Quantifying adsorption-diffusion-reaction of biomass-derived molecules at solid-liquid interfaces

量化固液界面生物质衍生分子的吸附扩散反应

• 批准号: 1805129
• 负责人: Susannah Scott
• 金额: $ 31.95万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1805129&HistoricalAwards=false
• 关键词: Quantifying; adsorption; diffusion; reaction; biomass

Distributed manufacturing of chemical building blocks from renewable feedstocks as an alternative to non-renewable fossil resources is an important long-term goal in building a sustainable domestic chemical industry. Transformations and separations of functionalized molecules, such as those derived from depolymerization of lignocellulosic biomass, can be accomplished using porous solids that selectively adsorb and convert them under mild conditions (relatively low temperatures). Such processes are usually conducted in the presence of semi-aqueous solvent systems, which themselves exert strong effects on partitioning, dynamics, and reactivity, significantly altering the effectiveness of heterogeneous catalysts in biomass conversion. The proposed research project aims at developing a fundamental understanding of molecular behavior at solid/liquid interfaces, which is essential for the rational development of durable heterogeneous catalysts and benign solvent systems for processing renewable feedstocks.The project focuses on understanding the nature of the co-adsorption of solvent and solvent molecules in selected microporous and mesoporous materials, in order to generate fundamental knowledge about the role of adsorption in controlling rates and directing selectivity. The objective is to describe and quantify the extent of molecular partitioning at solid-liquid interfaces in conjunction with pore confinement; explore the origins of selective adsorption and consequences for mobility of adsorbed molecules; and combine this information to create new insight into solvent effects in catalytic reactions involving selected oxygenated organic compounds. Thermodynamic measurements of enthalpies of adsorption/absorption in porous materials will be obtained from conventional adsorption equilibrium measurements in combination with isothermal titration calorimetry. The molecular nature of the interactions will be probed using both ex-situ and in-situ solid state Nuclear Magnetic Resonance (NMR) to distinguish between adsorbed/absorbed and free molecules, and to measure their relative proportions and rates of exchange. Density Functional Theory (DFT) and Molecular Dynamics (MD) simulations will be employed to interpret trends in partitioning and adsorption. Reaction kinetics will be recorded in situ and linked to interfacial composition and dynamic behavior. The effect of catalyst pore size and framework topology, hydrophilicity/hydrophobicity, the presence, identity, and density of extra-framework cations, will be explored. A graduate student researcher will be trained in the characterization of solid-liquid interfaces and will learn to make connections between thermodynamic and kinetic measurements. Undergraduate students from under-represented groups will receive mentoring and participate directly in the research.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.

可再生原料的分布式制造化学构建块，以替代非可再生化石资源，是建立可持续的国内化学工业的重要长期目标。可以使用有选择性吸附并在轻度条件（相对较低的温度）下转化的多孔固体来完成功能化分子的转化和分离，例如木质纤维素生物量解聚的转化和分离。这种过程通常是在存在半水溶剂系统的情况下进行的，该系统本身对分配，动力学和反应性产生了强大的影响，从而显着改变了异质催化剂在生物量转化中的有效性。 The proposed research project aims at developing a fundamental understanding of molecular behavior at solid/liquid interfaces, which is essential for the rational development of durable heterogeneous catalysts and benign solvent systems for processing renewable feedstocks.The project focuses on understanding the nature of the co-adsorption of solvent and solvent molecules in selected microporous and mesoporous materials, in order to generate fundamental knowledge about the role of控制速率和指导选择性的吸附。目的是描述和量化与孔隙限制在固液界面处分子分配的程度。探索选择性吸附和吸附分子迁移率的后果的起源；并结合这些信息，以在涉及选定的氧化有机化合物的催化反应中对溶剂作用创建新的见解。多孔材料吸附/吸收焓的热力学测量将从常规的吸附平衡测量与等温滴定热量法结合使用。相互作用的分子性质将使用前坐骨和原位固态核磁共振（NMR）探测，以区分吸附/吸收和自由分子，并测量其相对比例和交换速率。密度功能理论（DFT）和分子动力学（MD）模拟将用于解释分配和吸附中的趋势。反应动力学将原位记录，并与界面组成和动态行为相关。将探索催化剂孔径和框架拓扑，亲水性/疏水性，外部框架外阳离子的存在，身份和密度的影响。研究生研究人员将接受固定液体界面的表征培训，并将学会在热力学和动力学测量之间建立连接。来自代表性不足的团体的本科生将直接接受指导并参与研究。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优点和更广泛的影响审查标准通过评估来获得支持的。

项目成果

Solvent effects on catalytic activity and selectivity in amine-catalyzed d-fructose isomerization

• DOI: 10.1016/j.jcat.2022.12.029
• 发表时间: 2022-12
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: Peter Drabo;M. Fischer;Meike Emondts;Jegor Hamm;Mats Engelke;Marc Simonis;Long Qi;S. Scott

Evidence for Entropically Controlled Interfacial Hydration in Mesoporous Organosilicas

• DOI: 10.1021/jacs.1c11342
• 发表时间: 2022-01-18
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Moon, Hyunjin;Collanton, Ryan P.;Scott, Susannah L.
• 通讯作者: Scott, Susannah L.