CAS-SC: Elucidating the Electrocatalytic Coupling of Nitrate and Carbon Dioxide: Toward Electron Efficient C-N Coupling

CAS-SC：阐明硝酸盐和二氧化碳的电催化耦合：迈向电子高效的 C-N 耦合

• 批准号: 2247194
• 负责人: Nirala Singh
• 金额: $ 75万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-04-15 至 2026-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247194&HistoricalAwards=false
• 关键词: CAS; SC; Elucidating; Electrocatalytic; Coupling

With the support of the Chemical Catalysis Program in the Division of Chemistry, Nirala Singh, Bryan Goldsmith, and Suljo Linic of the University of Michigan are studying the production of urea, an important fertilizer, using renewable electricity, carbon dioxide, and nitrate from wastewater. Urea is currently manufactured using ammonia. Ammonia production for urea synthesis emits large quantities of carbon dioxide because ammonia is produced by first converting natural gas to hydrogen and carbon dioxide, then combining hydrogen and nitrogen at high temperatures. The proposed process will instead use low-temperature electrochemical methods powered by renewable electricity to couple carbon dioxide and nitrate to directly produce urea with much less carbon dioxide emissions. This research has the potential for a paradigm shift in the production of urea while mitigating two harmful air and water pollutants. The project will engage elementary schoolers about STEM (science, technology, engineering and mathematics) through the Grizzly Scholar program and provide high school students with research experience each summer through a Summer High School Apprentice Researchers Program. These educational programs aim to foster development of the next generation of STEM students. Under this project the team of Nirala Singh, Bryan Goldsmith, and Suljo Linic of the University of Michigan is studying electrocatalytic C-N coupling using carbon dioxide and nitrate. Through a joint computational and experimental approach, they will study the reaction mechanism of carbon dioxide and nitrate coupling on metal alloys with a target of increasing selectivity to urea. They will measure the effects of partial pressure of carbon dioxide and concentration of nitrate to identify potential reaction mechanisms and compare with atomistic modeling studies to identify rate-determining and selectivity-determining steps. They will use Raman and X-ray absorption spectroscopies to characterize the electrocatalysts under reaction conditions to better understand the reaction mechanism. They will also investigate the role that linear adsorbate scaling relations have on limiting the urea selectivity, and how the use of novel alloy compositions can avoid these limitations.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，密歇根大学的 Nirala Singh、Bryan Goldsmith 和 Suljo Linic 正在研究利用可再生电力、二氧化碳和废水中的硝酸盐生产尿素（一种重要的肥料） 。目前尿素是使用氨生产的。用于尿素合成的氨生产会排放大量二氧化碳，因为氨是通过首先将天然气转化为氢气和二氧化碳，然后在高温下结合氢气和氮气来生产的。拟议的工艺将改为使用由可再生电力驱动的低温电化学方法来耦合二氧化碳和硝酸盐，直接生产尿素，二氧化碳排放量要少得多。这项研究有可能改变尿素生产的范式转变，同时减少两种有害的空气和水污染物。该项目将通过灰熊学者计划让小学生了解 STEM（科学、技术、工程和数学），并通过暑期高中学徒研究人员计划为高中生提供研究经验。这些教育计划旨在促进下一代 STEM 学生的发展。在这个项目下，密歇根大学的 Nirala Singh、Bryan Goldsmith 和 Suljo Linic 团队正在研究使用二氧化碳和硝酸盐的电催化 C-N 偶联。通过联合计算和实验方法，他们将研究二氧化碳和硝酸盐在金属合金上偶联的反应机制，目标是提高尿素的选择性。他们将测量二氧化碳分压和硝酸盐浓度的影响，以确定潜在的反应机制，并与原子模型研究进行比较，以确定速率决定和选择性决定步骤。他们将使用拉曼和X射线吸收光谱来表征反应条件下的电催化剂，以更好地了解反应机理。他们还将研究线性吸附物结垢关系对限制尿素选择性的作用，以及如何使用新型合金成分来避免这些限制。该奖项反映了 NSF 的法定使命，并通过使用基金会的知识产权进行评估，被认为值得支持。优点和更广泛的影响审查标准。

项目成果

Identifying the active site of Cu/Cu2O for electrocatalytic nitrate reduction reaction to ammonia

• DOI: 10.1016/j.checat.2023.100850
• 发表时间: 2023-12
• 期刊: Chem Catalysis
• 作者: Gabriel F. Costa;Manuel Winkler;Thiago Mariano;M. R. Pinto;Igor Messias;João B. Souza;I. Neckel;Maria F.C. Santos;Cláudio F Tormena;Nirala Singh;Raphael Nagao