CAS: Electrocatalytic Oxygen Atom Transfer

在这个由化学部化学结构、动力学和机理B项目资助的合作项目中，来自伊利诺伊大学芝加哥分校化学系的Ksenija Glusac、Neal Mankad和Jordan i Cabana将研究新型分子/电极混合电催化剂，这种催化剂可以执行与能源转换(例如燃料电池)和化学工业应用(例如环氧化物的电合成)相关的化学反应。这种协作是协同的，团队中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射线光谱分析。拟议研究的多学科性质将使研究生的培训超越传统学科的界限。团队成员的目标是利用UIC独特的多样化学生群体，加强未被充分代表的群体在STEM研究中的参与。具有杂原子官能化的多孔石墨结构是用于储能应用的优秀碳基电极。然而，由于碳石墨化所需的极端热解温度，这些材料中催化中心的化学可调整性受到限制。在这里，研究小组将研究具有化学可调分子催化剂的碳电极的功能化，以用于电催化氧原子转移(e-OAT)。计划开展的活动包括：(1)使用共价键和圆周率相互作用扩展碳边和基面官能化的化学工具箱；(2)分子/碳杂化化合物的电化学性能；(3)使用UV/VIS、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三位在电催化、过渡金属催化和材料化学表征方面具有协同专业知识的主要研究人员以及匹兹堡大学的外部合作者John Keith博士共同努力的结果，他提供计算电化学方面的专业知识。从他的研究中学到的经验教训可以使未来的催化剂设计成为可能，例如，通过指导通过对此类系统中的纳米碳边缘和基面位置的热解后修改来纳入明确定义的催化位置。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 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.