EAGER: Electrocatalysis Modulated by Bifunctional Organic Monolayer: CO2 Reduction to C2

探索性研究早期概念拨款（EAGER）为支持我国向清洁能源过渡的新技术提供概念验证数据。清洁能源方程式的一部分涉及化石资源燃烧产生的二氧化碳（CO2）的捕获和转化。该项目通过探索将二氧化碳转化为广泛用于制造各种化学和燃料产品的小构件分子的电化学方法，进一步支持低碳排放化学制造的进展。这项研究的重点是新型催化剂设计，这种设计可以促进高度局部化的电场，从而可能比传统催化剂设计更有效地利用能量和提高二氧化碳转化效率。该项目还包括针对大学预科和大学阶段学生的清洁能源相关教育和推广活动。高电场可以重新排列化学物质的电子轨道，改变吸附物和催化表面之间的电子相互作用。这影响了（电）催化反应的热力学、动力学和机理。该项目研究了局部电场和暴露的表面位置对二氧化碳电还原反应（CO2RR）到C2产物的影响。该概念的研究结合了原子尺度模拟、电催化剂合成、光谱表征和电催化性能测试。催化剂是由双功能硫醇基单层（例如-S-CnH2n-NH2）固定在Cu纳米线（NW）阵列上制备的。这种催化结构增强了局部电场，因为在单层的头部和尾部官能团相反的电荷。同时调整硫醇分子的表面覆盖以暴露Cu台阶和缺陷位点。将通过(1)导出硫醇组成/结构与局部场强之间的关系，(2)确定硫醇对暴露的Cu位点的表面覆盖效应，以及(3)在反应条件下研究双功能有机单层修饰Cu NWs的性能和稳定性来评估组合方法加速co2r到c2的有效性。在研究的同时，研究人员将让研究生和本科生参与他们的研究，并参加麻省大学洛厄尔分校的沉浸式学者计划，以促进本科生的研究，包括女性和代表性不足的少数民族。研究人员还将把清洁能源技术和模块化电催化的重要性传达给幼儿园-九年级学生的推广活动，并通过各种教育媒体进行传播。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。

This Early-concept Grant for Exploratory Research (EAGER) provides proof-of-concept data for a novel technology supporting our nation’s transition to clean energy. Part of the clean energy equation involves the capture and conversion of carbon dioxide (CO2) produced from the combustion of fossil resources. The project further supports progress towards low carbon emission chemical manufacturing by exploring electrochemical conversion of CO2 to small building-block molecules used widely in the manufacture of a broad range of chemical and fuel products. The study focuses on novel catalyst designs that promote highly localized electric fields, thus potentially enabling more efficient energy utilization and greater CO2 conversion efficiency than obtained with conventional catalyst designs. The project also incorporates clean-energy related educational and outreach activities targeted at both pre-college and college level students. A high electric field can rearrange the electronic orbitals of chemical species and alter the electronic interactions between adsorbates and catalytic surfaces. This influences the thermodynamics, kinetics, and mechanisms of (electro)catalytic reactions. The project investigates the effects of local electric fields and exposed-surface sites on the CO2 electroreduction reaction (CO2RR) to C2 products. The concept is investigated using a combination of atomic-scale simulations, electrocatalyst synthesis, spectroscopic characterization, and electrocatalytic performance testing. The catalyst is prepared from a bifunctional thiol-based monolayer (e.g., -S-CnH2n-NH2) immobilized onto a Cu nanowire (NW) array. This catalytic structure enhances local electric fields due to opposing charges in the head and tail functional groups of the monolayer. Surface coverage of thiol molecules is simultaneously tuned to expose Cu step and defect sites. Effectiveness of the combined approach for accelerating CO2RR-to-C2 will be evaluated by (1) deriving relationships between thiol composition/structure and local field strength, (2) determining the thiol surface coverage effects on exposed Cu sites, and (3) investigating the performance and stability of the bifunctional organic monolayer modified Cu NWs under reaction conditions. In parallel with the research, the investigators will involve both graduate students and undergraduate students in their research, and participate in the Immersive Scholar Program at UMass Lowell to promote undergraduate research, including women and underrepresented minorities. The investigators will also convey the importance of clean energy technology and modular electrocatalysis into outreach activities for K-9 students and distribution via various educational media.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.