CAS: Collaborative Research: New Hybrid Catalysts for Sustainable Cross-Coupling Reactions: Using Atomic Layer Deposition to Immobilize and Enhance Molecular Catalysts

CAS：合作研究：用于可持续交叉偶联反应的新型混合催化剂：利用原子层沉积来固定和增强分子催化剂

• 批准号: 1954850
• 负责人: Aaron Vannucci
• 金额: $ 30.87万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2024-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954850&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; New; Hybrid

Chemicals like plastics and medicines are essential to modern life. However, large-scale chemical production can require large amounts of energy and can create toxic waste. Catalysts can reduce the energy needed to produce chemicals, reduce waste, and provide large cost savings for chemical manufacturers. The goal of this project is to develop new catalysts to make specific chemical products while also reducing both energy usage and the creation of toxic waste. This research is developing advanced catalysts that are both selective and easily recovered for repeated use. Further, these catalysts are being used in non-toxic and non-corrosive liquids, like water. Thus, these catalysts make chemical production safer for workers and reduce hazards to surrounding communities and the environment. This research program is studying how to design these catalysts for use in chemical reactions that are otherwise difficult to achieve under less hazardous and energy efficient conditions. This program pairs Dr. Aaron Vannucci at the University of South Carolina, an expert in chemical catalysis, with Dr. Mark Losego at the Georgia Institute of Technology, an expert in materials synthesis. Ph.D. students funded by this project are being jointly trained in both fields. This exchange of skills is expanding the scientific training for students in both groups and will impact future students at both universities. Dr. Vannucci is actively running outreach programs to train high school teachers in the chemical sciences. Dr. Losego is directing a materials analysis facility run by and for undergraduate students. These programs promote interest, education, and training in STEM fields at multiple levels. Skills exchanged during this project are being used to further enhance these hands-on STEM training programs. With joint funding from the Chemical Catalysis Program and the Established Program to Stimulate Competitive Research, Dr. Aaron Vannucci from the University of South Carolina and Dr. Mark Losego from the Georgia Institute of Technology are collaboratively developing knowledge about new hybrid catalysts that immobilize non-precious metal molecular catalysts on oxide nanoparticle supports with nano-scale metal oxide over-layers deposited via atomic layer deposition (ALD). These molecular/heterogeneous catalysts have already shown excellent recyclability for Suzuki cross-coupling reactions via simple filtration and washing. Physicochemical studies are being conducted to understand not only the ability for ALD layers to physically stabilize the catalyst molecules on the particle surfaces but also the synergistic chemical interactions between the ALD metal oxide over-layer and molecular catalyst that lead to enhanced catalytic activity. Specifically, the investigators are developing strategies using ALD processing and chemistry to control the local geometric and chemical environment around the active site to achieve difficult C(sp3)-C(sp3) and stereoconvergent coupling reactions relevant to medical research and drug discovery. These hybrid catalysts adhere to many green chemistry principles including the utilization of non-noble metals, operation in non-corrosive, aqueous solvents, and ease in separation and recyclability. This program also supports extended student and investigator exchanges at the collaborative institutions to cross-train the Ph.D. students in orthogonal scientific disciplines of chemical catalysis and vapor deposition processing. These knowledge and skill sets are being institutionalized in each lab group and broadly impact current and future generations of students. During these exchanges the visiting investigators are developing programs to further enhance existing outreach and training programs that support hands-on undergraduate education and high school teacher training.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.

塑料和药品等化学品对现代生活至关重要。 然而，大规模的化学品生产可能需要大量的能源，并可能产生有毒废物。 催化剂可以减少生产化学品所需的能源，减少废物，并为化学品制造商节省大量成本。 该项目的目标是开发新的催化剂来制造特定的化学产品，同时减少能源使用和有毒废物的产生。这项研究正在开发先进的催化剂，既有选择性，又容易回收重复使用。 此外，这些催化剂用于无毒和无腐蚀性的液体，如水。 因此，这些催化剂使化学品生产对工人更安全，并减少对周围社区和环境的危害。该研究计划正在研究如何设计这些催化剂用于化学反应，否则很难在危险性较低和节能的条件下实现。 该计划将南卡罗来纳州大学的化学催化专家Aaron Vannucci博士与格鲁吉亚理工学院的材料合成专家Mark Losego博士配对。 博士该项目资助的学生正在接受这两个领域的联合培训。这种技能交流正在扩大两组学生的科学培训，并将影响两所大学未来的学生。 Vannucci博士正在积极开展外展计划，以培训化学科学方面的高中教师。 Losego博士正在指导一个由本科生管理并为本科生服务的材料分析设施。 这些计划在多个层面上促进STEM领域的兴趣，教育和培训。在这个项目中交流的技能被用于进一步加强这些动手STEM培训计划。在化学催化计划和促进竞争性研究的既定计划的联合资助下，来自南卡罗来纳州大学的Aaron Vannucci博士和来自格鲁吉亚理工学院的Mark Losego博士正在合作开发关于新的混合催化剂的知识，该混合催化剂将非贵金属分子催化剂包覆在氧化物纳米颗粒载体上，并通过原子层沉积（ALD）。 这些分子/多相催化剂已经通过简单的过滤和洗涤显示出对于Suzuki交叉偶联反应的优异的可再循环性。正在进行物理化学研究，以了解不仅ALD层物理稳定颗粒表面上的催化剂分子的能力，而且ALD金属氧化物覆盖层和分子催化剂之间的协同化学相互作用，导致增强的催化活性。 具体来说，研究人员正在开发使用ALD处理和化学的策略，以控制活性位点周围的局部几何和化学环境，以实现与医学研究和药物发现相关的困难的C（sp3）-C（sp3）和立体会聚偶联反应。 这些混合催化剂遵循许多绿色化学原理，包括利用非贵金属、在非腐蚀性水性溶剂中操作以及易于分离和可回收性。 该计划还支持在合作机构扩大学生和研究人员交流，以交叉培训博士。化学催化和气相沉积工艺的正交科学学科的学生。 这些知识和技能组合正在每个实验组中制度化，并广泛影响当前和未来几代学生。 在这些交流期间，访问研究人员正在制定计划，以进一步加强现有的推广和培训计划，支持动手本科教育和高中教师培训。该奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

项目成果

A review on recent trends in selective hydrodeoxygenation of lignin derived molecules

• DOI: 10.1039/d3su00232b
• 发表时间: 2023
• 期刊: RSC Sustainability
• 作者: Jake G. Tillou;C. Ezeorah;Joseph J. Kuchta;Sachini C. D. Dissanayake Mudiyanselage;James D. Sitter

Immobilization of molecular catalysts on solid supports via atomic layer deposition for chemical synthesis in sustainable solvents

• DOI: 10.1039/d1gc02024b
• 发表时间: 2021-11-08
• 期刊: GREEN CHEMISTRY
• 影响因子: 9.8
• 作者: Ayare, Pooja J.;Gregory, Shawn A.;Vannucci, Aaron K.
• 通讯作者: Vannucci, Aaron K.