Electronic Metal-Support Interactions in Fischer-Tropsch Catalysis

费托催化中的电子金属-载体相互作用

• 批准号: 2310361
• 负责人: Konstantinos Goulas
• 金额: $ 53.95万
• 依托单位: Oregon State University
• 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: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2310361&HistoricalAwards=false
• 关键词: Electronic; Metal; Support; Interactions; Fischer

Fischer-Tropsch synthesis (FTS) is a widely employed chemical manufacturing process, primarily used to convert steam-reformed natural gas to long-chain hydrocarbons or organic molecules suitable for fuels, lubricants, and other chemical products. The FTS reaction is typically run at high pressures where the catalyzed reaction between carbon monoxide (CO) and hydrogen (H2) is favored. Such high pressures demand extremely large reactors and associated chemical plants to achieve the economies of scale needed for cost-effective manufacturing. The project investigates an alternative approach to FTS in which the catalyst properties are tuned to promote reaction at lower pressures. The lower pressures, in turn, potentially open the door to cost-effective FTS in smaller scale plants that can be located close to remote or stranded sources of natural gas or distributed sources of renewable biomass. A key benefit of low-pressure, distributed FTS resides in its capability to ensure security in chemical manufacturing as our nation transitions to net-zero carbon emission technologies for manufacturing fuels and chemicals. The project explores Electronic Metal-Support Interactions (EMSI) through the central hypothesis that a basic support will inject electron density into the metal clusters supported on them, and this electron donation will, in turn, result in stronger binding of CO onto the surface of the metal. Specifically, the investigators will synthesize and evaluate ruthenium (Ru) and cobalt (Co) catalysts supported on mixed metal oxides of the general formula MgxAlyO. The Mg:Al ratio will control the basicity of the supports and, in turn, the extent of electron donation into the supported Co and Ru. Changes in the electronic structure of the metals will be monitored by L-edge X-ray absorption spectroscopy (XAS). The experimental data (including direct assessment of CO binding strength via Fourier Transform Infrared Spectroscopy (FTIR) and CO temperature-programmed desorption (TPD)) will be validated with density functional theory (DFT) calculations and Bader analysis to confirm metal/support and adsorbate effects on the electron structure and charge transfer. The characterization and computational analyses will be followed by kinetic studies of the FT reaction under realistic operating conditions in a laboratory reactor. More broadly, the project will potentially lead to economic benefits for the U.S. by reducing capital and operating expenses for stranded natural gas upgrading to liquid fuels. The project will also train graduate, undergraduate, and high-school students in aspects of catalysis as related to chemical process engineering.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.

费托合成 (FTS) 是一种广泛采用的化学制造工艺，主要用于将蒸汽重整天然气转化为适用于燃料、润滑油和其他化学产品的长链碳氢化合物或有机分子。 FTS 反应通常在高压下进行，有利于一氧化碳 (CO) 和氢气 (H2) 之间的催化反应。 如此高压需要极大的反应器和相关化工厂，以实现经济高效的制造所需的规模经济。 该项目研究了费托合成的替代方法，其中调整催化剂性能以促进较低压力下的反应。 反过来，较低的压力可能为小型工厂中具有成本效益的 FTS 打开大门，这些工厂可以位于靠近偏远或搁浅的天然气来源或分布式可再生生物质来源的地方。 低压分布式 FTS 的一个主要优势在于，随着我们国家向燃料和化学品制造的净零碳排放技术过渡，它能够确保化学品制造的安全。 该项目通过中心假设探索电子金属支撑相互作用（EMSI），即基本支撑会将电子密度注入其支撑的金属簇中，而这种电子捐赠反过来会导致CO在其表面上有更强的结合。金属。 具体来说，研究人员将合成并评估负载在通式 MgxAlyO 的混合金属氧化物上的钌 (Ru) 和钴 (Co) 催化剂。 Mg:Al 比例将控制载体的碱度，进而控制向负载的 Co 和 Ru 提供电子的程度。 金属电子结构的变化将通过 L 边 X 射线吸收光谱 (XAS) 进行监测。 实验数据（包括通过傅里叶变换红外光谱 (FTIR) 和 CO 程序升温解吸 (TPD) 直接评估 CO 结合强度）将通过密度泛函理论 (DFT) 计算和 Bader 分析进行验证，以确认金属/载体和吸附物对电子结构和电荷转移的影响。 表征和计算分析之后将在实验室反应器的实际操作条件下进行 FT 反应的动力学研究。 更广泛地说，该项目将有可能通过减少搁浅天然气升级为液体燃料的资本和运营费用，为美国带来经济效益。该项目还将在与化学过程工程相关的催化方面对研究生、本科生和高中生进行培训。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。