CAREER: Predictive design and control of the electrode/electrolyte interface for improved electrocatalysis

电催化过程可以通过在工业化学品生产中使用可再生发电来满足对可持续燃料和化学品日益增长的需求。为了实现这一目标，该项目探索了电催化的基本方面，可以在电化学反应器（即电解槽）中部署，将废物二氧化碳（CO2）（一种温室气体）转化为有价值的乙烯，乙烯是塑料生产的前体。除了减少二氧化碳排放之外，电化学方法还为使用风能或太阳能打开了大门，从而有助于关闭碳循环。具体来说，该项目的重点是通过更好地了解电催化剂和含有可移动溶剂分子和离子的液体或聚合物电解质之间的界面上发生的复杂化学反应来提高电解槽的性能。该项目还将通过地平线项目展示化学中的溶剂和离子效应，以及克拉克森大学每年为高中生举办的为期两天的可持续化学生产研讨会，为学生提供实验和计算建模的实践研究经验，从而进一步加强科学和工程教育。电极/电解质界面的结构和组成决定了电催化反应的活性、选择性和机理。这项工作的总体目标是：1)定量理解驱动电催化中近表面观众离子和溶剂效应的化学和物理相互作用；2)改进和基准计算可处理的密度泛函理论（DFT）为基础的方法来预测这些效应；3)推进一种新的电化学技术，由研究者开发，以调整电极/电解质界面以增强电催化。为了实现这些目标，该项目将DFT建模与在定义明确的单晶电极和工业相关纳米颗粒催化剂上的实验相结合，以量化二氧化碳电还原过程中阳离子表面浓度和溶剂-阳离子-吸附质/表面相互作用的影响。了解了这一点，研究人员将使用他们实验室最近开发的一种技术，选择性地用有机分子“修饰”工业相关电催化剂的表面，从而可以预测溶剂和离子在该界面上的行为。这种方法不仅会对电催化中的阳离子、pH和溶剂效应产生基本的见解，而且还会产生一种计算上易于处理的方法来准确预测这些效应。总之，这些努力将确定电催化剂-电解质组合和有机改性剂，以提高二氧化碳电还原性能。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Electrocatalytic processes can satisfy the growing demand for sustainable fuels and chemicals by enabling the use of renewably generated electricity in industrial chemical production. To that goal, the project explores fundamental aspects of electrocatalysis that can be deployed in electrochemical reactors (i.e., electrolyzers) to convert the waste product carbon dioxide (CO2), a greenhouse gas, into valuable ethylene, a precursor for plastics production. Beyond CO2 emissions reduction, the electrochemical approach opens the door to using electricity from wind or solar power – thus helping to close the carbon cycle. Specifically, the project focuses on improving electrolyzer performance through better understanding of the complex chemistry occurring at the interface between the electrocatalyst and a liquid or polymer electrolyte containing mobile solvent molecules and ions. The project will additionally enhance science and engineering education through demonstrations of solvent and ion effects in chemistry via the Horizons program and hands-on research experiences in both experiment and computational modeling through a yearly 2-day workshop for high-school students on sustainable chemical production at Clarkson University. The structure and composition of the electrode/electrolyte interface are known to dictate the activity, selectivity, and mechanism of electrocatalytic reactions. The overarching goals of this work are to i) understand quantitatively the chemical and physical interactions that drive near-surface spectator ion and solvent effects in electrocatalysis, ii) refine and benchmark a computationally tractable density functional theory (DFT) based approach to predict these effects, and iii) advance a novel electrochemical technique, developed by the investigator, to tune the electrode/electrolyte interface for enhanced electrocatalysis. To achieve these goals, the project combines DFT modeling with experiments on both well-defined, single-crystal electrodes, and on industrially relevant nanoparticle catalysts, to quantify the cation surface concentration and the effects of solvent-cation-adsorbate/surface interactions during CO2 electroreduction. With this understanding, the investigators will use a technique – recently developed in their laboratory - to selectively “decorate” the surface of industrially-relevant electrocatalysts with organic molecules allowing predictive tailoring of the behavior of solvent and ions at this interface. This approach will not only yield fundamental insight into cation, pH, and solvent effects in electrocatalysis, but also generate a computationally tractable approach to accurately predict these effects. Together, those efforts will identify electrocatalyst-electrolyte combinations and organic modifiers which yield improved CO2 electroreduction performance.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.