Collaborative Research: Addressing Morphological Instability in Topologically Complex Electrocatalytic Nanostructures

合作研究：解决拓扑复杂电催化纳米结构的形态不稳定性

• 批准号: 1904578
• 负责人: Zhiyong Xia
• 金额: $ 15万
• 依托单位: Johns Hopkins University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904578&HistoricalAwards=false
• 关键词: Collaborative; Research; Addressing; Morphological; Instability

Non-Technical Summary:Commercialization of renewable energy storage and conversion devices, such as water electrolyzers and fuel cells, requires advancements in both efficiency and operational longevity. Performance as well as cost of these electrochemical energy devices is strongly tied to the electrocatalyst materials that drive the reactions producing energy or fuel. Electrocatalyst materials development has centered on the design of nanoscale catalysts that maximize the exposure and usage of precious metals, i.e. Platinum, of which they are composed. These unique nanoscale architectures, however, are susceptible to multiple mechanisms of degradation, the rate of which is typically inversely proportional to the activity of the catalyst. The goal of this project is to highlight these mechanisms of degradation for electrocatalysts possessing complex nano-architectures. With a better understanding of how these materials degrade, mitigation strategies can be proposed, improving durability and breaking away from the inverse proportional relationship between electrocatalyst activity and durability. Insight developed through the proposed work will have a significant impact on the effort to bridge the gap between highly active and highly stable materials where integration of these morphologically stable yet complex and active electrocatalysts into electrochemical energy conversion and storage devices will yield significant improvements in both precious metal loading and device operational longevity. The proposed work will provide one PhD student and several undergraduate students with a broad and interdisciplinary research experience in interfacial electrochemistry and nanomaterial synthesis for renewable energy technologies. Through a partnership with the Lindy Center at Drexel, the PI will highlight the principles of renewable and carbon neutral energy storage and conversion and promote interest in STEM for grade 4-12 community members.Technical Summary:This project will investigate the mechanisms by which three-dimensional, porous, morphologically complex electrocatalytic nanomaterials degrade under relevant electrochemical conditions. The products of this proposed research will highlight the limiting atomic processes and provide insight for the development of mitigation strategies that maintain morphological and compositional integrity with negligible impact on the intrinsic activity of the catalysts. The research objective of the proposed work is to develop a more detailed fundamental understanding of the convolution of electrochemical dissolution and surface diffusion driven coarsening for these three-dimensional nanomaterials that are in a constant state of meta-stability. It is hypothesized that electrochemical coarsening is driven by a dissolution/redeposition process rather than a pure surface diffusion driven process. Through a combination of experimental, local and global measurements, and computational analysis, this project will qualitatively and quantitatively assess the impact of relevant operational parameters on the morphological and compositional evolution of nanoporous materials. This proposed concept has a broad parameter space, composed of a complex web of intertwined interactions. Computational manipulation of this parameter space, through kMC, will be used to explore the underlying physics of electrochemical coarsening: a) the distance along the surface the dissolved species travels before redepositing, b) response time of dissolution and deposition, c) flux of local dissolution for a given UPL, d) the coordination of the preferred defect site, e) flow rate of electrolyte solution (simply by a time-dependent removal of dissolved species), and f) type of surface impurity.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.

非技术性总结：可再生能源储存和转换设备（如水电解槽和燃料电池）的商业化需要提高效率和运行寿命。这些电化学能量装置的性能以及成本与驱动产生能量或燃料的反应的电催化剂材料密切相关。电催化剂材料的开发集中在纳米级催化剂的设计上，该纳米级催化剂最大限度地暴露和使用贵金属，即铂，它们由其组成。然而，这些独特的纳米级结构易受多种降解机制的影响，降解速率通常与催化剂的活性成反比。这个项目的目标是突出这些机制的降解具有复杂的纳米结构的电催化剂。随着对这些材料如何降解的更好理解，可以提出缓解策略，提高耐久性并摆脱电催化剂活性和耐久性之间的反比关系。通过所提出的工作开发的见解将对弥合高活性和高稳定性材料之间的差距的努力产生重大影响，其中将这些形态稳定但复杂且活性的电催化剂整合到电化学能量转换和存储设备中，将显著改善贵金属负载和设备运行寿命。拟议的工作将为一名博士生和几名本科生提供可再生能源技术界面电化学和纳米材料合成方面的广泛和跨学科的研究经验。通过与德雷克塞尔大学林迪中心的合作，PI将突出可再生能源和碳中性能源储存和转换的原则，并促进4-12年级社区成员对STEM的兴趣。技术摘要：本项目将研究三维，多孔，形态复杂的电催化纳米材料在相关电化学条件下降解的机制。这项拟议研究的产品将突出限制原子过程，并提供洞察力的缓解策略，保持形态和组成的完整性，对催化剂的固有活性的影响可以忽略不计的发展。拟议的工作的研究目标是开发一个更详细的基本理解的卷积的电化学溶解和表面扩散驱动的粗化这些三维纳米材料，是在一个恒定的亚稳定状态。据推测，电化学粗化是由溶解/再沉积过程，而不是一个纯粹的表面扩散驱动的过程。通过实验、局部和全局测量以及计算分析相结合，该项目将定性和定量评估相关操作参数对纳米多孔材料形态和成分演变的影响。这个概念有一个广泛的参数空间，由相互交织的复杂网络组成。通过kMC对该参数空间的计算操作将用于探索电化学粗化的基本物理：a）溶解物质在再沉积之前沿表面行进的沿着，B）溶解和沉积的响应时间，c）对于给定UPL的局部溶解通量，d）优选缺陷位置的配位，e）电解质溶液的流速（简单地通过随时间变化的溶解物质的去除），和f）表面杂质的类型。该奖项反映了NSF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。