CAS: Molecular Catalysts to Control Dinitrogen Reduction and Ammonia Oxidation

CAS：控制氮还原和氨氧化的分子催化剂

• 批准号: 1956161
• 负责人: Michael Mock
• 金额: $ 47.57万
• 依托单位: Montana State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2023-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1956161&HistoricalAwards=false
• 关键词: CAS; Molecular; Catalysts; Control; Dinitrogen

The Established Program to Stimulate Competitive Research (EPSCoR) and the Chemical Catalysis Program in the Chemistry Division, both of the National Science Foundation, support this project led by Professor Michael Mock of Montana State University. Professor Mock leads an effort to develop fuels that are derived from nitrogen in the air and ammonia that is produced from that nitrogen. The overarching goal is to explore new systems for energy storage. The focus is on the synthesis and analysis of new metal catalysts for the interconversion of nitrogen gas and ammonia. The new catalysts are based on ruthenium, nickel, iron, and chromium. Compounds consisting of these metals are proposed to exhibit novel behavior that facilitates the interconversion of nitrogen and ammonia. Of specific interest are strategies for the attachment and removal of hydrogen atoms. One approach involves creating chemical relays that carry the hydrogen from the metal to the nitrogen. The chemical synthesis of these relays is a specialty of Professor Mock. In addition to the research, Professor Mock is developing outreach activities to engage students at area schools, teaching them about energy technologies. He also is recruiting Native American undergraduate students from Montana Tribal Colleges to work in his laboratory. By providing hands-on experience in chemistry and catalysis to Native Americans, the project is strengthening the technical workforce in the United States. Professor Michael Mock of Montana State University is leading an effort to develop a nitrogen-based cycle to store energy in N-H bonds by synthesizing new molecular catalysts for the fundamental processes involved in the interconversion of dinitrogen (N2) and ammonia (NH3). The goal of this research is the development of molecular catalytic systems for N2 reduction and NH3 oxidation with a common strategy of delivery of H-atoms to N2 and and the removal of H-atoms from NH3 ligands. This project seeks to understand the reaction mechanisms of these processes by characterizing metal-NxHy intermediates, and measuring thermodynamic N-H bond strengths to advance catalyst design. The proposed work on catalytic N2 reduction schemes uses chemically robust chromium complexes. In the development of NH3 oxidation catalysts, the use of Ru and Ni-based platforms is advancing the goal of understanding homolytic N–H bond cleavage and N–N coupling steps en route to N2 formation. In addition to this research, Professor Mock is developing science outreach activities to engage students at area schools and Tribal Colleges about alternative forms of energy and new chemical technologies that have a positive impact on the environment and society. Professor Mock is recruiting Native American undergraduate students to his lab from Montana Tribal Colleges through summer internships to gain hands-on experience in chemistry and catalysis.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.

美国国家科学基金会化学部的既定刺激竞争性研究计划（EPSCoR）和化学催化计划支持蒙大拿州立大学迈克尔·莫克教授领导的这一项目。 莫克教授领导了一项工作，开发从空气中的氮气和由氮气产生的氨中提取的燃料。总体目标是探索新的能源存储系统。 重点研究用于氮气和氨相互转化的新型金属催化剂的合成和分析。新催化剂基于钌、镍、铁和铬。由这些金属组成的化合物被认为表现出促进氮和氨相互转化的新颖行为。特别令人感兴趣的是氢原子的附着和去除策略。一种方法涉及创建化学继电器，将氢从金属输送到氮气。 这些继电器的化学合成是莫克教授的专长。 除了研究之外，莫克教授还开展外展活动，吸引地区学校的学生参与，向他们传授能源技术知识。 他还从蒙大拿州部落学院招募美国原住民本科生到他的实验室工作。 通过向美洲原住民提供化学和催化方面的实践经验，该项目正在加强美国的技术劳动力。 蒙大拿州立大学的 Michael Mock 教授正在领导一项工作，通过合成新的分子催化剂，开发一种基于氮的循环，以 N-H 键储存能量，用于二氮 (N2) 和氨 (NH3) 相互转化的基本过程。本研究的目标是开发用于 N2 还原和 NH3 氧化的分子催化系统，其共同策略是将 H 原子传递到 N2 并从 NH3 配体中去除 H 原子。该项目旨在通过表征金属-NxHy 中间体并测量热力学 N-H 键强度来了解这些过程的反应机制，以推进催化剂设计。拟议的催化 N2 还原方案工作使用化学性质稳定的铬络合物。在NH3氧化催化剂的开发中，Ru和Ni基平台的使用正在推进理解均裂N-H键断裂和N2形成过程中的N-N偶联步骤的目标。除了这项研究之外，莫克教授还开展科学推广活动，让地区学校和部落学院的学生了解对环境和社会产生积极影响的替代能源形式和新化学技术。莫克教授正在通过暑期实习从蒙大拿州部落学院招募美国原住民本科生到他的实验室，以获得化学和催化方面的实践经验。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智力价值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

Synthesis, characterization, and liquid injection field desorption ionization mass spectrometry analysis of pincer ligated group 6 (Cr, Mo, W) carbonyl complexes

• DOI: 10.1177/14690667221149498
• 发表时间: 2023-01
• 期刊: European Journal of Mass Spectrometry
• 影响因子: 1.3
• 作者: Olivia L. Duletski;N. Arulsamy;Michael T. Mock

Catalytic Ammonia Oxidation to Dinitrogen by a Nickel Complex

镍络合物催化氨氧化制氮

• DOI: 10.1002/anie.202213462
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Stephens, David N.;Szilagyi, Robert K.;Roehling, Paige N.;Arulsamy, Navamoney;Mock, Michael T.
• 通讯作者: Mock, Michael T.