CAS: Electrocatalytic Oxygen Atom Transfer

这个合作项目由化学学部化学结构、动力学和机理B项目资助，来自伊利诺伊大学芝加哥分校化学系的Ksenija Glusac、Neal Mankad和Jordi Cabana将研究新的分子/电极混合电催化剂，这种催化剂可以进行与能量转换（如燃料电池）和化学工业应用（如环氧化合物的电合成）相关的化学反应。这种合作是协同的，团队的每个成员都为团队带来了不同的专业知识，从电化学到无机催化再到x射线光谱学。拟议研究的多学科性质将使研究生的培养超越传统的学科界限。团队成员的目标是利用UIC独特的多元化学生群体，提高代表性不足群体在STEM研究中的参与度。杂原子功能化的多孔石墨结构是一种极好的碳基储能电极。然而，由于碳石墨化所需的极端热解温度，这些材料中催化位点的化学可调性受到限制。在这里，研究小组将研究碳电极的功能化与化学可调分子催化剂的电催化氧原子转移（e-OAT）。计划的活动包括：(i)利用共价连接剂和pi相互作用扩大碳边和基面功能化的化学工具箱；（ii）分子/碳杂化物对e-OAT的电化学性能；（iii）使用紫外/可见，中红外和x射线光谱电化学方法对反应中间体进行详细的机理研究。这项研究是UIC的三位主要研究人员在电催化、过渡金属催化和材料化学表征方面的协同专业知识以及匹兹堡大学的外部合作者John Keith博士在计算电化学方面的专业知识的共同努力。从他的研究中获得的经验教训可以为未来的催化剂设计提供支持，例如，通过在这种系统中对纳米碳边缘和基面位点进行热解后改性来指导明确的催化位点的结合。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 collaborative project, funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Ksenija Glusac, Neal Mankad and Jordi Cabana from the Department of Chemistry at the University of Illinois at Chicago (UIC) will investigate new molecular/electrode hybrid electrocatalysts that can perform chemical reactions relevant to energy conversion (e.g. fuel cells) and chemical industry applications (e.g. electrosynthesis of epoxides). The collaboration is synergistic, with each member of the team bringing distinct expertise to the team, ranging from electrochemistry to inorganic catalysis to X-ray spectroscopy. The multidisciplinary nature of the proposed research will enable the training of graduate students beyond the traditional disciplinary boundaries. Team members aim to leverage the uniquely diverse student body at UIC to enhance the participation of underrepresented groups in STEM research.Porous graphitic structures functionalized with heteroatoms are excellent carbon-based electrodes for energy storage applications. However, the chemical tunability of catalytic sites in these materials is limited due to extreme pyrolytic temperatures needed for carbon graphitization. Here, the research team will investigate the functionalization of carbon electrodes with chemically tunable molecular catalysts for electrocatalytic oxygen atom transfer (e-OAT). The planned activities involve: (i) expansion of the chemical toolbox for functionalization of carbon edge and basal planes using covalent linkers and pi-interactions; (ii) electrochemical performance of molecule/carbon hybrids toward e-OAT; (iii) detailed mechanistic studies of reaction intermediates using UV/Vis, mid-IR and X-ray spectro-electrochemical methods. The research is a collaborative effort among the three principal investigators at UIC with synergic expertise in electrocatalysis, transition metal catalysis and chemical characterization of materials, as well as an external collaborator, Dr. John Keith, University of Pittsburgh, who provides expertise in computational electrochemistry. The lessons learned from his research study could enable future catalyst design, for example, by guiding the incorporation of well-defined catalytic sites via post-pyrolysis modification of the nanocarbon edge and basal plane sites in such systems.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.