GOALI: Engineered Metal-Ligand Interfaces for Selective Electrochemical Reactions

职务名称：使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素等产品方面做得很好。 这些反应是由阳光驱动的，并为生命提供了一个关键的平衡-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;大气中的二氧化碳水平上升了约30%，现在世界上超过50%的人口依靠人造肥料获得食物。 不幸的是，目前还没有商业化的工艺可以复制大自然利用阳光、大气中的气体和水来制造燃料、塑料或肥料的能力。然而，这仍然是科学和技术的一个巨大挑战，要取得一定程度的成功，仍然需要资金。这个GOALI奖是由路易斯安那州立大学和A M学院的John Flake教授和Ye Xu教授以及Joe Sauer博士和Albemarle公司的Anne Sauer博士组成的团队。 这项工作的目的是模仿自然，设计新的催化剂，可以从这些基本原料生产有价值的产品。 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，这些分子促进一种特定产物的选择性形成。 为反应提供动力的能量理想地仅由来自太阳能或风能的电力提供（没有化石燃料）。 该研究将揭示电催化剂的基本行为，学术和工业研究人员团队将致力于将“绿色”工艺商业化，以使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，用于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）利用这种理解来设计电催化剂。 该团队将探索金属类型，纳米团簇大小，配体化学及其在电解反应中的行为的作用，使用理论和实验相结合的方法。虽然近年来人们对电化学CO2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未得到很好的理解。 同样，N2还原所涉及的机制也知之甚少。研究人员将使用伏安法、表面分析和其他产品表征工具，探索还原途径与纳米团簇尺寸/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）的关系。 这项工作将包括使用同步辐射源XANES（X射线吸收近边光谱）分析探测反应发生时的电催化反应的特殊操作中光谱研究。 这些实验结果将通过基于密度泛函理论（DFT）的建模技术进行补充，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。 这项工作的结果将对反应机制产生新的见解，预测和控制选择性的框架，以及生产燃料，肥料和化学品的新电催化剂。

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.