ERI: Aqueous Phase Reforming of Multi-Component Carboxylic Acid Systems over Pt Catalysts

由于生物质来源的复杂化学成分，可再生燃料和化学品制造带来了巨大的挑战。生物炼油厂显示出将生物质可再生地转化为生物燃料和化学品的前景；然而，由于废水中含有高浓度的溶解含氧碳氢化合物，效率严重低下。水相重整(APR)提供了一种解决方案，将这些废水在催化剂的作用下转化为可再生氢气。传统催化剂表现出较差的APR性能，因为在催化剂表面和废水流之间的界面上，不同的生物质基化学品之间存在着强烈的纳米级化学相互作用。为了加快高性能APR催化剂的开发，该项目将把实验上可控的条件，如组成和温度，与催化界面的结构和反应活性联系起来。这将通过研究铂-水界面上一系列基于生物质的分子之间的纳米级相互作用来实现。此外，该项目将通过应用虚拟现实来加强科学和工程教育，使学生能够在纳米尺度上可视化分子系统，并将他们的观察与宏观尺度的化学性质联系起来。尽管APR具有潜力，但研究往往忽略了真正的生物质原料的多组分性质，导致催化剂性能不佳。利用多尺度计算建模和实验协作，该项目将提供关于水相性质和固-液催化界面之间相互作用的见解。具体地说，该项目侧重于表征二元羧酸混合物在铂-水界面上的竞争吸附和分解势能面。实验上可控的条件(即组成和温度)将通过原子尺度的电子计算(即密度泛函理论)和力场分子动力学模拟相结合的方式与铂-水界面的结构和反应性联系起来。所获得的见解将为抗失活APR催化剂的设计提供指导，并促进对复杂界面上的竞争吸附和催化反应的理解。此外，这项研究符合生物质利用和氢经济发展的社会目标，以及针对研究生和本科生的综合教育和推广努力，包括那些来自代表不足的群体的学生。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Renewable fuel and chemical manufacturing raises significant challenges due to the complex chemistry of biomass sources. Biorefineries show promise for renewably converting biomass to biofuels and chemicals; however, significant inefficiencies are present, as the wastewater streams have high concentrations of dissolved oxygenated hydrocarbons. Aqueous phase reforming (APR) offers a solution by converting these wastewater streams into renewable hydrogen with catalysts. Traditional catalysts display poor APR performance due to strong, nanoscale chemical interactions between different biomass-based chemicals at the interface between the catalyst surface and the wastewater stream. To accelerate the development of high performing APR catalysts, the project will connect experimentally controllable conditions, such as the composition and temperature, to the structure and reactivity of catalytic interfaces. This will be achieved by investigating the nanoscale interactions between a series of biomass-based molecules at a platinum-water interface. Furthermore, the project will enhance science and engineering education by applying virtual reality to enable students to visualize molecular systems at the nanoscale and connect their observations to macroscale chemical properties. Despite APR's potential, studies often overlook the multi-component nature of real biomass-based feedstocks, leading to suboptimal catalyst performance. Leveraging multiscale computational modeling and experimental collaboration, the project will provide insights regarding the interplay between aqueous phase properties and solid-liquid catalytic interfaces. Specifically, the project focuses on characterizing the competitive adsorption and potential energy surface for decomposition of binary carboxylic acid mixtures at a platinum-water interface. Experimentally controllable conditions (i.e., composition and temperature) will be connected to the structure and reactivity of the platinum-water interface via a combination of atomic-scale electronic calculations (i.e. density functional theory) and force field molecular dynamics simulations. Insights gained will inform the design of deactivation-resistant APR catalysts and advance understanding of competitive adsorption and catalytic reactions at complex interfaces. Furthermore, this research aligns with societal goals of biomass utilization and hydrogen economy development, with integrated education and outreach efforts targeting graduate and undergraduate students, including those from underrepresented groups.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.