Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Nano Lett. 2012 Sep 12;12(9):4417-23. doi: 10.1021/nl203920s. Epub 2012 Jan 12.
We present an electron tomography method that allows for the identification of hundreds of electrocatalyst nanoparticles with one-to-one correspondence before and after electrochemical aging. This method allows us to track, in three-dimensions, the trajectories and morphologies of each Pt-Co nanocatalyst on a fuel cell carbon support. In conjunction with the use of atomic-scale electron energy loss spectroscopic imaging, our experiment enables the correlation of performance degradation of the catalyst with changes in particle/interparticle morphologies, particle-support interactions, and the near-surface chemical composition. We found that aging of the catalysts under normal fuel cell operating conditions (potential scans from +0.6 to +1.0 V for 30,000 cycles) gives rise to coarsening of the nanoparticles, mainly through coalescence, which in turn leads to the loss of performance. The observed coalescence events were found to be the result of nanoparticle migration on the carbon support during potential cycling. This method provides detailed insights into how nanocatalyst degradation occurs in proton exchange membrane fuel cells (PEMFCs) and suggests that minimization of particle movement can potentially slow down the coarsening of the particles and the corresponding performance degradation.
我们提出了一种电子断层扫描方法,该方法可以在电化学老化前后识别出数百个具有一一对应关系的电催化剂纳米颗粒。这种方法使我们能够在三维空间中跟踪每个燃料电池碳载体上的 Pt-Co 纳米催化剂的轨迹和形态。结合原子尺度电子能量损失光谱成像的使用,我们的实验能够将催化剂的性能退化与颗粒/颗粒间形态、颗粒-载体相互作用以及近表面化学成分的变化相关联。我们发现,在燃料电池的正常工作条件下(在 30,000 个循环中从 +0.6 到 +1.0 V 进行电位扫描)对催化剂进行老化会导致纳米颗粒的粗化,主要是通过聚结,这反过来又导致性能下降。观察到的聚结事件是纳米颗粒在电位循环过程中在碳载体上迁移的结果。该方法深入了解了纳米催化剂在质子交换膜燃料电池(PEMFC)中是如何降解的,并表明最小化颗粒的运动可能会减缓颗粒的粗化和相应的性能下降。