CAREER: Molecular Understanding and Catalyst Design for the Direct Synthesis of H2O2

摘要（弗莱厄蒂; 1553137）目前，每年有数百万吨危险的氯化化合物用于纸浆、纸张和日用化学品制造中的选择性氧化和漂白反应。 过氧化氢（H2 O2）是氯化化合物的“绿色”替代品，但由于目前的生产方法仅在非常大的规模上具有经济可行性，因此并未广泛使用。 拟议的研究将调查一种替代的催化方法-从氢气和氧气直接合成过氧化氢-这将使过氧化氢的现场生产能够在更小、更常见的加工设施中使用。 拟议的研究与教育计划相结合，重点是建立研究和研究指导技能的年轻妇女。研究将结合联合收割机催化动力学和原位光谱测量系统的调查，以确定：1）直接合成H2 O2的机理，2）表面、溶剂和液相中间体在形成反应性中间体中的作用，和3）催化剂组成和溶剂性质对反应速率和选择性的综合影响。 最初的工作将集中在钯（Pd）和钯-金（PdAu）簇作为活性催化材料，但从这些材料中获得的知识将用于生成指导原则和活性描述符，以确定PdAu催化剂的廉价替代品。 为了实现这些目标，动力学和（非原位和原位）红外光谱技术的组合将被用来探测负载金属簇的液-固界面处的催化化学。 这项调查将涉及设计参数，如：金属簇的大小和组成，亲电吸附物的作用，和溶剂的性质，如pH值和极性。 虽然这些研究专门针对H2 O2的直接合成，但这项工作将为未来在液-固界面进行广泛的氧化和还原化学研究开发所需的工具和专业知识。

Abstract (Flaherty; 1553137)Currently millions of tons of hazardous chlorinated compounds are used for selective oxidation and bleaching reactions in the manufacture of pulp, paper, and commodity chemicals each year. Hydrogen peroxide (H2O2) represents a "green" alternative to chlorinated compounds, but it is not widely used because the current production method is economically viable only at very large scales. The proposed study will investigate an alternative catalytic approach - direct synthesis of H2O2 from hydrogen (H2) and oxygen (O2) gases - that would enable H2O2 production on-site for use in smaller, more common processing facilities. The proposed research is integrated with educational programs focusing on young women with emphasis on building research and research-mentoring skills.The research will combine catalytic kinetic and in situ spectroscopic measurements in a systematic investigation to determine: 1) the mechanism for direct synthesis of H2O2, 2) the roles of surfaces, solvents, and liquid-phase intermediates in forming reactive intermediates, and 3) the combined effects of catalyst composition and solvent properties on reaction rates and selectivities. The initial work will focus on palladium (Pd) and palladium-gold (PdAu) clusters as the active catalytic materials, but learning derived from those materials will be used to generate guiding principles and activity descriptors to identify inexpensive alternatives to PdAu catalysts. To achieve these goals, a combination of kinetic and (ex situ and in situ) infrared spectroscopic techniques will be employed to probe the catalytic chemistry at the liquid-solid interfaces of supported metal clusters. This investigation will involve design parameters such as: size and composition of the metal clusters, the role of electrophilic adsorbates, and solvent properties such as pH and polarity. Although these studies specifically target the direct synthesis of H2O2, the work will develop tools and expertise needed for future investigations of a broad range of oxidative and reductive chemistries at liquid-solid interfaces.