Collaborative Research: CAS: Graphite-Conjugated Macrocycle Electrocatalysts for Nitrate Reduction

合作研究：CAS：石墨共轭大环电催化剂用于硝酸盐还原

• 批准号: 2102442
• 负责人: Jeremy Smith
• 金额: $ 25.97万
• 依托单位: Indiana University
• 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: 2021-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102442&HistoricalAwards=false
• 关键词: Collaborative; Research; CAS; Graphite; Conjugated

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Yulia Pushkar of Purdue University, Professor Jeremy Smith of Indiana University and Associate Professor Elena Jakubikova of North Carolina State University are studying catalysts that will use electrical energy for the conversion of aqueous nitrate to useful or benign products such as ammonia. Nitrate is a water pollutant that occurs largely as a result of agricultural fertilizer use. The proposed research takes a first step to addressing this problem through the development of robust and efficient electrocatalysts that to convert nitrate to desirable compounds via reductive chemistry. Scientific insights gained through these studies will likely impact the development of other electrocatalysts for other useful electrochemical conversions. Outreach activities include a partnership with the public radio program “A Moment of Science” and the development of YouTube videos on the nitrogen cycle.This project combines the expertise of three research groups in synthetic, electrochemical, spectroscopic, and computational studies on the development of environmentally relevant electrocatalysts. A modular class of graphite-conjugated macrocyclic complexes will be characterized by a range of physical methods, including synchrotron-based X-ray spectroscopy. Together with experimentally calibrated electronic structure calculations, these data will provide information on the coordination environment, structure, and electron configuration of the metal ion. Redox properties will be characterized by electrochemical measurements, with computational methods providing detailed insights into the electronic structures of different oxidation states. In addition to standard electrochemical and computational methods for mechanistic interrogation, in situ spectroscopic characterization is expected to provide detailed information on the nature of intermediates in the catalytic cycle. Mechanistic investigations into materials that are selective for nitrate reduction will provide insight that is expected to aid in the rational design of catalysts having improved activity. Outreach activities are to including a partnership with a public radio broadcast and the development of publicly accessible educational videos are expected to reach a wide audience and inform the public broadly about electrocatalysis and its utility in developing environmentally beneficial reductive nitrogen chemistry.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，普渡大学的Yulia Pushkar教授、印第安纳大学的Jeremy Smith教授和北卡罗来纳州立大学的Elena Jakubikova副教授正在研究利用电能将硝酸盐水转化为有用或无害产品(如氨)的催化剂。硝酸盐是一种水污染物，主要由于农业化肥的使用而产生。这项拟议的研究为解决这一问题迈出了第一步，方法是开发强大而高效的电催化剂，通过还原化学将硝酸盐转化为理想的化合物。通过这些研究获得的科学见解可能会影响其他电催化剂的开发，用于其他有用的电化学转化。外展活动包括与公共广播节目《科学时刻》的合作，以及开发关于氮循环的YouTube视频。该项目结合了三个研究小组在环境相关电催化剂开发方面的合成、电化学、光谱和计算研究的专业知识。一类模块化的石墨共轭大环化合物将通过一系列物理方法进行表征，包括基于同步加速器的X射线光谱分析。结合实验校准的电子结构计算，这些数据将提供有关金属离子的配位环境、结构和电子构型的信息。氧化还原性能将通过电化学测量来表征，计算方法将提供对不同氧化态的电子结构的详细见解。除了用于机械询问的标准电化学和计算方法外，原位光谱表征有望提供关于催化循环中中间体性质的详细信息。对硝酸盐还原选择性材料的机械研究将提供洞察力，有望有助于合理设计具有更高活性的催化剂。外展活动将包括与公共广播电台的合作，以及开发公众可访问的教育视频，预计将覆盖广泛的受众，并向公众广泛介绍电催化及其在开发环境有益的还原氮化学方面的效用。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

Electrocatalytic Reduction of Nitrogen Oxyanions with a Redox-Active Cobalt Macrocycle Complex

用氧化还原活性钴大环配合物电催化还原氮氧阴离子

• DOI: 10.1021/acs.inorgchem.2c00199
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Partovi, Sheyda;Xiong, Ziqing;Kulesa, Krista M.;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Electrocatalytic reduction of nitrate by in situ generated cobalt nanoparticles

原位生成的钴纳米粒子电催化还原硝酸盐

• DOI: 10.1039/d2cc00853j
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Ghosh, Moumita;Ibrar, Maha;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Electrocatalytic nitrate reduction with Co-based catalysts: comparison of DIM, TIM and cyclam ligands

钴基催化剂电催化硝酸盐还原：DIM、TIM 和 cyclam 配体的比较

• DOI: 10.1039/d1dt02175c
• 发表时间: 2021
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Kwon, Hyuk-Yong;Braley, Sarah E.;Madriaga, Jose P.;Smith, Jeremy M.;Jakubikova, Elena
• 通讯作者: Jakubikova, Elena

A Spectroscopically Observed Iron Nitrosyl Intermediate in the Reduction of Nitrate by a Surface-Conjugated Electrocatalyst

• DOI: 10.1021/jacs.2c03487
• 发表时间: 2022-09-26
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ghosh, Moumita;Braley, Sarah E.;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Buffer Assists Electrocatalytic Nitrite Reduction by a Cobalt Macrocycle Complex

• DOI: 10.1021/acs.inorgchem.2c00909
• 发表时间: 2022-08-10
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Braley, Sarah E.;Kwon, Hyuk-Yong;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.