Collaborative Research: INFEWS N/P/H2O: Electrochemical Approaches to Sustainable Dinitrogen Fixation

合作研究：INFEWS N/P/H2O：可持续二氮固定的电化学方法

• 批准号: 1665135
• 负责人: Alexander Miller
• 金额: $ 30万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665135&HistoricalAwards=false
• 关键词: Collaborative; Research; INFEWS; H2O; Electrochemical

In this project funded by the Chemical Catalysis Program of the Chemistry Division, scientists from the University of North Carolina at Chapel Hill (UNC), Yale University, and Rutgers University are collaborating to develop approaches to sustainable electrochemical fixation of nitrogen (N2). Sustainable nitrogen fixation is central to the nexus of challenges in food, energy, and water chemistry. Current global food production is enabled by the use of synthetic fertilizer that is produced by nitrogen fixation processes that generate ammonia (NH3) from nitrogen and hydrogen (H2), but leave a dramatic negative impact on energy and the environment, consuming about 2% of the world?s fossil fuel-derived energy supply. In this project, Prof. Alexander Miller (UNC), Profs. James Mayer and Patrick Holland (Yale), and Profs. Alan Goldman and Gal Hochman (Rutgers) are exploring new, sustainable methods for nitrogen fixation. New chemistry will be developed that could enable the development of electrochemical nitrogen fixation processes that do not require consumption of fossil fuels to produce ammonia and nitrates. Sustainability and policy analysis will assess the potential for transformative impact on global agriculture and energy sectors (including consideration of ammonia as a possible liquid transportation fuel). The project will train graduate students and postdoctoral researchers in interdisciplinary problem-based scientific methods and positively impact institutional infrastructure. The topic and the results of the research will be used as a platform to teach non-scientists about the importance of chemical catalysis in industry, agriculture, and modern society in general. The interdisciplinary research team has strengths in catalyst design and synthesis, electrocatalysis, mechanistic studies, and sustainability and policy analysis. The chemical approach to N2 fixation involves transition-metal-electrocatalyzed reductive splitting of N2 into nitrido intermediates. These nitrido intermediates can undergo (a) nitride reduction to NH3 by proton-coupled electron transfer (PCET), or (b) nitride oxidation toward nitric acid. Middle-to-late transition metal complexes of robust and tunable pincer ligands will be an experimental focus, with complementary computational studies to correlate reactivity with molecular properties and guide catalyst development. The cost of potential electrochemical N2 fixation processes will be analyzed, to estimate the dependence on a range of factors such as diversity of electricity sources, intermittency of sustainable energy, and governmental policy.

在这个由化学部化学催化计划资助的项目中，来自查佩尔山的北卡罗来纳州大学、耶鲁大学和罗格斯大学的科学家正在合作开发可持续电化学固定氮（N2）的方法。可持续固氮是粮食、能源和水化学挑战的核心。目前的全球粮食生产是通过使用合成肥料来实现的，合成肥料是通过固氮过程产生的，固氮过程从氮和氢（H2）产生氨（NH3），但对能源和环境产生巨大的负面影响，消耗了世界上约2%的资源。的化石燃料衍生能源供应。在这个项目中，亚历山大米勒教授（教授），教授。James Mayer和帕特里克荷兰（耶鲁大学），以及教授。Alan Goldman和Gal Hochman（罗格斯大学）正在探索新的、可持续的固氮方法。将开发新的化学物质，从而能够开发不需要消耗化石燃料来生产氨和硝酸盐的电化学固氮过程。可持续性和政策分析将评估对全球农业和能源部门产生变革性影响的潜力（包括考虑将氨作为可能的液体运输燃料）。该项目将培训研究生和博士后研究人员跨学科的问题为基础的科学方法，并积极影响体制基础设施。该研究的主题和结果将被用作一个平台，教导非科学家关于化学催化在工业，农业和现代社会中的重要性。跨学科研究团队在催化剂设计和合成，电催化，机理研究以及可持续性和政策分析方面具有优势。N2固定的化学方法涉及过渡金属电催化的N2还原分裂成氮化物中间体。这些氮化物中间体可以经历（a）通过质子耦合电子转移（PCET）将氮化物还原成NH 3，或（B）氮化物氧化成硝酸。稳健和可调的钳形配体的中晚期过渡金属络合物将是实验重点，补充计算研究将反应性与分子性质相关联，并指导催化剂的开发。将分析潜在的电化学N2固定过程的成本，以估计对一系列因素的依赖性，如电源的多样性，可持续能源的可靠性和政府政策。

项目成果

Considering Electrocatalytic Ammonia Synthesis via Bimetallic Dinitrogen Cleavage

• DOI: 10.1021/acscatal.0c02606
• 发表时间: 2020-10-02
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Bruch, Quinton J.;Connor, Gannon P.;Miller, Alexander J. M.
• 通讯作者: Miller, Alexander J. M.

A bis(arylphosphinito)amide pincer ligand that binds nickel forming six-membered metallacycles

一种双（芳基亚膦基）酰胺钳配体，可结合镍形成六元金属环

• DOI: 10.1016/j.poly.2020.114380
• 发表时间: 2020
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Bruch, Quinton J.;Miller, Alexander J.M.
• 通讯作者: Miller, Alexander J.M.

Electrochemical C–H bond activation via cationic iridium hydride pincer complexes

通过阳离子氢化铱钳配合物电化学激活C–H键

• DOI: 10.1039/c9sc03076j
• 发表时间: 2019
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Lindley, Brian M.;Walden, Andrew G.;Brasacchio, Ann Marie;Casuras, Andrea;Lease, Nicholas;Chen, Chun-Hsing;Goldman, Alan S.;Miller, Alexander J.
• 通讯作者: Miller, Alexander J.

A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone

• DOI: 10.1021/acs.inorgchem.7b02889
• 发表时间: 2018-02-19
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Bruch, Quinton J.;Lindley, Brian M.;Miller, Alexander J. M.
• 通讯作者: Miller, Alexander J. M.

Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer

• DOI: 10.1021/jacs.9b10031
• 发表时间: 2019-12-25
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Bruch, Quinton J.;Connor, Gannon P.;Miller, Alexander J. M.
• 通讯作者: Miller, Alexander J. M.