Research Initiation Award: A Computational Study of Hydroformylation of Ethylene Over Heterogeneous Bimetallic Catalysts

研究启动奖为传统黑人学院和大学的初级和中期职业教师提供支持，他们正在建立新的研究项目或重新指导和重建现有的研究项目。期望该奖项有助于提高教师的研究能力和效率，改善所在机构的研究和教学，并使本科生参与研究经验。佛罗里达农业和机械大学获得的这个奖项有可能增加人们对氢甲酰化的理解，氢甲酰化是一种生产醛的工业过程。该项目将开设材料建模的本科和研究生课程，提供计算材料科学和催化方面的研究培训，并与当地社区学院和高中建立内部和外部合作。氢甲酰化是合成气与烯烃反应生成醛的过程。目前，氢甲酰化是使用Rh和或co基过渡金属配合物作为催化剂进行的。该反应的均相性导致催化剂分离和回收困难，活性金属损失，金属物种污染和催化溶液的腐蚀性。不牺牲活性和选择性的多相催化体系的发展将避免与均相催化剂相关的缺点，具有很高的应用价值。本项目采用第一性原理密度泛函理论（DFT）计算和动力学蒙特卡罗（KMC）模拟等计算方法，对非均相Rh和Rh基双金属模型催化剂上乙烯氢甲酰化生成c3 -氧合物的催化科学有了基本的了解。DFT计算将提供反应网络的能量学，KMC模拟将用于获得实验反应条件下的反应动力学。理论计算将提供对乙烯氢甲酰化的原子洞察力，并帮助确定简单的催化描述符，可用于筛选潜在的双金属催化剂，这些催化剂对乙烯转化为c3氧合物具有活性和选择性。此外，从这项研究中获得的知识也将阐明其他高级烯烃的氢甲酰化。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Research Initiation Awards provide support for junior and mid-career faculty at Historically Black Colleges and Universities who are building new research programs or redirecting and rebuilding existing research programs. It is expected that the award helps to further the faculty member's research capability and effectiveness, improve research and teaching at the home institution, and involves undergraduate students in research experiences. The award to Florida Agricultural and Mechanical University has potential to increase the understanding of hydroformylation which is an industrial process to produce aldehydes. The project will create undergraduate and graduate courses in materials modeling, provide research training in computational materials science and catalysis and create internal and external collaborations with local community colleges and high schools. Hydroformylation is a process to produce aldehydes by the reaction of synthesis gas with alkenes. Currently, hydroformylation is carried out using Rh and or Co-based transition metal complexes as a catalyst. The homogeneous nature of this reaction leads to difficulties in catalyst separation and recovery, active metal losses, metal species contamination, and corrosivity of catalytic solutions. The development of heterogeneous catalytic systems without sacrificing the activity and selectivity will avoid the drawbacks associated with homogeneous catalysts and be highly useful. This project employs computational methods such as first-principles density functional theory (DFT) calculations and kinetic Monte Carlo (KMC) simulations to gain a fundamental understanding of catalytic science of ethylene hydroformylation to C3-oxygenates on heterogeneous Rh and Rh-based bimetallic model catalysts. The DFT calculations will provide the energetics of the reaction network and KMC simulations will be employed to obtain the kinetics of the reaction at experimental reaction conditions. The theoretical calculations will provide atomistic insight into ethylene hydroformylation and help identify simple catalytic descriptors that can be used to screen potential bimetallic catalysts that are active and selective for ethylene conversion to C3-oxygenates. Moreover, the knowledge gained from this study will also shed light on the hydroformylation of other higher alkenes.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.