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名为“同位素动力学拆分”(IKR)的新氢-氢分离技术建立科学基础。由于中子的附加质量，在氢原子转移反应中，氚的反应往往较慢。该研究小组将对氢在氧化铝表面的迁移和扩散进行实验和计算研究，以了解控制H原子和D原子迁移速度的重要因素。这将包括开发方法来控制催化H2/D2活化位和氧化物表面上的H/D反应位之间的间距。然后，该团队将使用几种计算和机器学习技术来筛选尖晶石氧化物，这是一类具有广泛电子性质的过渡掺杂氧化铝材料，以了解它们的H/D原子传输特性。有希望的候选氧化物将被合成，它们的氢迁移率将得到充分评估，并与开始开发IKR的预测进行比较。这两个主要调查人员都将从代表不足的少数族裔(URM)群体中招收研究生和本科生。主要研究人员也是优秀的本科生导师，并将继续邀请UG的学生参与这个项目。这项合作研究将集中在氢在可调尖晶石氧化物表面的迁移和扩散的实验和计算研究上，旨在开发同位素动力学分辨(IKR)的新概念。IKR将是一种动力学工具，能够利用H/D在金属氧化物上传输的大的动力学同位素效应来分离H/D同位素。这项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，研究小组将使用密度泛函理论计算结合机器学习技术来筛选具有合适电子结构的尖晶石氧化物。将合成有希望的候选化合物，并通过仔细的动力学测量和动力学蒙特卡罗模拟来评估它们的氢迁移率。将致力于合成方法的开发，使研究团队能够指导氢气被激活的初级反应中心和发生氢化的二级反应中心之间的间距。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势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 will be focused on experimental and computational studies of hydrogen mobility and diffusion across tunable spinel oxide surfaces, with the intention to develop the novel concept of isotopic kinetic resolution (IKR). IKR will be a kinetic tool capable 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 structure. 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.