EAGER: Towards Sustainable Carbon-Negative Chemical Manufacturing by Creating Synergy between Carbon Dioxide Utilization and Biorefinery

开发经济上可行的技术，从大气中的二氧化碳和可再生能源制造负碳燃料和商品化学品是一项重大挑战，具有重要的社会和环境可持续性影响。该研究项目探讨了二氧化碳利用和生物精炼操作之间的协同作用，用于生产特定类别的化学品，甲酸盐。 二氧化碳是从生物精炼操作中释放出来的，因此这种“生物源”二氧化碳正在被探索作为原料。该研究项目旨在系统地探索和模拟综合二氧化碳捕获和转化为甲酸盐的过程化学。 除了通过出版物和演讲向更广泛的受众传播这项研究的结果外，研究人员还将从太平洋西北部路易斯斯托克斯少数民族参与计划联盟（PNW LSAMP）招募本科生。LSAMP的使命是为代表性不足的少数民族增加上大学的途径。研究小组还承诺为社区大学的学生提供两个暑期实习机会，以进行与本项目相关的研究。本研究项目的主要目标是研究碳酸根离子的反应性，碳酸根离子是通过在乙醇水溶液中用胺或氨捕获二氧化碳而形成的，用于催化加氢生产甲酸酯。该研究项目的重点是研究综合二氧化碳捕获和氢化过程的过程化学和反应机理，其中碳酸乙酯离子是在近环境温度下在胺-生物乙醇-水溶剂中高度选择性生产甲酸酯的关键中间体。通过理论和实验研究，阐明了二氧化碳捕获过程中碳酸乙酯离子的形成机理。碳载钯纳米催化剂的结构-活性关系正在使用先进的实验工具，如原位核磁共振光谱和傅立叶变换红外光谱进行探索。特别是，钯纳米晶体的表面刻面对二氧化碳-胺-乙醇-水系统中的生物碳酸盐和碳酸乙酯吸附物的活化的影响正在研究中。通过创造增值碳利用和生物精炼过程之间的协同作用，这种研究方法可能会导致生产负碳化学品的新技术的发展。

The development of economically viable techniques for manufacturing carbon-negative fuels and commodity chemicals from atmospheric carbon dioxide and renewable energy is a grand challenge with important societal and environmental sustainability implications. This research project explores the synergy between carbon dioxide utilization and biorefining operations for producing a particular class of chemicals, formates. Carbon dioxide is released from biorefining operations, so this "biogenic" carbon dioxide is being explored as a feedstock. The research project project aims to systematically explore and model the process chemistry of integrated carbon dioxide capture and conversion into formates. In addition to disseminating the results of this research to a broader audience via publications and presentations, the researchers will recruit undergraduate from the Pacific Northwest Louis Stokes Alliance for Minority Participation program (PNW LSAMP). The mission of LSAMP is to increase pathways to college for underrepresented minorities. The research group also commits to offering two summer internships for community college students to do research associated with this project.The main objective of this research project is to investigate the reactivity of carbonate ions, formed by capturing carbon dioxide with amines or ammonia in aqueous ethanol solutions, for the production of formates by catalytic hydrogenation. The research project focuses on studying the process chemistry and reaction mechanism of the integrated carbon dioxide capture and hydrogenation process, in which ethyl carbonate ions are the key intermediates for the highly selective production of formates in amine-bioethanol-water solvents at near ambient temperatures. The mechanism of the formation of ethyl carbonate ions during the carbon dioxide capture process is being elucidated through theoretical and experimental studies. The structure-activity relationship of carbon supported palladium nano-catalysts is being explored using advanced experimental tools, such as in-situ nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy. In particular, the influence of the surface facets of palladium nanocrystals on the activation of biocarbonate and ethyl carbonate adsorbates in the carbon dioxide-amine-ethanol-water systems is being studied. By creating synergy between value-added carbon utilization and biorefining processes, this research approach may lead to the development of new technologies for manufacturing carbon-negative chemicals.