Collaborative Research: Tuning Hydrogen Mobility on Au/Spinel Catalysts to Develop the Isotopic Kinetic Resolution of H2 and D2

在化学系化学催化项目的资助下，宾夕法尼亚州立大学的钱德勒教授和休斯顿大学的格拉博教授将合作为一种称为“同位素动力学分辨率”(IKR) 的新型 H-D 分离技术奠定科学基础。 由于中子质量增加，氘在氢原子转移反应中往往反应更慢。研究小组将对氢在氧化铝表面的迁移率和扩散进行实验和计算研究，以了解控制氢原子和 D 原子传输速度的重要因素。 这将包括开发控制氧化物表面催化 H2/D2 活化位点和 H/D 反应位点之间间距的方法。 然后，该团队将使用多种计算和机器学习技术筛选尖晶石氧化物（一类具有广泛电子特性的过渡掺杂氧化铝材料）的 H/D 原子传输特性。 将合成有前途的候选氧化物，并对其氢迁移率进行全面评估，并与开始开发 IKR 的预测进行比较。 两位主要研究人员将从代表性不足的少数群体（URM）中招募研究生和本科生。主要研究人员也是颇有成就的本科生导师，并将继续让 UG 学生参与该项目。该合作研究项目将侧重于氢在可调尖晶石氧化物表面的迁移率和扩散的实验和计算研究，旨在开发同位素动力学分辨率 (IKR) 的新概念。 IKR 是一种动力学工具，能够利用金属氧化物上 H/D 传输的大动力学同位素效应来分离 H/D 同位素。该技术的进一步发展也可能导致选择性加氢催化剂的新设计策略。为了建立这个新工具，该团队将使用密度泛函理论计算与机器学习技术相结合来筛选具有合适电子结构的尖晶石氧化物。将合成有前途的候选者，并通过仔细的动力学测量和动力学蒙特卡罗模拟来评估其氢迁移率。将投入大量精力致力于开发合成方法，使研究团队能够控制初级反应中心（氢气被激活）和次级反应中心（发生氢化）之间的距离。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

With funding from the Chemical Catalysis program in the Division of Chemistry, Professor Chandler at Penn State University and Professor Grabow at the University of Houston will collaborate to build the scientific foundations for a new H-D separation technique termed “isotopic kinetic resolution” (IKR). Due to the added mass of the neutron, deuterium tends to react more slowly in H-atom transfer reactions. The research team will conduct an experimental and computational study of hydrogen mobility and diffusion across aluminum oxide surfaces to understand the important factors in controlling the speed of H- and D- atom transport. This will include developing methods to control the spacing between catalytic H2/D2 activation sites and H/D reaction sites on the oxide surface. The team will then screen spinel oxides, a class of transition doped aluminum oxide materials with wide ranging electronic properties, for their H/D-atom transport properties using several computational and machine-learning techniques. Promising candidate oxides will be synthesized and their H-mobility fully evaluated and compared to predictions to begin developing the IKR. Both principal investigators will recruit graduate and undergraduate students from underrepresented minority (URM) groups. The principal investigators are also accomplished undergraduate mentors and will continue to involve UG students in this project.This collaborative research project will be focused on experimental and computational studies of hydrogen mobility and diffusion across tunable spinel oxide surfaces, with the aim of developing the novel concept of isotopic kinetic resolution (IKR). IKR is a kinetic tool capable of separating H/D isotopes by leveraging the large kinetic isotope effect for H/D transport on metal oxides. Further development of this technique may also lead to new design strategies for selective hydrogenation catalysts. To establish this new tool, the team will use density functional theory calculations combined with machine-learning techniques to screen for spinel oxides with suitable electronic structures. Promising candidates will be synthesized and their H-mobility evaluated through careful kinetic measurements and kinetic Monte Carlo simulations. Significant effort will be dedicated to the development of synthetic methods that will allow the research team to direct the spacing between primary reaction centers, where H2 is activated, and secondary reaction centers, where hydrogenation occurs.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.