SusChEM: Defect-laden 2D Catalysts for Carbon Sequestration and Safer Hydrogenation

在化学部化学催化项目的资助下，中佛罗里达大学的布莱尔、拉赫曼和泰塔尔博士参与了一项垂直整合的工作，旨在了解二维结构中缺陷的催化作用。这种目前被丢弃的“废”二氧化碳可能是制造各种产品的有用材料。 通过将二氧化碳与使用太阳能产生的氢气化学结合，可以在不需要石油的情况下实现燃料和塑料等产品，并且二氧化碳将从废物流中去除并用作起始材料。 这将使二氧化碳被视为一种宝贵的资源，而不是一种需要管理的废物。 这种方法的关键是应用一种基于有缺陷的片状材料的新型催化剂。 通过在氮化硼等材料中引入缺陷，Blair博士、Rahman博士和Tetard博士正在探索新的化学途径，这可能为二氧化碳经济铺平道路。 拉赫曼博士正在研究这些新催化剂的理论基础。Tetard博士正在分子水平上研究它们的结构和反应性，Blair博士正在将这些发现应用于真实的世界。 正在研究的催化剂可能取代现有的有毒金属催化剂，消除与金属相关的健康风险，并转移二氧化碳释放到大气中。 正在制定针对处境不利者的暑期研究项目。 Blair，Rahman和Tetard正在积极努力将弱势少数群体融入STEM领域。该团队正在研究h-BN（氮化硼）中的缺陷如何对二氧化碳和氢气生产线性醇产生催化活性，以及烯烃加氢的独特无金属活化。 这些缺陷很难描述，需要采用分层方法来充分理解该系统。 基于DFT的计算用于生成反应能量学和动力学蒙特卡罗模拟进行评估的时间演变的表面物种的缺陷，作为一个函数的温度和压力相关的布莱尔博士的实验。 Blair博士和Tetard博士获得的实验数据与理论结果相关联，以便在原子水平上对催化系统有一个完整的理解。 Tetard博士正在开发使用扫描透射电子显微镜和功能化尖端原子力显微镜直接成像和测量缺陷以及结合物质的方法。 一种新的技术相结合的原子力显微镜（AFM）的硬件与拉曼和红外光谱正在开发中，允许纳米尺度的分析结合的物种的条件下，相关的宏观反应。 布莱尔博士正在研究二氧化碳和烯烃加氢的多克间歇反应的动力学和反应产物。 对二维材料中缺陷催化作用的多尺寸范围理解将促进二氧化碳捕获和利用的创新。

With funding from the Chemical Catalysis Program of the Chemistry Division, Drs. Blair, Rahman, and Tetard of the University of Central Florida are involved in a vertically integrated effort aimed at understanding catalysis over defects in 2D structures. This "waste" carbon dioxide, which is presently discarded, could be a useful material for making a variety of products. By chemically combining carbon dioxide with hydrogen generated using solar energy, products such as fuels and plastics could be realized without the need for petroleum, and carbon dioxide would be removed from the waste stream and used as a starting material. This would enable carbon dioxide to be seen as a valuable resource instead of a waste product to be managed. Key to this approach is the application of a new type of catalyst based on sheet-like materials with imperfections. By introducing imperfections into materials like boron nitride, which is currently used as a lubricant and in cosmetics, Drs. Blair, Rahman, and Tetard are accessing new chemical pathways that may pave the way towards a carbon dioxide economy. Dr. Rahman is investigating the theoretical underpinnings of these new catalysts. Dr. Tetard is studying their structure and reactivity at a molecular level and Dr. Blair is moving the findings toward implementation in the real world. The catalysts being investigated may supplant existing toxic metal catalysts, eliminate the health risks associated with the metals, and divert carbon dioxide from being released into the atmosphere. Summer research projects targeting those with disadvantaged backgrounds are being developed. Drs. Blair, Rahman, and Tetard are actively working to integrate disadvantaged minority individuals in STEM fields. This team is investigating how defects in h-BN (boron nitride) produce catalytic activity towards the production of linear alcohols from carbon dioxide and hydrogen as well as the unique, metal-free activation of olefins for hydrogenation. These defects are very difficult to characterize and a tiered approach is required to fully understand this system. DFT-based calculations are used to generate reaction energetics and kinetic Monte Carlo simulations are performed to evaluate the temporal evolution of surface species on defects, as a function of temperatures and pressures relevant to Dr. Blair's experiments. Experimental data acquired by Drs. Blair and Tetard are linked to the theoretical results in order to develop a complete understanding of the catalytic system at the atomic level. Dr. Tetard is developing methods for direct imaging and measurement of defects as well as bound species using scanning transmission electron microscopy and functionalized-tip atomic force microscopy. A new technique combining atomic force microscopy (AFM) hardware with Raman and infrared spectroscopy is being developed to allow nano-scale analysis of bound species under conditions relevant to macroscopic reactions. Dr. Blair is studying the kinetics and reaction products of multi-gram batch reactions for carbon dioxide as well as olefin hydrogenation. A multi-size ranged understanding of catalysis over defects in 2D materials will foster innovation in the capture and utilization of carbon dioxide.