Bifunctionality of Intermetallic Pd-In/Indium-Oxide Catalysts for CO2 Hydrogenation to Methanol

CO2 加氢制甲醇金属间化合物 Pd-In/Ind-Oxide 催化剂的双功能

• 批准号: 2323274
• 负责人: Jason Weaver
• 金额: $ 62.37万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-12-01 至 2026-11-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2323274&HistoricalAwards=false
• 关键词: Bifunctionality; Intermetallic; Pd; Indium; Oxide

Developing catalytic processes to efficiently convert carbon dioxide (CO2) to chemicals and fuels is essential for mitigating CO2 emissions and enabling technologies that utilize renewable energy. The direct conversion of CO2 to methanol is particularly attractive because methanol can serve as a fuel in existing power generation systems and is used as a feedstock in the commercial-scale synthesis of a wide-range of important chemicals. Currently, however, catalytic processes to directly hydrogenate CO2 to methanol are unsuitable for commercial use. The major difficulty is that most catalytic materials lack the stability and activity to operate at the low temperatures needed for CO2-based methanol synthesis. In this project, the investigators are developing a fundamental understanding of the selective hydrogenation of CO2 to methanol using bifunctional metal/metal-oxide catalysts. Exploiting the distinct chemical functionality of the metallic and oxide components of these catalysts is necessary for efficiently and selectively converting CO2 to methanol. The investigators are providing opportunities for high school and undergraduate students to participate in their research and are focused on recruiting students from underrepresented groups to engage in these activities. These outreach activities seek to promote the science, technology, engineering and math (STEM) disciplines. The project aims to develop a fundamental understanding of Pd-promoted In2O3 (indium oxide) catalysts and determine how the chemical bifunctionality of these surfaces can be exploited to enhance the selective hydrogenation of CO2 to methanol. The key idea is that coexisting In2O3 and intermetallic PdxIny phases will act cooperatively to enhance the hydrogenation of CO2 to methanol by exchanging reaction intermediates and providing interfacial surface sites with unique chemical properties, and that the catalytic behavior can be modified by the PdxIny structure and stoichiometry. This research involves investigations of the structural and chemical properties of Pd-modified In2O3 prepared as planar crystalline surfaces as well as nanocrystalline powders. These materials are investigated using a combination of experimental and theoretical methods including ultrahigh vacuum surface science and catalyst characterization, reactor studies and operando surface spectroscopy, as well as density functional theory and microkinetic modeling. A primary aim of the project is to establish fundamental structure-function relationships to guide the design of Pd-In2O3 catalysts for the selective hydrogenation of CO2 to methanol. The project involves stringent comparisons of the results of first-principles modeling with experimental results obtained from planar crystalline surfaces and more complex nanoparticles to develop a robust understanding of the direct hydrogenation of CO2 to methanol.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.

开发催化过程以有效地将二氧化碳（CO2）转换为化学物质和燃料，对于减轻使用可再生能源的技术和促进技术至关重要。二氧化碳向甲醇的直接转化特别有吸引力，因为甲醇可以用作现有发电系统的燃料，并用作商业尺度合成大量重要化学物质的原料。然而，目前，直接氢化二氧化碳至甲醇的催化过程不适合商业用途。主要的困难是，大多数催化材料都缺乏在基于二氧化碳基于二氧化碳的甲醇合成所需的低温下运行的稳定性和活性。在这个项目中，研究人员使用双功能金属/金属氧化催化剂对CO2的选择性氢化开发了基本理解。利用这些催化剂的金属和氧化物成分的不同化学功能对于有效，有选择地将CO2转化为甲醇是必要的。调查人员正在为高中和本科生提供参与研究的机会，并专注于招募来自代表性不足的团体的学生从事这些活动。这些外展活动旨在促进科学，技术，工程和数学（STEM）学科。该项目旨在对PD促进的In2O3（氧化物）催化剂进行基本理解，并确定如何利用这些表面的化学双方功能，以增强二氧化碳对甲醇的选择性氢化。关键的想法是，通过交换反应中间体并提供独特的化学特性，可以合作地共存IN2O3和金属间PDXINY相，以合作，以增强CO2与甲醇的氢化，并为PDXINY结构和固定仪可修改催化性能。这项研究涉及研究以平面晶体表面以及纳米晶体粉末制备的PD修饰In2O3的结构和化学性质。使用实验和理论方法（包括超高真空表面科学和催化剂表征），反应堆研究和操作表面光谱以及密度功能理论和微动力学建模的结合，研究了这些材料。该项目的主要目的是建立基本的结构 - 功能关系，以指导PD-IN2O3催化剂的设计，以选择将CO2的选择性氢化为甲醇。该项目涉及对第一原理建模结果与从平面晶体表面获得的实验结果和更复杂的纳米颗粒获得的实验结果的严格比较，以对二氧化碳直接氢化为甲醇的直接氢化进行强有力的理解。这奖反映了NSF的法定任务，并通过使用基金会的智力效果和宽阔的范围来评估支持，并以评估值得评估。