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.

Fischer-Tropsch合成（FTS）是一种广泛使用的化学制造工艺，主要用于将蒸汽改革的天然气转换为长链碳氢化合物或适合燃料，润滑剂和其他化学产品的有机分子。 FTS反应通常在高压下进行，其中有利于一氧化碳（CO）和氢（H2）之间的催化反应。 如此高的压力需要极大的反应堆和相关的化学工厂，以实现成本效益的制造所需的规模经济。 该项目研究了一种替代方法，其中对催化剂特性进行调整以促进较低压力的反应。 反过来，较低的压力有可能为较小规模的植物中的成本效益的FT打开大门，这些植物可以靠近天然气或可再生生物量的遥远或滞留的天然气来源或分布来源。 分布式FTS的一个主要好处是其能力确保化学制造的安全性，因为我们的国家向制造燃料和化学品的净零碳排放技术过渡。 该项目通过中心假设探索了电子金属支持的相互作用（EMSI），即基本支持将电子密度注入支撑上支撑的金属簇中，而这种电子捐赠将导致CO在金属表面上更强的结合。 具体而言，研究人员将合成并评估氟芬氏菌（RU）和钴（CO）催化剂，这些催化剂（CO）催化剂在一般式MGXALYO的混合金属氧化物上支撑。 Mg：Al比率将控制支撑物的碱性，然后将电子捐赠范围捐赠到支持的CO和RU中。 金属电子结构的变化将通过L边缘X射线吸收光谱（XAS）监测。 实验数据（包括通过傅立叶变换红外光谱（FTIR）和CO温度填充解吸（TPD）直接评估CO结合强度的直接评估，将通过密度功能理论（DFT）计算和糟糕的分析来验证，以确认金属/支持和吸附对电子结构和电荷转移的影响。 表征和计算分析将在实验室反应器中现实的工作条件下对FT反应进行动力学研究。 更广泛地说，该项目将通过减少滞留天然气升级到液体燃料的资本和运营费用，从而为美国带来经济利益。该项目还将在与化学过程工程有关的催化方面培训毕业生，本科和高中生。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的评估评估标准的评估值得支持的。