Collaborative Research: Controlling Metal-Oxide Interface Chemistry for New C-H Activation Catalysts

在清洁能源向可再生和可持续的净零碳燃料和化学品过渡期间，世界将继续依赖碳氢化合物资源。 因此，通过有效的化学加工来制造易于运输的液体燃料和化学品，有很大的机会减少我国巨大天然气储备的碳足迹。 该项目解决了天然气化学加工中的一个关键挑战-根据需要打破碳氢键，以制造更高价值的燃料和化学品。 催化技术是高效节能天然气提质的关键。 为此，该项目研究了一种新型碳氢化合物转化催化剂，这种催化剂有可能使天然气在现场转化为液体燃料和化学品，从而极大地提高能源效率并显著减少温室气体排放。该项目还将投资于针对经济上处于不利地位的本科生的研究经验，这些学生中女性和少数民族的比例不成比例。 本科生将参与一个同行指导网络，这可以在促进本科生的成功特别有效，特别是当团队中的学生有不同的文化和社会经济背景。该项目将结合联合收割机的研究人员的实验和计算专业知识，开发新的异质C-H活化催化剂的基础上的独特性质的Au/氧化物界面，这将是调整，以最大限度地提高活性，通过改变氧化物的组成。 密度泛函理论和新的原位红外技术的组合将被用来量化H2活化参数在一系列精心挑选的Au/MOx催化剂。 H-H和C-H键活化是密切相关的过程，因此广泛的方法是首先研究氧化物成分如何调节H2活化的热力学和动力学，然后将这些知识扩展到设计有效的C-H活化界面。机器学习技术将使用这些结果来调查数千种氧化物成分的H2活化化学，这将直接洞察控制金属氧化物界面复杂相互作用的潜在物理化学过程。再加上旨在为计算模型提供信息和改进的实验，研究将超越影响C-H活化的因素（如支持还原性，支持碱度，M-OH键灵活性）的识别，以评估每个系统变量的相对影响。 将用一套根据吸附性能选择的烃类和催化苯甲醇氧化测试所得C-H键活化化学。 理想情况下，该项目将产生一个研究协议，将结合联合收割机有效的计算筛选和实验验证的金属载体催化剂组合量身定制的有效C-H键活化在广泛的碳氢化合物和有机分子。这个奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

The world will continue to rely on hydrocarbon resources during the Clean Energy Transition to renewable and sustainable net-zero carbon fuels and chemicals. Thus, there is a substantial opportunity to reduce the carbon footprint of our Nation’s tremendous natural gas reserves through efficient chemical processing to manufacture readily transportable liquid fuels and chemicals. The project addresses a key challenge in natural gas chemical processing – breaking the carbon-hydrogen bonds as needed to manufacture higher-value fuels and chemicals. Catalytic technology is critical to energy efficient natural gas upgrading. To that end, the project investigates a new class of hydrocarbon conversion catalysts that can potentially enable natural gas to be converted to liquid fuels and chemicals in the field, thereby generating enormous boosts in energy efficiency and a significant reduction in greenhouse gas emissions. The project also will invest in research experiences targeted to economically disadvantaged undergraduate students, who are disproportionately women and under-represented minorities. The undergraduates will be engaged in a peer-mentoring network, which can be particularly effective in promoting undergraduate success, especially when the students in the team have diverse cultural and socio-economic backgrounds. The project will combine the investigators’ experimental and computational expertise to develop new heterolytic C-H activation catalysts based on the unique properties of Au/oxide interfaces, which will be tuned to maximize activity by varying the composition of the oxide. A combination of density functional theory and new in-situ IR techniques will be employed to quantify H2 activation parameters over a carefully chosen series of Au/MOx catalysts. H-H and C-H bond activation are closely related processes, so the broad approach is to first study how oxide composition tunes the thermodynamics and kinetics of H2 activation, and then extend this knowledge to design effective interfaces for C-H activation. Machine learning techniques will use these results to survey H2 activation chemistry for thousands of oxide compositions, which will provide direct insight into underlying physio-chemical processes that govern complex interactions at the metal-oxide interface. Coupled with experiments intentionally designed to inform and refine the computational models, the research will go beyond identification of factors that impact C-H activation (such as support reducibility, support basicity, M-OH bond flexibility) to assess the relative impact of each system variable. The resulting C-H bond activation chemistry will be tested with a suite of hydrocarbons chosen for their adsorption properties and with catalytic benzyl alcohol oxidation. Ideally, the project will generate a research protocol that will combine efficient computational screening and experimental validation of metal-support catalyst combinations tailored for efficient C-H bond activation across a broad range of hydrocarbon and organic molecules.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.