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

职业：直接合成 H2O2 的分子理解和催化剂设计

• 批准号: 1553137
• 负责人: David Flaherty
• 金额: $ 51.47万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-03-01 至 2022-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1553137&HistoricalAwards=false
• 关键词: CAREER; Molecular; Understanding; Catalyst; Design

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.

摘要 (Flaherty; 1553137) 目前，每年有数百万吨有害氯化化合物用于纸浆、纸张和日用化学品制造过程中的选择性氧化和漂白反应。 过氧化氢 (H2O2) 是氯化化合物的“绿色”替代品，但并未广泛使用，因为目前的生产方法仅在大规模生产时才具有经济可行性。 拟议的研究将研究一种替代催化方法——从氢气 (H2) 和氧气 (O2) 直接合成 H2O2——这将使 H2O2 能够在现场生产，用于更小、更常见的加工设施。 拟议的研究与以年轻女性为重点的教育计划相结合，重点是培养研究和研究指导技能。该研究将结合催化动力学和原位光谱测量进行系统研究，以确定：1）直接合成 H2O2 的机制，2）表面、溶剂和液相中间体在形成反应性中间体中的作用，以及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。 最初的工作将重点关注钯 (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，将采用动力学和（非原位和原位）红外光谱技术的组合来探测负载金属簇的液-固界面处的催化化学。 这项研究将涉及设计参数，例如：金属簇的尺寸和组成、亲电吸附物的作用以及溶剂特性（例如 pH 和极性）。 尽管这些研究专门针对 H2O2 的直接合成，但这项工作将开发未来研究液-固界面上广泛的氧化和还原化学所需的工具和专业知识。