CAS: Photochemical CO2 Reduction Using Biomimetic NAD+/NADH Analogs

凭借这一奖项，化学学部的化学催化项目资助了伊利诺伊大学芝加哥分校的Ksenija Glusac博士，通过一种受大自然启发的方法，特别是植物利用阳光将二氧化碳转化为有用的碳水化合物的光合作用，来开发二氧化碳还原化学。这个项目探索如何利用太阳能来满足我们的能源需求。Glusac研究小组旨在将二氧化碳转化为甲醇，这是一种易于运输和处理的液体燃料。该项目的主要挑战是，除了甲醇之外，二氧化碳还可以形成许多其他产品。Glusac博士正在探索催化剂，以选择性地进行所需的化学反应，从而高效地形成甲醇。这些催化剂是由地球上丰富的元素制成的，目的是使它们在未来的设备中得到广泛应用。催化剂需要吸收太阳发出的光，然后利用吸收的能量进行有用的化学反应。催化剂/半导体混合材料可以吸收阳光，并利用吸收的能量将二氧化碳转化为甲醇，目前正在研究中。作为该项目的一部分，格鲁萨克博士还在为学生和普通大众开发光化学领域的在线教育材料。光化学是化学的一个分支，研究光与分子的相互作用。受自然光合作用的启发，伊利诺斯-芝加哥大学的Ksenija Glusac博士正在研究无金属NADH类似物的光催化二氧化碳还原，这种类似物是利用水作为电子和质子源，由NAD+类似物光产生的。该项目的主要假设是，利用提出的氢化物转移机制，二氧化碳的减少可以选择性地导向甲醇的生产。研究重点分为两个部分：一个解决催化的“黑暗”部分，即有机氢化物减少二氧化碳，第二个探索通过这些氢化物的光化学再生来关闭催化循环。实验方法包括研究有机氢化物的热力学水合性，并研究氢化物向CO2或活化形式CO2转移的动力学。Glusac团队正在开发一种系统，利用NAD+（烟酰胺腺嘌呤二核苷酸）类似物和Lewis碱的组合，利用质子偶联方法实现有机氢化物的电化学再生，利用中隙和宽隙半导体实现有机氢化物的光化学再生。该研究为热力学上坡还原过程与可见光能量的耦合提供了新的机制。Glusac博士的教育活动包括开发光化学领域的在线讲座材料。这些视频讲座使对光化学基础和应用感兴趣的学生和一般人群能够传播知识。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。

With this award, the Chemical Catalysis Program in the Division of Chemistry is funding Dr. Ksenija Glusac of the University of Illinois-Chicago to develop carbon dioxide-reduction chemistry through an approach inspired from nature, particularly from photosynthesis through which plants use sunlight to convert CO2 into useful carbohydrates. This project explores ways in which energy from the sun can be utilized to meet our energy demand. The Glusac research group aims to convert carbon dioxide to methanol, a liquid fuel that can be easily transported and handled. The main challenge in this project is that, in addition to methanol, many other products can be formed from carbon dioxide. Dr. Glusac is exploring catalysts to perform the desired chemical reaction selectively to form methanol with high efficiency. These catalysts are being made from earth-abundant elements, with the aim of enabling their widespread use in future devices. The catalyst needs to absorb light emitted by the sun and then use the absorbed energy to perform useful chemistry. Catalyst/semiconductor hybrid materials that can absorb sunlight and use the absorbed energy for the desired conversion of carbon dioxide to methanol are being investigated. As part of this project, Dr. Glusac is also developing online educational materials for students and general population in the area of photochemistry, a branch of chemistry that investigates how light interacts with molecules. Inspired by natural photosynthesis, Dr. Ksenija Glusac of the University of Illinois-Chicago is investigating photocatalytic CO2 reduction by metal-free NADH analogs that are photogenerated from NAD+ analogs using water as an electron and proton source. The main hypothesis of this project is that, using a proposed hydride transfer mechanism, the CO2 reduction can be selectively directed toward methanol production. The research thrusts are grouped into two sections: one addressing the “dark” portion of catalysis, namely the reduction of CO2 by organic hydrides, and the second exploring the closure of the catalytic cycle via photochemical regeneration of those hydrides. The experimental approach involves studying the thermodynamic hydricities of organic hydrides and investigating the kinetics of hydride transfer to either CO2 or an activated form of CO2. The Glusac team is developing systems to effect thermal CO2 hydrogenation using a combination of NAD+ (nicotinamide adenine dinucleotide) analogues and Lewis bases, with electrochemical regeneration of organic hydrides using a proton-coupled approach, and photochemical regeneration of organic hydrides using mid- and wide-gap semiconductors. This study is providing new mechanisms for coupling thermodynamically uphill reduction processes with visible light energy. Dr. Glusac's educational activities involve the development of online lecture materials in the area of photochemistry. These video lectures are enabling the dissemination of knowledge to students and the general population interested in the fundamentals and applications of photochemistry.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.