CAREER: CAS-Climate: Structure-Property-Performance Relationships of Iron- and Copper-Based Hybrid Mie-Resonator Photocatalysts for C-C and C-N Coupling Reactions

职业：CAS-气候：用于 C-C 和 C-N 偶联反应的铁基和铜基混合米氏谐振器光催化剂的结构-性能-性能关系

• 批准号: 2237454
• 负责人: Marimuthu Andiappan
• 金额: $ 58.02万
• 依托单位: Oklahoma State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-01-15 至 2027-12-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2237454&HistoricalAwards=false
• 关键词: CAREER; CAS; Climate; Structure; Property

Carbon-carbon (C-C) and carbon-nitrogen (C-N) cross-coupling reactions are important reactions used in the chemical and pharmaceutical industries to produce a variety of valuable products. These products include pharmaceuticals, polymers, and agrochemicals. The current methods used in the industry for cross-coupling reactions require high-temperature processes and expensive metal catalysts such as palladium (Pd). This project develops iron- and copper-based inexpensive photocatalysts for C-C and C-N cross-coupling reactions. These photocatalysts use visible light as energy input to drive cross-coupling reactions under atmospheric temperature and pressure reaction conditions. The development of iron- and copper-based photocatalysts will result in significant reductions in the overall cost, energy requirements, and greenhouse gas emissions from the cross-coupling processes. The project includes educational activities that build upon the proposed research to infuse photocatalysis and solar energy concepts into the chemical engineering curriculum at Oklahoma State University (OSU). The proposed curriculum will prepare the students for the 21st century`s challenges and directly benefit the undergraduate and graduate students at OSU.The C-C and C-N cross-coupling reactions have been conventionally carried out by homogeneous Pd complex-catalyzed batch processes. There remains a critical need to develop inexpensive heterogeneous nanocatalysts for these cross-coupling reactions since nanocatalysts are the ideal catalysts for the most desired continuous flow processes. This project will focus on the design of earth-abundant and inexpensive iron- and copper-based hybrid Mie-resonator nanoparticles as heterogeneous visible light photocatalysts for C-C and C-N cross-coupling reactions. Specifically, the project will develop the structure-property-performance relationships by examining the size/shape of hybrid Mie-resonator nanoparticles against their charge carriers generation rate, the electron-transfer efficiency, and the photocatalytic rate for the C-C and C-N cross-coupling reactions. To accomplish this research objective, the project will utilize a combination of experimental and theoretical tools, including nanoparticles geometry-controlled synthesis techniques, finite-difference time-domain optical simulations, in-situ spectroscopic techniques, and photoreactor studies. The project will also establish the conditions of photocatalytic stability for the iron- and copper-based hybrid Mie-resonator nanoparticles to operate under the cross-coupling reaction conditions. The photocatalytic stability of the hybrid Mie-resonator nanoparticles of different sizes and shapes (spheres and cubes) will be investigated as a function of light intensity. The stability and the possible phase transformation at high light intensity will be characterized using in-situ UV-Vis extinction spectroscopy. The outcomes of this specific research objective will identify the combination of optimal geometries and optimal light intensity that can maintain the photocatalytic stability of iron- and copper-based hybrid Mie-resonator nanoparticles for the C-C and C-N cross-coupling reactions.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.

碳-碳（C-C）和碳-氮（C-N）交叉偶联反应是化学和制药工业中用于生产各种有价值产品的重要反应。这些产品包括药品、聚合物和农用化学品。目前业界使用的交叉偶联反应方法需要高温过程和昂贵的金属催化剂，例如钯（Pd）。该项目开发用于 C-C 和 C-N 交叉偶联反应的铁基和铜基廉价光催化剂。这些光催化剂使用可见光作为能量输入，在大气温度和压力反应条件下驱动交叉偶联反应。铁基和铜基光催化剂的开发将显着降低交叉偶联过程的总体成本、能源需求和温室气体排放。该项目包括以拟议研究为基础的教育活动，将光催化和太阳能概念融入俄克拉荷马州立大学 (OSU) 的化学工程课程中。拟议的课程将使学生为应对 21 世纪的挑战做好准备，并直接使俄勒冈州立大学的本科生和研究生受益。C-C 和 C-N 交叉偶联反应传统上是通过均相 Pd 络合物催化的间歇过程进行的。由于纳米催化剂是最理想的连续流动过程的理想催化剂，因此仍然迫切需要开发用于这些交叉偶联反应的廉价多相纳米催化剂。该项目将重点设计地球储量丰富且廉价的铁基和铜基混合米氏谐振器纳米粒子，作为 C-C 和 C-N 交叉偶联反应的异质可见光光催化剂。具体来说，该项目将通过检查混合米氏谐振器纳米颗粒的尺寸/形状及其载流子生成速率、电子转移效率以及 C-C 和 C-N 交叉耦合的光催化速率来开发结构-性能-性能关系。反应。为了实现这一研究目标，该项目将结合实验和理论工具，包括纳米颗粒几何控制合成技术、有限差分时域光学模拟、原位光谱技术和光反应器研究。该项目还将建立铁基和铜基混合米氏谐振器纳米粒子在交叉耦合反应条件下运行的光催化稳定性条件。将研究不同尺寸和形状（球形和立方体）的混合米氏谐振器纳米颗粒的光催化稳定性作为光强度的函数。高光强度下的稳定性和可能的​​相变将使用原位紫外-可见消光光谱进行表征。这一具体研究目标的成果将确定最佳几何形状和最佳光强度的组合，以维持铁基和铜基混合米氏谐振器纳米颗粒在 C-C 和 C-N 交叉偶联反应中的光催化稳定性。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。