Collaborative Research: CAS-Climate: Structure, Dynamics, and Reaction Mechanism of Supported Single Atom for Photocatalytic CO2 Reduction

在这个由化学学部化学结构、动力学和机理B项目资助的合作项目中，马奎特大学化学系的黄杰尔教授和圣地亚哥州立大学化学系的谷静教授旨在构建和研究新一代单原子催化剂，用于可见光驱动二氧化碳还原，形成高效、选择性和稳定性的化学燃料。利用太阳能进行光催化CO2减排是解决全球变暖问题和满足未来能源需求的最具吸引力的策略之一。这项研究还辅以各种教育和推广活动，包括鼓励研究生和本科生，特别是代表性不足的少数群体，从事STEM研究，并为从小到高中的学生/教师提供机会，提高他们对催化和可再生能源技术的总体理解。负载单原子（SAs）已经成为一类新型催化剂，为光驱动二氧化碳减排提供了新的希望。先前研究的重点主要是记录催化剂的效率、稳定性和选择性，而不是强调SA结构与其光催化性能相关性的基本机理研究。为了解决这些知识上的空白，顾教授和黄教授利用他们在材料设计和合成方面的互补专业知识，利用时间分辨光谱技术实现了以下目标：1)通过改变sa的内在性质、金属-载体相互作用以及与不同尺寸的纳米颗粒的比较，系统地调整负载sa的几何和电子结构；2)利用时间分辨光学和x射线吸收光谱技术对催化活性位点的电荷分离和结构动力学进行了研究，并对催化活性位点的中间结构进行了高时空分辨率的解析；3)评价负载型SA催化剂的结构与其光物理性质和催化功能的直接相关性，建立CO2还原的结构-性能-功能关系。这些研究结果将对开发更有效的光催化还原CO2的负载型sa具有重要的价值。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this collaborative project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Jier Huang of the Department of Chemistry at Marquette University and Professor Jing Gu of the Department of Chemistry at San Diego State University aim to construct and investigate new generation single atom catalysts for visible light driven carbon dioxide (CO2) reduction to form chemical fuels with high efficiency, selectivity, and stability. Photocatalytic CO2 reduction by harnessing solar energy represents one of the most attractive strategies that may simultaneously address the global warming issue and fulfill the future energy demand. The research is supplemented by diverse educational and outreach activities, including encouraging graduate and undergraduate students, especially underrepresented minority groups, into careers in STEM research, and providing opportunities for students/teachers ranging from elementary to high schools to advance their general understanding of catalysis and renewable energy technologies. Supported single atoms (SAs) have emerged as a novel class of catalysts, offering new promise for light-driven CO2 reduction. The focus of prior research is largely on documenting the efficiency, stability, and the selectivity of the catalysts, not the fundamental mechanistic studies that underlines the correlation of SA structure and their photocatalytic performance. To address such gaps in knowledge, Professor Gu and Professor Huang target the following objectives by leveraging their complementary expertise in materials design and synthesis with time resolved spectroscopy: 1) systematically tuning the geometric and electronic structures of supported SAs via altering the intrinsic nature of SAs, the metal-support interaction, and the comparison with nanoparticles with various sizes; 2) examining the charge separation and structural dynamics, and resolving the intermediate structures at catalytic active sites with high temporal and spatial resolution using time resolved optical and X-ray absorption spectroscopy; and 3) evaluating the direct correlation of the structures of the supported SA catalysts with their photophysical properties and catalytic function to establish structure-property-function relationships for CO2 reduction. Results obtained from these efforts will be of significant value in developing more effective supported SAs for photocatalytic CO2 reduction.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.