GOALI: Engineered Metal-Ligand Interfaces for Selective Electrochemical Reactions

GOALI：用于选择性电化学反应的工程金属-配体界面

• 批准号: 1438385
• 负责人: John Flake
• 金额: $ 44.34万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1438385&HistoricalAwards=false
• 关键词: GOALI; Engineered; Metal; Ligand; Interfaces

Title: Electrochemical Conversion of Carbon Dioxide and Nitrogen to High-Value Products Using Engineered Metal-Ligand Interfaces Plants do a wonderful job of converting gases like carbon dioxide and nitrogen into products like cellulose and nutrients. The reactions are driven by sunlight and provide a critical balance to life - including oxygen in the atmosphere and our food supply. In the last century, man is responsible for significant changes in the balance; atmospheric carbon dioxide levels have risen by about 30% and more than 50% of the world population now relies on man-made fertilizers for food. Unfortunately, there are no commercial processes that can duplicate the ability of nature to use sunlight, atmospheric gases and water to make fuels, plastics or fertilizers. However, this remains a grand challenge for science and technology and efforts to achieve some measure of success still require funding. This GOALI award is made to a team comprised of Professors John Flake and Ye Xu and Dr. Joe Sauer of Louisiana State University and A&M College and Dr. Anne Sauer of Albemarle Corporation. The aim of this work is to mimic nature and design new catalysts that can produce valuable products from these basic feedstocks. Catalyst surfaces and interfaces will be created using highly active metal clusters and functional ligand molecules that promote the selective formation of one particular product over another. The energy to power the reaction is ideally provided solely by electricity from solar or wind energy (no fossil fuels). The research will shed light on the fundamental behavior of electrocatalysts and the team of academic and industry investigators will work to commercialize "green" processes to make chemicals, fertilizers and fuels using purely renewable resources. The overarching goals of this project are to: (1) build a fundamental framework for understanding the behavior of ligand-functionalized metal nanoclusters as electrocatalysts and (2) leverage this understanding to create electrocatalysts by design. The team will explore the roles of metal type, nanocluster size, ligand chemistry and their behavior in electrolytic reactions using a combined theoretical and experimental approach. While there has been a renewed interest in electrochemical CO2 reduction in recent years (including for solar fuels), the reaction pathways and selectivity-controlling mechanisms are not well understood. Likewise, the mechanisms involved in N2 reduction are also poorly understood. The investigators will explore reduction pathways as a function of nanocluster size/type (Au, Ag, Cu, Ni, Fe) and ligand chemistry (e.g. thiols, sulfides, amides, amines, imines and other sulfo- or amino-functional groups) using voltammetry, surface analyses and other product characterization tools. The work will include a special in-operando spectroscopic study of electrocatalytic reactions using synchrotron-source XANES (X-ray Absorption Near Edge Spectroscopy) analysis to probe reactions as they occur. These experimental results will be complemented by density functional theory (DFT) based modeling techniques to generate an in-depth understanding of the nature of the active electrode interface, the key steps in the electrochemical reduction of CO2 and N2, and the cooperative effects between the electrode and the ligand. The versatility and accuracy of modern DFT methods will be leveraged to identify the fundamental factors that systematically control the efficiency and selectivity of the reactions, and subsequently to predict the performance of new electrode/ligand combinations. Results from this work will yield new insights into reactions mechanisms, a framework for predicting and controlling selectivity, and new electrocatalysts to produce fuels, fertilizers, and chemicals.

标题：利用工程金属-配体界面将二氧化碳和氮气电化学转化为高价值产品植物在将二氧化碳和氮气等气体转化为纤维素和营养物质等产品方面做得非常出色。 这些反应由阳光驱动，为生命提供了关键的平衡——包括大气中的氧气和我们的食物供应。 在上个世纪，人类对平衡的重大变化负有责任。大气中的二氧化碳含量上升了约30%，世界上50%以上的人口现在依靠人造肥料获取食物。 不幸的是，没有任何商业过程可以复制大自然利用阳光、大气气体和水来制造燃料、塑料或肥料的能力。然而，这对科学技术来说仍然是一个巨大的挑战，要取得一定程度的成功仍然需要资金。该 GOALI 奖颁发给由路易斯安那州立大学和 A&M 学院的 John Flake 教授、Ye Xu 教授和 Joe Sauer 博士以及 Albemarle Corporation 的 Anne Sauer 博士组成的团队。 这项工作的目的是模仿自然并设计新的催化剂，可以从这些基本原料中生产有价值的产品。 催化剂表面和界面将使用高活性金属簇和功能性配体分子来创建，以促进一种特定产物相对于另一种产物的选择性形成。 理想情况下，为反应提供动力的能量仅由太阳能或风能（无化石燃料）提供。 该研究将揭示电催化剂的基本行为，学术和行业研究人员团队将致力于将“绿色”工艺商业化，利用纯可再生资源制造化学品、肥料和燃料。该项目的总体目标是：（1）建立一个基本框架来理解配体功能化金属纳米团簇作为电催化剂的行为，以及（2）利用这种理解通过设计来创建电催化剂。 该团队将采用理论和实验相结合的方法，探索金属类型、纳米团簇尺寸、配体化学及其在电解反应中的行为。尽管近年来人们对电化学二氧化碳还原（包括太阳能燃料）重新产生了兴趣，但反应途径和选择性控制机制尚不清楚。 同样，人们对氮还原的机制也知之甚少。研究人员将使用伏安法、表面分析和其他产品表征工具，探索作为纳米团簇尺寸/类型（Au、Ag、Cu、Ni、Fe）和配体化学（例如硫醇、硫化物、酰胺、胺、亚胺和其他磺基或氨基官能团）函数的还原途径。 这项工作将包括使用同步加速器源 XANES（X 射线吸收近边光谱）分析来探测反应发生时的电催化反应的特殊操作内光谱研究。 这些实验结果将得到基于密度泛函理论（DFT）的建模技术的补充，以深入了解活性电极界面的性质、CO2和N2电化学还原的关键步骤以及电极和配体之间的协同效应。 现代 DFT 方法的多功能性和准确性将被用来确定系统控制反应效率和选择性的基本因素，并随后预测新电极/配体组合的性能。 这项工作的结果将为反应机制、预测和控制选择性的框架以及生产燃料、肥料和化学品的新型电催化剂带来新的见解。