the Absence of a Solvent

创建茂金属固溶体：在没有溶剂的情况下茂镍迁移到二茂铁晶格中

DOI：
10.1021/acs.jpcc.2c07441
发表时间：
2023
期刊：
The Journal of Physical Chemistry C
影响因子：
0
作者：
Harmon-Welch, Gabrielle E.;Hoefler, John C.;Trujillo, Martha R.;Bhuvanesh, Nattamai;Bakhmutov, Vladimir I.;Blümel, Janet
通讯作者：
Blümel, Janet

Synthesis and characterization of tridentate phosphine ligands incorporating long methylene chains and ethoxysilane groups for immobilizing molecular rhodium catalysts

DOI：
10.1016/j.mcat.2019.110629
发表时间：
2019-12-01
期刊：
MOLECULAR CATALYSIS
影响因子：
4.6
作者：
Guenther, J.;Reibenspies, J.;Blumel, J.
通讯作者：
Blumel, J.

Hydrogen peroxide adducts of triarylphosphine oxides

DOI：
10.1039/c9dt03070k
发表时间：
2019-10-14
期刊：
DALTON TRANSACTIONS
影响因子：
4
作者：
Arp, Fabian F.;Bhuvanesh, Nattamai;Blumel, Janet
通讯作者：
Blumel, Janet

Molecular Dynamics and Surface Interactions of Nickelocene Adsorbed on Silica: A Paramagnetic Solid-State NMR Study

二氧化硅上吸附的茂镍的分子动力学和表面相互作用：顺磁固态核磁共振研究

DOI：
10.1021/acs.langmuir.2c00301
发表时间：
2022
期刊：
Langmuir
影响因子：
3.9
作者：
Benzie, Jordon W.;Harmon-Welch, Gabrielle E.;Hoefler, John C.;Bakhmutov, Vladimir I.;Blümel, Janet
通讯作者：
Blümel, Janet

Ferrocene Adsorbed on Silica and Activated Carbon Surfaces: A Solid-State NMR Study of Molecular Dynamics and Surface Interactions