Synergy between oxide and nitride phases of a novel composite cathode for high-temperature electrocatalytic NH3 synthesis

用于高温电催化NH3合成的新型复合阴极的氧化物和氮化物相之间的协同作用

• 批准号: 1932638
• 负责人: Umit Ozkan
• 金额: $ 49.04万
• 依托单位: Ohio State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1932638&HistoricalAwards=false
• 关键词: Synergy; between; oxide; nitride; phases

This project focuses on a strategy for producing ammonia from N2 and H2O electrocatalytically at atmospheric pressure. The conventional route for ammonia (NH3) production is the Haber-Bosch (HB) process, which involves converting nitrogen and hydrogen through a thermo-catalytic reaction at high temperatures and high pressures. The demand for ammonia has been continuously increasing due to its widespread use in several industrial sectors including agriculture (approximately 80% of the produced ammonia is used to make fertilizer), transportation, pharmaceuticals, explosives, as well as the energy sector as a promising indirect hydrogen storage medium. Considering the increasing demand for NH3 and the highly energy-intensive nature of the conventional process with significant CO2 emissions, a cleaner and less energy-intensive alternative will have a significant economic and environmental impact. In addition, this project has the potential to provide new insights into the material synthesis and characterization, the mechanistic steps and the electro-catalytic phenomena, which can be translated to other catalytic and electrocatalytic systems for environmentally-important processes such as electrocatalytic reduction of NOx and CO2 electrolysis. Research activities proposed here will be integrated with established education and outreach programs at the Ohio State University with the ultimate goal of increasing student participation, retention and graduation in STEM fields. The overall goal of the project is to develop highly active and selective cathode electro-catalysts for the high-temperature electrosynthesis of ammonia in solid oxide electrolysis cell (SOEC)-type reactors. The high-temperature (400-600 degrees C) electrocatalytic ammonia synthesis will involve dissociation of H2O to form H+ and O2- and the electrocatalytic activation of N2, followed by reaction with H+ to form NH3. In this scheme, O2- ions are conducted through the oxide ion conducting electrolyte to the anode, where they form molecular oxygen. In this study, we will examine a composite cathode system which is composed of perovskite oxides and metallic/bimetallic nitride/oxynitrides and we will investigate the synergy between these phases. The rationale of using a composite system is that the perovskite oxide phase will catalyze the H2O dissociation and provide oxide ion and electronic conductivity while the nitride/oxynitride phase will promote the N2 activation and provide nitrogen ion mobility. To the best of our knowledge, such a synergistic effect has never been reported before. Our approach to study the high-temperature electrocatalytic production of ammonia concept and to investigate an oxide/nitride composite cathode for this purpose will involve an iterative process of material synthesis, ex-situ/in-situ/operando characterization and electrocatalytic activity tests. The knowledge gained in this project will help open up a new route ammonia synthesis from N2 and H2O. It will also help develop similar electrolysis/electrocatalytic cells for environmentally-important processes such as electrocatalytic reduction of NOx and co-electrolysis of CO2 and H2O for syngas production. In addition to its potential contribution to the high-temperature electrocatalytic ammonia synthesis literature, the proposed study has significant potential to provide valuable insights in electrocatalysis, materials synthesis, surface chemistry and kinetics.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.

该项目着重于在大气压下通过电催化产生氨和H2O的氨的策略。氨（NH3）生产的常规途径是Haber-Bosch（HB）过程，它涉及在高温和高压下通过热催化反应转化氮和氢。由于氨的广泛使用在包括农业（大约80％的生产氨用于制造肥料），运输，药品，爆炸物以及能源部门作为一种有希望的独立氢储存介质，因此，对氨的需求一直不断增加。考虑到对NH3的需求不断增长，并且具有重大二氧化碳排放的传统过程的高能源密集型性质，更清洁且能源较低的替代方案将产生重大的经济和环境影响。此外，该项目有可能提供有关材料合成和表征，机械步骤和电催化现象的新见解，可以将其转化为其他催化和电催化系统，以进行环境重要过程，例如NOX和CO2电解的电催化降低。 此处建议的研究活动将与俄亥俄州立大学的既定教育和外展计划融合，其最终目标是增加学生参与，保留和毕业在STEM领域。 该项目的总体目标是开发高度活性和选择性阴极的电催化剂，以用于固体氧化物电解电池（SOEC）型反应器中氨的高温电催化剂。高温（400-600摄氏度）电催化氨合成将涉及H2O解离以形成H+和O2-，以及N2的电催化激活，然后与H+反应形成NH3。在此方案中，O2离子是通过导电到阳极的氧化离子进行的，它们会形成分子氧。 在这项研究中，我们将检查由钙钛矿氧化物和金属/双金属氮化物/氧硝酸盐组成的复合阴极系统，我们将研究这些相之间的协同作用。使用复合系统的理由是，钙钛矿氧化物相将催化H2O解离并提供氧化物离子和电子电导率，而氮化物/氧气相位将促进N2激活并提供氮离子离子迁移率。据我们所知，这种协同作用从未有过报道。我们研究氨概念的高温电催化产生的方法，并研究出于此目的的氧化物/氮化物复合阴极的方法，将涉及材料合成，前静脉/原位/Operando/Operando表征和电催化活性测试的迭代过程。该项目中获得的知识将有助于开放N2和H2O的新路线氨合成。它还将有助于开发类似的电解/电催化细胞，以进行环境重要的过程，例如NOX的电催化降低和二氧化碳和H2O的共催化溶液以生产Syngas。除了其对高温电催化氨合成文献的潜在贡献外，这项拟议的研究还具有重要的潜力，可以在电催化，材料合成，表面化学和动力学方面提供宝贵的见解。该奖项反映了NSF的法定任务，并通过使用基础的智力效果和广泛的范围来评估支持，并具有值得评估的支持。

项目成果

A review of the current trends in high-temperature electrocatalytic ammonia production using solid electrolytes

• DOI: 10.1016/j.jcat.2020.04.025
• 发表时间: 2020-07-01
• 期刊: JOURNAL OF CATALYSIS
• 影响因子: 7.3
• 作者: Gunduz, Seval;Deka, Dhruba J.;Ozkan, Umit S.
• 通讯作者: Ozkan, Umit S.

Synergy between the proton conducting and a mixed electronic and oxygen ionic conducting phases in a composite anode for electrocatalytic propane ODH

• DOI: 10.1016/j.apcata.2023.119169
• 发表时间: 2023-04-04
• 期刊: APPLIED CATALYSIS A-GENERAL
• 影响因子: 5.5
• 作者: Kim，Jaesung;Deka，Dhruba J.;Ozkan，Umit S.
• 通讯作者: Ozkan，Umit S.

Electrocatalytic Oxidative Coupling of Methane on NiFe Exsolved Perovskite Anode: Effect of Water

甲烷在 NiFe 溶解的钙钛矿阳极上的电催化氧化偶联：水的影响

• DOI: 10.1002/cctc.202201336
• 发表时间: 2023
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Kim, Jaesung;Ferree, Matthew;Gunduz, Seval;Millet, Jean‐Marc M.;Aouine, Mimoun;Co, Anne C.;Ozkan, Umit S.
• 通讯作者: Ozkan, Umit S.

In-situ Exsolution of Bimetallic CoFe nanoparticles on (La,Sr)FeO3 perovskite: Its effect on Electrocatalytic Oxidative Coupling of Methane

• DOI: 10.1016/j.apcatb.2022.122026
• 发表时间: 2022-10
• 期刊: Applied Catalysis B: Environmental
• 作者: Jaesung Kim;Y. Kim;M. Ferree;S. Gunduz;A. Co;Minkyu Kim;U. Ozkan

Composite Cathodes with Oxide and Nitride Phases for High-Temperature Electrocatalytic Ammonia Production from Nitrogen and Water

用于氮和水高温电催化制氨的氧化物和氮化物相复合阴极

• DOI: 10.1149/2754-2734/ac6618
• 发表时间: 2022
• 期刊: ECS Advances
• 作者: Gunduz, Seval;Deka, Dhruba J.;Ferree, Matt;Kim, Jaesung;Millet, Jean-Marc M.;Co, Anne C.;Ozkan, Umit S.
• 通讯作者: Ozkan, Umit S.