CAREER: Catalytic Resonance-Enhanced Activation of Hydrocarbon Resources

利用最近丰富的美国页岩气资源作为化学生产原料，需要使用催化升级策略。与原料和产品的化学成分和地理分布有关的限制要求开发能够利用这些新资源的创新催化战略。受具有成本竞争力的可再生电力的持续增长的推动，使用电化学策略来激活烃资源提供了一个独特的机会，通过避免与热驱动的化学转化同义的高压和高温来降低化学制造的环境影响和成本。此外，电化学方法更能抵抗传统化学制造供应链中构成弹性和安全威胁的重大中断事件。因此，在这项研究计划中，电驱动化学反应策略的发展具有重大的变革潜力。然而，烃资源的直接电化学催化改质目前受到反应速率慢和对所需产物的选择性差的限制。这项研究将促进催化共振的发展，从而及时调节催化剂的能量，以最大限度地提高反应速率和对所需产物的选择性。这项研究将可持续化学转化，可再生能源和催化动力学的概念整合到一个教育计划，将吸引学生在马萨诸塞大学和周边地区。通过开发教育在线内容，使用简单有效的教学技术来传播能源相关应用背后的基础科学，将扩大外联工作的影响。这项研究将侧重于发展对碳氢化合物电化学氧化成增值含氧化合物的催化共振的基本理解。虽然驱动电化学反应的可再生和成本有效的能量是容易获得的，但是与烃的电化学氧化相关的催化转换速率（例如，烷烃、烯烃）限制了该方法。确实表现出可观的电催化活性的金属催化剂受到由于烃过度氧化成作为不期望产物的二氧化碳而缺乏对部分氧化产物的选择性的困扰。在稳态条件下，对催化活性和选择性的挑战有着相似的起源：平衡必要的吸附物覆盖率、动力学驱动力以及催化循环中涉及的法拉第和非法拉第基本步骤的组合。催化工作电极的受控能量振荡抑制了速率决定因素，允许通过访问在静态条件下不能维持的非平衡状态来进行独立调谐。虽然这项研究将集中在碳氢化合物的氧化，这项工作将发展的理解和能力，需要扩展的概念，催化共振到其他重要的化学transformation.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的知识价值和更广泛的影响审查标准的支持。

Leveraging the recent abundance of U.S. shale gas resources as a chemical production feedstock requires the use of catalytic upgrading strategies. Constraints related to chemical composition and geographical distribution of both the feedstocks and products require the development of innovative catalytic strategies that can take advantage of these new resources. Motivated by the continuous growth of cost-competitive renewable electric power, the use of electrochemical strategies to enable the activation of hydrocarbon resources provides a unique opportunity to reduce the environmental impact and cost of chemical manufacturing by avoiding the high pressures and temperatures synonymous with thermally driven chemical transformations. Furthermore, the electrochemical approach is more resistant to major disruption events that pose resilience and safety threats in traditional chemical manufacturing supply chains. Therefore, the development of electrically driven chemical reaction strategies in this research program has significant transformative potential. Direct electrochemical catalytic upgrading of hydrocarbon resources, however, currently is limited by both slow reaction rates and poor selectivity to desired products. This study will advance the development of catalytic resonance, whereby the energetics of a catalyst is modulated in time to maximize the reaction rate and selectivity towards the desired product. This study will integrate concepts of sustainable chemical transformation, renewable energy sources, and catalytic kinetics into an educational plan that will engage students both at UMass and the surrounding area. The impact of outreach efforts will be expanded by developing educational online content, using simple and effective teaching techniques to communicate the fundamental science behind energy related applications.This study will focus on developing a fundamental understanding of catalytic resonance for the electrochemical oxidation of hydrocarbons into value-added oxygenates. While renewable and cost-effective energy to drive the electrochemical reactions is readily available, the rate of catalytic turnover associated with the electrochemical oxidation of hydrocarbons (e.g., alkanes, alkenes) limits the approach. Metal catalysts that do exhibit appreciable electrocatalytic activity are plagued by the lack of selectivity to partial oxidation products due to the over-oxidation of hydrocarbons into carbon dioxide as an undesirable product. Under steady-state conditions, the challenges to catalytic activity and selectivity share a similar origin: balancing the necessary adsorbate coverages, kinetic driving force, and the combination of faradaic and non-faradaic elementary steps involved in the catalytic cycle. Controlled energetic oscillations of the catalytic working electrode decouples the rate-determining factors, allowing for their independent tuning by accessing non-equilibrium states that cannot be sustained under static conditions. While this study will focus on hydrocarbon oxidation, the work will develop the understanding and capabilities needed for extending the concept of catalytic resonance to other important chemical transformations.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.