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.

在化学催化计划的支持下，密歇根大学的尼拉拉·辛格（Nirala Singh），布莱恩·戈德史密斯（Nirala Singh），布莱恩·戈德史密斯（Bryan Goldsmith）和Suljo Linic正在研究尿素的生产，这是一种重要的肥料，使用可再生的电力，二氧化碳和硝酸盐的硝酸盐和废水中的硝酸盐。尿素目前是使用氨制造的。尿素合成的氨产生产生大量二氧化碳，因为氨是通过首先将天然气转化为氢和二氧化碳，然后在高温下结合氢和氮。所提出的过程将使用由可再生电力供电的低温电化学方法对二氧化碳和硝酸盐进行配对，以直接生产尿素，少于二氧化碳排放量要少得多。这项研究有可能在减轻两种有害的空气和水污染物的同时改变尿素的生产范式。该项目将通过灰熊学者计划与小学学生有关STEM（科学，技术，工程和数学）的知识，并通过夏季高中学徒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Nirala Singh，Bryan Goldsmith和Suljo Linic团队正在使用二氧化碳和硝酸盐研究电催化C-N偶联。通过一种联合计算和实验方法，他们将研究金属合金上二氧化碳和硝酸盐偶联的反应机制，其靶标是对尿素的选择性提高。他们将衡量二氧化碳和硝酸盐浓度的部分压力的影响，以鉴定潜在的反应机制并与原子建模研究进行比较，以识别速率确定的和选择性指定的步骤。他们将使用拉曼和X射线吸收光谱镜在反应条件下表征电催化剂，以更好地了解反应机理。他们还将调查线性吸附剂比例关系在限制尿素选择性方面的作用，以及如何使用新型合金组成的使用可以避免这些局限性。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的评估来通过评估来支持的。

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