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

EAGER：双功能有机单层调节的电催化：CO2 还原为 C2

• 批准号: 2103478
• 负责人: Fanglin Che
• 金额: $ 27.05万
• 依托单位: University of Massachusetts Lowell
• 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: 2021-03-15 至 2024-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2103478&HistoricalAwards=false
• 关键词: EAGER; Electrocatalysis; Modulated; Bifunctional; Organic

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.

探索性研究早期概念补助金（EAGER）为支持我们国家向清洁能源过渡的新技术提供了概念验证数据。 清洁能源方程式的一部分涉及捕获和转化化石资源燃烧产生的二氧化碳（CO2）。 该项目通过探索将二氧化碳电化学转化为广泛用于制造各种化学和燃料产品的小分子，进一步支持在低碳排放化学制造方面取得进展。 该研究的重点是促进高度局部化电场的新型催化剂设计，从而可能实现比传统催化剂设计更有效的能源利用和更高的CO2转化效率。 该项目还包括针对大学预科和大学学生的与清洁能源有关的教育和外联活动。高电场可以重排化学物种的电子轨道，并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表面位置对CO2电还原反应（CO2 RR）生成C2产物的影响。 这个概念是使用原子尺度的模拟，电催化剂合成，光谱表征和电催化性能测试相结合的研究。该催化剂由双官能硫醇基单层（例如，- S-CnH 2n-NH 2）固定到Cu纳米线（NW）阵列上。这种催化结构由于单层的头部和尾部官能团中的相反电荷而增强局部电场。硫醇分子的表面覆盖率同时被调整以暴露Cu台阶和缺陷位点。 用于加速CO2 RR至C2的组合方法的有效性将通过以下来评估：（1）推导硫醇组成/结构与局部场强之间的关系，（2）确定硫醇表面覆盖对暴露的Cu位点的影响，以及（3）研究双官能有机单层改性的Cu纳米线在反应条件下的性能和稳定性。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，包括妇女和代表性不足的少数民族。调查人员还将传达清洁能源技术和模块化电催化的重要性到外展活动的K-9学生和分布通过各种教育媒体。这个奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

项目成果

Leveraging bismuth immiscibility to create highly concave noble-metal nanoparticles

• DOI: 10.1016/j.chempr.2024.02.002
• 发表时间: 2024-02
• 期刊: Chem
• 影响因子: 23.5
• 作者: Melissa E. King;Yuting Xu;Porvajja Nagarajan;Noah L. Mason;Anthony J. Branco;Connor S. Sullivan;Samantha M. Silva;Sangmin Jeong;Fanglin Che;Michael B. Ross

Beyond C–C coupling in CO2 reduction

超越 C–C 耦合减少二氧化碳排放

• DOI: 10.1038/s44286-023-00019-9
• 发表时间: 2024
• 期刊: Nature Chemical Engineering
• 作者: Xu, Yuting;Che, Fanglin
• 通讯作者: Che, Fanglin

Hybrid Organic‐Inorganic Heterogeneous Interfaces for Electrocatalysis: A Theoretical Study of CO 2 Reduction to C 2

用于电催化的有机-无机杂化多相界面：CO 2 还原为 C 2 的理论研究

• DOI: 10.1002/cctc.202101224
• 发表时间: 2021
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Wan, Mingyu;Gu, Zhiyong;Che, Fanglin
• 通讯作者: Che, Fanglin