CAS: Biologically Inspired Aminopyridine Complexes for CO2 Reduction

CAS：用于减少二氧化碳排放的生物启发氨基吡啶复合物

• 批准号: 2102707
• 负责人: Smaranda Marinescu
• 金额: $ 47.5万
• 依托单位: University of Southern California
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102707&HistoricalAwards=false
• 关键词: CAS; Biologically; Inspired; Aminopyridine; Complexes

With the support of the Chemical Catalysis program in the Division of Chemistry, Smaranda C. Marinescu of the University of Southern California will study the development of biologically inspired catalytic systems for the conversion of harmful carbon dioxide into chemical fuels. The development of clean energy technologies as an alternative to fossil fuels is a critical need in the face of rapid planetary warming. Solar energy has received much attention as a clean energy source, but the focus has largely been on electricity generation. This narrow focus does not adequately meet the need for renewable fuels for transportation, heating, and industrial uses, which make up ~70% of energy needs. A sustainable energy future will require a non-fossil fuel method for the formation of chemical feedstocks, and the electrochemical reduction of abundant small molecules such as carbon dioxide (CO2) and water (H2O), using the solar-derived electricity is a viable pathway to do so. This approach will allow for storing of solar energy in chemical bonds in a similar way as nature accomplishes through photosynthesis, where the energy of photons is used to drive the reduction of CO2 to a variety of high-energy products. Inspired by biological systems, the Marinescu group will develop molecular catalysts that involve hydrogen-bonding networks which are capable of small molecule activation through multiple proton and electron transfers. This project will focus on the development of a series of biologically inspired metal complexes with pendant amines, which will allow for understanding the effect of proton relays on multi-electron, multi-proton reactions. The ligand framework allows for excellent control of electronic and positioning effects, which will facilitate structure-activity studies. Integrated into this research plan is an educational program focused on providing research opportunities to both students and teachers from local community colleges with a high percentage of minority students, and a mentoring program for women at the postdoctoral level to increase the participation of this underrepresented group in science. These outreach and mentoring activities will impact a significant number of individuals over the long term: teachers and generations of their students, along with researchers from USC. Importantly, students involved in these efforts will develop a culture of contributing to their scientific and non-scientific communities that is expected to last beyond their formative years.With the support of the Chemical Catalysis program in the Division of Chemistry, Smaranda C. Marinescu of the University of Southern California will study the effect of pendant proton relays on the CO2 reduction with cobalt aminopyridine macrocycles. Recent work in the Marinescu group has demonstrated that a series of cobalt complexes with zero to four pendant secondary amines (NH) displays a linear correlation between the rate of CO2 reduction and the number of pendant NH moieties. Experiment and theory suggest that the pendant NH groups do not directly transfer protons to CO2, but instead bind acid molecules from solution, leading to the formation of a catalyst-acid adduct, held together through a hydrogen-bonding network, that enables direct proton transfer from acid to the activated CO2 substrate. The research goal is to understand the factors that govern the catalytic properties of these complexes, in terms of activity and selectivity for CO2 reduction, by characterizing and altering the electronic environment (the primary and secondary coordination spheres) of these metal aminopyridine macrocycles. This project focuses on the synthesis and characterization of a variety of aminopyridine complexes with pendant hydrogen bond donors or cationic groups to understand the effects of these moieties on the catalyst activity and selectivity. The science education goals will focus on: (1) organizing a summer workshop for students from Cerritos College, a public community college with a high percentage of students from underrepresented groups and hosting a Cerritos College student in the Marinescu laboratory to perform undergraduate research for an 8-week period during the summer; and (2) developing a mentoring program for women at the postdoctoral level to increase the participation of women in science.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.

在化学系化学催化项目的支持下，南加州大学的斯马兰达·C·马里内斯库将研究开发生物灵感催化系统，将有害二氧化碳转化为化学燃料。在全球迅速变暖的情况下，开发清洁能源技术作为化石燃料的替代品是一项迫切的需要。太阳能作为一种清洁能源备受关注，但主要集中在发电上。这种狭隘的关注不足以满足交通、供暖和工业使用的可再生燃料的需求，这些燃料占能源需求的70%左右。可持续的能源未来将需要一种非化石燃料方法来形成化学原料，而利用太阳能产生的电力电化学还原二氧化碳(CO2)和水(H2O)等丰富的小分子是一种可行的途径。这种方法将允许以化学键的方式存储太阳能，其方式与自然界通过光合作用实现的方式类似，光合作用利用光子能量来推动二氧化碳还原为各种高能产品。受生物系统的启发，Marinescu团队将开发涉及氢键网络的分子催化剂，这种网络能够通过多次质子和电子转移来激活小分子。该项目将专注于开发一系列具有生物灵感的带有侧胺的金属络合物，这将使人们能够了解质子继电器对多电子、多质子反应的影响。配体框架可以很好地控制电子和定位效应，这将有助于结构-活性研究。纳入这一研究计划的是一个教育方案，重点是向少数民族学生比例较高的当地社区大学的学生和教师提供研究机会，以及为博士后水平的女性提供指导方案，以增加这一代表不足的群体对科学的参与。从长远来看，这些外展和指导活动将影响到相当数量的个人：教师及其几代学生，以及南加州大学的研究人员。重要的是，参与这些努力的学生将发展一种为他们的科学和非科学社区做出贡献的文化，预计这种文化将持续到他们的形成时期。在化学系化学催化项目的支持下，南加州大学的斯马兰达·C·马里内斯库将研究悬挂质子继电器对钴氨基吡啶大环二氧化碳减排的影响。Marinescu小组最近的工作表明，一系列含有0到4个侧链仲胺(NH)的钴配合物显示出二氧化碳还原速度与侧链NH部分的数量之间的线性关系。实验和理论表明，悬挂的NH基团不会直接将质子转移到二氧化碳，而是与溶液中的酸分子结合，形成催化剂-酸加合物，通过氢键网络结合在一起，使质子能够从酸直接转移到活化的二氧化碳底物。研究的目的是通过表征和改变这些金属氨基吡啶大环的电子环境(一次配位球体和二次配位球体)，从二氧化碳还原的活性和选择性方面了解控制这些配合物的催化性能的因素。本项目致力于合成和表征各种带有侧链氢键供体或阳离子基团的氨基吡啶配合物，以了解这些基团对催化剂活性和选择性的影响。科学教育的目标将集中在：(1)为Cerritos学院的学生组织暑期研讨会，Cerritos学院是一所公立社区大学，学生来自代表不足的群体的比例很高，并在夏季期间在Marinescu实验室接待Cerritos学院的一名学生进行为期8周的本科生研究；以及(2)为博士后女性制定一个指导计划，以增加女性对科学的参与。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。

项目成果

Primary- and secondary-sphere effects of amine substituent position on rhenium bipyridine electrocatalysts for CO2 reduction

胺取代基位置对联吡啶铼电催化剂 CO2 还原的初级和次级影响

• DOI: 10.1016/j.poly.2022.115933
• 发表时间: 2022
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Hellman, Ashley N.;Intrator, Jeremy A.;Choate, Jeremiah C.;Velazquez, David A.;Marinescu, Smaranda C.
• 通讯作者: Marinescu, Smaranda C.

Effects of Protonation State on Electrocatalytic CO 2 Reduction by a Cobalt Aminopyridine Macrocyclic Complex

质子化状态对钴氨基吡啶大环配合物电催化CO 2 还原的影响

• DOI: 10.1021/acs.inorgchem.1c01977
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Liu, Jeffrey J.;Chapovetsky, Alon;Haiges, Ralf;Marinescu, Smaranda C.
• 通讯作者: Marinescu, Smaranda C.