CAREER:Engineering Interphases for Li-Mediated Nitrogen Reduction at Ambient Conditions

职业：常温条件下锂介导氮还原的工程中间相

• 批准号: 2204756
• 负责人: Karthish Manthiram
• 金额: $ 62.5万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-10-01 至 2025-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2204756&HistoricalAwards=false
• 关键词: CAREER; Engineering; Interphases; Li; Mediated

Chemical manufacturing is a key contributor to the Nation's economy, producing everything from fertilizers and pharmaceuticals to plastics and fuels. Despite the successes of the chemical industry to produce chemicals and materials critical to everyday living, there are issues associated with the carbon-footprint and centralization of chemical manufacturing. Many chemical processes are run in centralized plants at large scale because smaller capacities are not economically viable. An example is the Haber-Bosch process that produces a large portion of the ammonia needed for nitrogen-containing fertilizers. The process is run at high temperatures and pressures and at large scale in a centralized fashion. Furthermore, the Haber-Bosch process contributes to 1 - 2% of global carbon dioxide emissions. Electrochemical synthesis of ammonia could enable competitive manufacture at a lower carbon footprint and with a smaller production capacity. By applying an electrical potential to drive reactions instead of using temperature and pressure, chemical processes can be run at milder conditions, at smaller scales, and closer to the end user, e.g. in a distributed fashion. This CAREER project will focus on fundamental research to study ways to improve selectivity and production rates of an electrochemical process for ammonia production using a lithium based electrochemical system. Methods developed in the project will advance how to selectively synthesize one chemical (ammonia) over another at the highly reactive electrode-electrolyte interface. The research knowledge will be adapted to be used in an outreach program focused on teaching the importance of mass and energy balances to middle school students. Understanding where everyday chemicals and materials come from and how they are produced will allow for critical evaluation of their impact on society and the environment. To date, synthesis methods using electrochemical nitrogen reduction suffer from poor selectivity and low reaction rates in aqueous electrolytes due to the competing hydrogen evolution reaction. In order to improve selectivity for nitrogen reduction, this project will investigate ammonia synthesis in nonaqueous electrolytes, as the proton activity can be well-controlled, with a lithium metal-mediated chemistry, which allows for nitrogen fixation at ambient conditions. The effect of the electrolyte composition on the solid-electrolyte interphase (SEI) species present on the lithium-covered electrode will be studied with both in situ and ex situ spectroscopic methods. The SEI structure and composition is hypothesized to control the selectivity for nitrogen reduction versus competing hydrogen evolution. The project will address the nature of the transport limitations and its impact on the coupled transport-kinetics. As a result of this work, fundamental understanding of the necessary interfacial steps for efficient electrochemical ammonia production in a nonaqueous solvent will be obtained. This understanding will translate to other electrosynthetic reactions in nonaqueous electrolytes that take place at SEIs. The project is structured into three aims. Aim 1 addresses engineering the solid electrolyte interphase to promote desired interfacial reactions. Aim 2 will study the design of omniphobic electrodes for non-aqueous solvents to achieve fast nitrogen transport to the active sites. Finally, Aim 3 will focus on the mass and energy balances for anode and electrolyte design.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.

化学制造是造成国家经济的关键因素，从肥料和药品到塑料和燃料，都产生了一切。尽管化学工业在生产对日常生活至关重要的化学物质和材料方面取得了成功，但与化学制造的碳足迹和集中化有关的问题仍然存在。由于较小的能力在经济上不可行，因此许多化学过程在集中式植物中进行。一个例子是Haber-Bosch过程，该过程产生了含氮肥料所需的大部分氨。该过程是在高温和压力下运行的，并以集中的方式进行大规模运行。此外，Haber -Bosch过程占全球二氧化碳排放量的1-2％。氨的电化学合成可以以较低的碳足迹和较小的生产能力来实现竞争性制造。通过应用电势驱动反应而不是使用温度和压力，化学过程可以在较小的条件下，较小的尺度和更接近最终用户的情况下运行，例如以分布式方式。该职业项目将重点介绍基础研究，以研究使用基于锂的电化学系统来提高氨产生电化学过程的选择性和生产率的方法。项目中开发的方法将推进如何在高反应性电极 - 电解质界面上选择性合成一种化学（氨）。研究知识将适用于一项旨在教授质量和能量平衡对中学生的重要性的外展计划。了解日常化学物质和材料的来源以及它们的生产方式将允许对它们对社会和环境的影响进行批判性评估。迄今为止，由于相互竞争的氢进化反应，使用电化学氮降低的合成方法的选择性差和低反应速率较低。为了提高减少氮的选择性，该项目将研究非液压电解质中的氨合成，因为质子活性可以很好地控制，并使用锂金属介导的化学反应，这允许在环境条件下固氮。电解质组成对存在于锂覆盖电极的固体电解质相（SEI）物种的影响将通过原位和原位光谱方法进行研究。假设SEI结构和组成可以控制氮还原与竞争氢进化的选择性。该项目将解决运输局限性的性质及其对耦合运输运动学的影响。这项工作的结果是，将获得对非液态溶剂中有效电化学氨的必要界面步骤的基本理解。这种理解将转化为SEIS发生的非水晶电解质中的其他电合成反应。该项目分为三个目标。 AIM 1解决了工程固体电解质之间的关系，以促进所需的界面反应。 AIM 2将研究非水溶剂的杂质电极的设计，以实现快速的氮转运到活跃位点。最后，AIM 3将重点关注阳极和电解质设计的质量和能量平衡。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响标准，被认为值得通过评估来获得支持。

项目成果

Sustainable ammonia synthesis: Just around the corner?

可持续氨合成：指日可待？

• DOI: 10.1016/j.joule.2022.09.001
• 发表时间: 2022
• 期刊: Joule
• 影响因子: 39.8
• 作者: Klein, Channing K.;Manthiram, Karthish
• 通讯作者: Manthiram, Karthish

Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction

• DOI: 10.1021/acscatal.2c00389
• 发表时间: 2022-05-06
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Lazouski, Nikifar;Steinberg, Katherine J.;Manthiram, Karthish
• 通讯作者: Manthiram, Karthish

Imaging of nitrogen fixation at lithium solid electrolyte interphases via cryo-electron microscopy

通过冷冻电子显微镜对锂固体电解质界面的固氮成像

• DOI: 10.1038/s41560-022-01177-5
• 发表时间: 2023
• 期刊: Nature Energy
• 影响因子: 56.7
• 作者: Steinberg, Katherine;Yuan, Xintong;Klein, Channing K.;Lazouski, Nikifar;Mecklenburg, Matthew;Manthiram, Karthish;Li, Yuzhang
• 通讯作者: Li, Yuzhang

Spatial Variation in Cost of Electricity-Driven Continuous Ammonia Production in the United States

• DOI: 10.1021/acssuschemeng.1c08032
• 发表时间: 2022-06-20
• 期刊: ACS SUSTAINABLE CHEMISTRY & ENGINEERING
• 影响因子: 8.4
• 作者: Bose, Abhishek;Lazouski, Nikifar;Mallapragada, Dharik S.
• 通讯作者: Mallapragada, Dharik S.

Cost and Performance Targets for Fully Electrochemical Ammonia Production under Flexible Operation

• DOI: 10.1021/acsenergylett.2c01197
• 发表时间: 2022-08-12
• 期刊: ACS ENERGY LETTERS
• 影响因子: 22
• 作者: Lazouski, Nikifar;Limaye, Aditya;Mallapragada, Dharik S.
• 通讯作者: Mallapragada, Dharik S.