Chemical and electronic states in chalcogenide-based electrocatalytic systems during CO2 reduction

CO2 还原过程中基于硫族化物的电催化系统的化学和电子态

• 批准号: 1800357
• 负责人: Jordi Cabana
• 金额: $ 45万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-15 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800357&HistoricalAwards=false
• 关键词: Chemical; electronic; states; chalcogenide; based

The generation of carbon dioxide is one undesirable outcome of the combustion of fossil fuels to fulfill the energy needs of modern society. Artificial photosynthesis offers means to limit the corresponding impact in the environment by reconverting the carbon dioxide to energy-rich chemicals, creating a closed cycle that is inspired by nature. The technological viability of this concept hinges on the development of catalysts that promote the conversion of carbon dioxide at fast rates and high energy efficiency. The investigators have recently discovered a way to make catalysts consisting of nanosized flakes of earth abundant metal compounds. These "artificial leaves" have shown promise as replacements for expensive noble metals such as platinum, but optimization of the composition and detailed structure of these materials is hampered by a lack of fundamental understanding of the chemical principles by which they work. The research will employ a variety of experiments and analysis tools to better understand those principles and use the knowledge gained to identify catalysts that perform better and are more stable in the working environment of an electrochemical cell. The work contributes to moving society toward an increasingly sustainable future based on a closed carbon cycle. The research activities are intertwined with broad efforts to expose future generations of scientists to cutting-edge methodologies, through research internships for undergraduate and high school students, field trips from K-12 schools to university facilities, and a summer workshop on electrochemistry. Recruitment is vigorous among the highly diverse community at the University of Illinois at Chicago, to reach populations underrepresented in STEM.Two-dimensional transition metal dichalcogenides (TMDC) in contact with ionic liquid electrolytes exceed the performance of state-of-the-art electrocatalysts toward the reduction of carbon dioxide to synthesis gas. However, the fundamental underpinnings of this outstanding performance have not yet been fully ascertained, especially synergies between the ionic liquid electrolyte and the catalyst. The project will employ a combination of spectroscopic techniques to build a library of critical states that underpin the mechanisms of carbon dioxide reduction in TMDC/ionic liquid systems. The evolution of the states is assessed by combining ex situ and operando experiments, and the effect of chemical permutations is evaluated. The outcomes increase the fundamental knowledge of a new and unexplored class of candidates for an important electrocatalytic reaction. The topics of this research also drive an educational plan that fosters excitement about the scientific enterprise in future generations of scientists and technologists. The researchers participate in outreach events at Chicago-area elementary and high schools, spanning from the support of science teachers in the classroom to field trips to laboratories at the University of Illinois at Chicago (UIC). They actively mentor undergraduate students at UIC to enhance their ability to find career paths after graduation, for instance, through research opportunities relevant to the goals of this project, maximizing the exposure of the student to cutting-edge methodologies. These activities will have a special focus on members of Chicago's Hispanic communities, a large population that is severely underrepresented in STEM fields.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.

二氧化碳的产生是化石燃料燃烧以满足现代社会的能量需求的一个不期望的结果。人工光合作用通过将二氧化碳转化为富含能量的化学物质，创造了一个受自然启发的封闭循环，从而提供了限制对环境的相应影响的方法。这一概念的技术可行性取决于催化剂的开发，这些催化剂可促进二氧化碳的快速转化和高能效。研究人员最近发现了一种制造催化剂的方法，这种催化剂由地球上丰富的金属化合物的纳米级薄片组成。 这些“人造叶子”已经显示出作为昂贵贵金属（如铂）替代品的前景，但由于缺乏对它们工作的化学原理的基本理解，这些材料的成分和详细结构的优化受到阻碍。该研究将采用各种实验和分析工具来更好地理解这些原理，并利用所获得的知识来确定在电化学电池的工作环境中表现更好且更稳定的催化剂。 这项工作有助于推动社会走向一个基于封闭碳循环的日益可持续的未来。研究活动与广泛的努力交织在一起，通过本科生和高中生的研究实习，从K-12学校到大学设施的实地考察，以及电化学夏季研讨会，使未来几代科学家接触尖端方法。招聘是在伊利诺伊大学芝加哥的高度多样化的社区中蓬勃发展，以达到在STEM中代表性不足的人群。二维过渡金属二硫属化物（TMDC）与离子液体电解质接触超过了最先进的电催化剂对二氧化碳还原为合成气的性能。然而，这种出色性能的根本基础尚未完全确定，特别是离子液体电解质和催化剂之间的协同作用。该项目将采用光谱技术的组合来建立一个临界状态库，该库支持TMDC/离子液体系统中二氧化碳减少的机制。通过结合非原位和操作性实验来评估状态的演变，并评估化学排列的影响。结果增加了一个新的和未开发的一类重要的电催化反应的候选人的基本知识。这项研究的主题还推动了一项教育计划，该计划旨在培养未来几代科学家和技术人员对科学事业的兴奋。研究人员参加了芝加哥地区小学和高中的外展活动，从课堂上科学教师的支持到芝加哥伊利诺伊大学（UIC）实验室的实地考察。他们积极指导UIC的本科生，以提高他们在毕业后找到职业道路的能力，例如，通过与该项目目标相关的研究机会，最大限度地提高学生对尖端方法的接触。这些活动将特别关注芝加哥西班牙裔社区的成员，这是一个在STEM领域严重代表性不足的庞大人口。该奖项反映了NSF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

Capturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox

• DOI: 10.1038/s41563-022-01278-2
• 发表时间: 2022-06-20
• 期刊: NATURE MATERIALS
• 影响因子: 41.2
• 作者: Li, Biao;Kumar, Khagesh;Tarascon, Jean-Marie
• 通讯作者: Tarascon, Jean-Marie

Highly Active Rhenium-, Ruthenium-, and Iridium-Based Dichalcogenide Electrocatalysts for Oxygen Reduction and Oxygen Evolution Reactions in Aprotic Media

• DOI: 10.1021/acs.chemmater.9b04117
• 发表时间: 2020-03
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Leily Majidi;Z. Hemmat;R. Warburton;Khagesh Kumar;Alireza Ahmadiparidari;L. Hong;Jinglong Guo;P. Zapol;R. Klie;J. Cabana;J. Greeley;L. Curtiss;A. Salehi‐khojin

Facile Electrochemical Mg-Ion Transport in a Defect-Free Spinel Oxide

无缺陷尖晶石氧化物中轻松的电化学镁离子传输

• DOI: 10.1021/acs.chemmater.2c00237
• 发表时间: 2022
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Kwon, Bob Jin;Yin, Liang;Roy, Indrani;Leon, Noel J.;Kumar, Khagesh;Kim, Jae Jin;Han, Jinhyup;Gim, Jihyeon;Liao, Chen;Lapidus, Saul H.
• 通讯作者: Lapidus, Saul H.

Unprecedented Multifunctionality in 1D Nb 1‐ x Ta x S 3 Transition Metal Trichalcogenide Alloy

• DOI: 10.1002/adfm.202205214
• 发表时间: 2022-06
• 期刊: Advanced Functional Materials
• 影响因子: 19
• 作者: Z. Hemmat;Alireza Ahmadiparidari;Shuxi Wang;Khagesh Kumar;Michael Zepeda;Chengji Zhang;Naveen K. Dandu;Sina Rastegar;Leily Majidi;Ahmad Q Jaradat;Anh Ngo;K. Thornton;L. Curtiss;J. Cabana;Zhehao Huang;A. Salehi‐khojin

Intercalation of Ca into a Highly Defective Manganese Oxide at Room Temperature

室温下 Ca 嵌入高度缺陷的氧化锰中

• DOI: 10.1021/acs.chemmater.1c03803
• 发表时间: 2022
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Kwon, Bob Jin;Yin, Liang;Bartel, Christopher J.;Kumar, Khagesh;Parajuli, Prakash;Gim, Jihyeon;Kim, Sanghyeon;Wu, Yimin A.;Klie, Robert F.;Lapidus, Saul H.
• 通讯作者: Lapidus, Saul H.