CAS: Collaborative Research: Solar CO2 Reduction by Atomically Dispersed Metal Sites on Few-Layer Carbon Nitride

在化学系化学催化项目的支持下，新汉普郡大学的李功虎、伍斯特理工学院的N·亚伦·德斯金斯和石溪大学的阿纳托利·弗伦克尔将研究基于地球丰富元素的新型催化剂，以循环二氧化碳生产能源丰富的燃料。催化剂将通过将孤立的金属离子放置在能够吸收阳光并稳定金属离子的聚合物材料上来制备。该催化剂的结构将在布鲁克海文国家实验室使用先进技术进行研究，并辅之以计算模型。该项目将使用二氧化碳作为可再生的氯化碳原料，并利用光作为这种化学转化的唯一能量输入。通过这一过程，预计太阳能将转化为化学能，并以化学键的形式储存。该项目专注于催化领域的基础研究，为培养STEM(科学、技术、工程和数学)领域的学生提供了一个通用的平台。该项目还将为妇女和少数族裔充分参与清洁能源、催化和纳米科学提供极好的机会。在化学系化学催化计划的支持下，新汉普郡大学的李贡虎博士、伍斯特理工学院的N·亚伦·德斯金斯和石溪大学的阿纳托利·弗伦克尔将研究含有分子定义的活性中心的多相光催化剂，目标是建立一个高效太阳能燃料发电系统。创新的光催化剂将通过在几层石墨化碳氮化物上配位原子分散的钴中心来制备，它不仅是可见光的吸收体，而且是与钴中心配位并激活催化的配位体。合成的光催化剂将用X射线吸收精细结构(XAFS)光谱和计算模拟进行研究，并评估其催化二氧化碳还原为有用的化学品和燃料的能力。合作小组将专注于在氮化碳上构建高活性的Co-N4部分，以阐明这些钴中心的结构-功能关系。通过拟议的研究，研究小组试图回答以下基本问题：原子分散在少层氮化碳上的钴位置所需的结构，碳掺杂对光催化性能的影响，以及这些钴位置上二氧化碳还原的机理。实验和理论相结合的方法有望改善对此类催化剂结构的总体理解，以及这些结构如何与分子水平上的活性相关。该项目具有开发用于小分子活化和太阳能转换的活性催化剂的潜力。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis program in the Division of Chemistry, Gonghu Li of the University of New Hampshire, N. Aaron Deskins of Worcester Polytechnic Institute and Anatoly Frenkel of Stony Brook University will study new catalysts based on earth-abundant elements to recycle carbon dioxide to produce energy-rich fuels. The catalysts will be prepared by placing isolated metal ions on a polymeric material that can absorb sunlight and stabilize the metal ions. The catalyst structure will be investigated using advanced techniques at the Brookhaven National Laboratory aided by computational modeling. This project will employ carbon dioxide as a renewable C1 feedstock and utilize light as the only energy input for this chemical transformation. Through this process, it is expected that solar energy will be converted into chemical energy and stored in the form of chemical bonds. This project focuses on fundamental research in catalysis and provides a versatile platform for training students in STEM (science, technology, engineering and mathematics) fields. The project will also provide excellent opportunities for full participation of women and underrepresented minorities in clean energy, catalysis and nanoscience.With the support of the Chemical Catalysis program in the Division of Chemistry, Drs. Gonghu Li of the University of New Hampshire, N. Aaron Deskins of Worcester Polytechnic Institute and Anatoly Frenkel of Stony Brook University will study heterogeneous photocatalysts containing molecularly defined active sites with the goal of building a system for efficient solar fuel generation. Innovative photocatalysts will be prepared by coordinating atomically dispersed cobalt sites on few-layer graphitic carbon nitride, which is to serve not only as a visible-light absorber but also a “ligand” to coordinate with and activate the cobalt centers for catalysis. The synthesized photocatalysts will be investigated using X-ray absorption fine structure (XAFS) spectroscopy and computational modeling, and evaluated in their ability to catalyze the reduction of carbon dioxide to useful chemicals and fuels. The collaborative team will focus on constructing highly active Co-N4 moieties on carbon nitride to elucidate structure-function relationships of such cobalt sites. Through the proposed studies, the research team seeks to answer fundamental questions regarding the desired structure of atomically dispersed cobalt sites on few-layer carbon nitride, the effect of carbon-doping on photocatalytic properties, and the mechanism of carbon dioxide reduction at such cobalt sites. The combined experimental and theoretical approach holds promise to improve general understanding of the structures of such catalysts and how these structures correlate with activity at the molecular level. This project has the potential to develop active catalysts for small molecule activation and solar energy conversion.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.