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

SusChEM：用于碳封存和更安全加氢的充满缺陷的二维催化剂

• 批准号: 1465105
• 负责人: Richard Blair
• 金额: $ 49.98万
• 依托单位: The University of Central Florida Board of Trustees
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465105&HistoricalAwards=false
• 关键词: SusChEM; Defect; laden; 2D; Catalysts

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.

借助化学部化学催化计划的资金，博士。佛罗里达州中部大学的布莱尔，拉赫曼和特塔德参与了一项旨在理解2D结构缺陷催化的垂直整合努力。目前已丢弃的这种“废物”二氧化碳可能是生产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相结合，可以在不需要石油的情况下实现燃料和塑料等产品，并将二氧化碳从废物流中除去并用作起始材料。 这将使二氧化碳被视为有价值的资源，而不是要管理的废物。 这种方法的关键是基于具有瑕疵的类似板状材料的新型催化剂。 通过将瑕疵引入诸如硝酸硼之类的材料，该材料当前用作润滑剂和化妆品，Drs。布莱尔（Blair），拉赫曼（Rahman）和特塔德（Tetard）正在进入新的化学途径，这些途径可能铺平了二氧化碳经济的道路。 拉赫曼博士正在研究这些新催化剂的理论基础。 Tetard博士正在研究分子水平的结构和反应性，而Blair博士正在将发现转移到现实世界中的实施。 被调查的催化剂可能会取代现有的有毒金属催化剂，消除与金属相关的健康风险，并将二氧化碳转移到大气中。 夏季研究项目针对有弱势背景的人。 博士。布莱尔（Blair），拉赫曼（Rahman）和特塔德（Tetard）正在积极努力将处境不利的少数族裔纳入STEM领域。该团队正在研究H-BN（氮化硼）中缺陷如何产生催化活性，以产生来自二氧化碳和氢的线性醇，以及烯烃的独特无金属激活以进行氢化。 这些缺陷很难表征，需要采取分层的方法才能充分理解该系统。 基于DFT的计算用于产生反应能量学，并进行动力学蒙特卡洛模拟，以评估表面物种在缺陷上的时间演化，这是温度和与Blair博士实验相关的压力的函数。 DRS获得的实验数据。 Blair和Tetard与理论结果有关，以便在原子水平上完全了解催化系统。 Tetard博士正在开发用于直接成像和测量缺陷的方法，以及使用扫描透射电子显微镜和官能化尖端原子力显微镜的结合物种。 正在开发一种新技术，将原子力显微镜（AFM）硬件与拉曼和红外光谱进行开发，以允许在与宏观反应有关的条件下对绑定物种的纳米级分析。 布莱尔博士正在研究二氧化碳以及烯烃氢化的多克批次反应的动力学和反应产物。 多种大小的范围对2D材料中缺陷的催化范围的了解将促进二氧化碳的捕获和利用。

项目成果

Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride

缺陷六方氮化硼的非均相无金属氢化

• DOI: 10.1021/acsomega.6b00315
• 发表时间: 2016
• 期刊: ACS Omega
• 影响因子: 4.1
• 作者: Nash, David J.;Restrepo, David T.;Parra, Natalia S.;Giesler, Kyle E.;Penabade, Rachel A.;Aminpour, Maral;Le, Duy;Li, Zhanyong;Farha, Omar K.;Harper, James K.
• 通讯作者: Harper, James K.