Tuning Peripheral Functionality of Molecular and Interfacial Electrocatalysts to Influence Reaction Pathways

调整分子和界面电催化剂的外围功能以影响反应途径

• 批准号: RGPIN-2021-03691
• 负责人: Nichols, Eva
• 金额: $ 1.75万
• 依托单位: University of British Columbia
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748026
• 关键词: Tuning; Peripheral; Functionality; Molecular; Interfacial

The development of more efficient and selective catalysts for electrochemical reduction of carbon oxides is critical to lowering global greenhouse gas emissions and transitioning away from fossil fuels. New catalyst designs and a more detailed understanding of fundamental reaction mechanisms are needed in order to realize the goal of a commercially viable carbon oxide electrolyzer. The proposed research program will design and study homogeneous and heterogeneous electrocatalysts by bringing together synthetic, electrochemical, and spectroscopic approaches. We will aim to precisely tune the local reaction environment through targeted installation of specific chemical groups that can alter the outcome of reaction pathways. By investigating the mechanistic differences in well-defined systems, we hope to eventually inform rational design of catalysts with activities and selectivities rivaling the best enzymatic systems. Our research program comprises three focus areas spanning homogeneous and heterogeneous catalysis. The first objective is to modify the second coordination sphere of homogeneous catalysts through introduction of a second metal center and to examine the electrocatalytic activity for a range of carbon oxide reduction reactions (CO2, CO, bicarbonate, etc.). It is proposed that the presence of two metal centers rather than one will enable new cooperative interactions with carbon oxide substrates that could potentially enable previously unobserved reactivity. The second objective is to study reaction mechanisms on the aforementioned catalysts to understand the role of the second coordination sphere groups in detail. These efforts will be enabled by electrochemical and advanced spectroscopic techniques, including time-resolved infrared (TR-IR) spectroscopy. In parallel, we will work on a third objective, which is to extend these ideas of chemical control over local reaction environment to heterogeneous electrode interfaces. Specifically, we will employ attenuated total reflectance-surface enhanced IR absorption spectroscopy (ATR-SEIRAS) under operating conditions to investigate how reaction pathways on the surface can be manipulated by molecular design. We seek to become an internationally recognized lab with a unique skillset that includes advanced time-resolved and surface-enhanced FT-IR capabilities to address challenging problems at the forefront of renewable energy catalysis. The proposed research will provide excellent training opportunities to prepare HQP (highly qualified personnel) for jobs in Canadian chemical and clean technology industries and in academia.

开发更有效和更有选择性的碳氧化物电化学还原催化剂对于减少全球温室气体排放和摆脱化石燃料至关重要。为了实现具有商业可行性的二氧化碳电解槽的目标，需要新的催化剂设计和对基本反应机理的更详细的了解。拟议的研究计划将通过结合合成、电化学和光谱方法来设计和研究均相和非均相的电催化剂。我们的目标是通过有针对性地安装可以改变反应途径结果的特定化学基团来精确调整局部反应环境。通过研究定义明确的体系中的机理差异，我们希望最终能够提供合理的设计，使催化剂的活性和选择性可与最好的酶体系相媲美。我们的研究计划包括三个重点领域，跨越均相催化和多相催化。第一个目标是通过引入第二金属中心来修饰均相催化剂的第二配位球，并考察其对一系列一氧化碳还原反应(二氧化碳、一氧化碳、重碳酸盐等)的电催化活性。有人提出，两个金属中心的存在而不是一个金属中心的存在将使新的与一氧化碳底物的合作作用成为可能，这可能使以前未观察到的反应成为可能。第二个目标是研究上述催化剂上的反应机理，以详细了解第二配位球基的作用。这些努力将通过电化学和先进的光谱技术实现，包括时间分辨红外光谱(TR-IR)。同时，我们将致力于第三个目标，即将这些对局部反应环境进行化学控制的想法扩展到不同种类的电极界面。具体地说，我们将在操作条件下使用衰减全反射表面增强红外吸收光谱(ATR-SEIRAS)来研究如何通过分子设计来操纵表面上的反应路径。我们寻求成为国际公认的实验室，拥有独特的技能，包括先进的时间分辨和表面增强的FT-IR能力，以解决可再生能源催化领域的前沿挑战问题。拟议的研究将提供极好的培训机会，为加拿大化学和清洁技术行业以及学术界的工作准备HQP(高素质人员)。