Riedl Christoph, Siebenhofer Matthäus, Nenning Andreas, Schmid Alexander, Weiss Maximilian, Rameshan Christoph, Limbeck Andreas, Kubicek Markus, Opitz Alexander Karl, Fleig Juergen
Institute of Chemical Technologies and Analytics, TU Wien Getreidemarkt 9-E164 1060 Vienna Austria
CEST Kompetenzzentrum für Elektrochemische Oberflächentechnologie GmbH, TFZ - Wiener Neustadt Viktor-Kaplan-Strasse 2 2700 Wiener Neustadt Austria.
J Mater Chem A Mater. 2022 Jun 23;10(28):14838-14848. doi: 10.1039/d2ta03335f. eCollection 2022 Jul 19.
In this study, five different mixed conducting cathode materials were grown as dense thin films by pulsed laser deposition (PLD) and characterized impedance spectroscopy directly after growth inside the PLD chamber (i-PLD). This technique enables quantification of the oxygen reduction kinetics on pristine and contaminant-free mixed conducting surfaces. The measurements reveal excellent catalytic performance of all pristine materials with polarization resistances being up to two orders of magnitude lower than those previously reported in the literature. For instance, on dense LaSrCoO thin films, an area specific surface resistance of ∼0.2 Ω cm at 600 °C in synthetic air was found, while values usually >1 Ω cm are measured in conventional measurement setups. While surfaces after i-PLD measurements were very clean, ambient pressure X-ray photoelectron spectroscopy (AP-XPS) measurements found that all samples measured in other setups were contaminated with sulfate adsorbates. impedance spectroscopy during AP-XPS revealed that already trace amounts of sulfur present in high purity gases accumulate quickly on pristine surfaces and lead to strongly increased surface polarization resistances, even before the formation of a SrSO secondary phase. Accordingly, the inherent excellent catalytic properties of this important class of materials were often inaccessible so far. As a proof of concept, the fast kinetics observed on sulfate-free surfaces were also realized in measurements with a gas purification setup and further reduces the sulfur concentration in the high purity gas.
在本研究中,通过脉冲激光沉积(PLD)制备了五种不同的混合导电阴极材料致密薄膜,并在PLD腔室内生长后直接采用阻抗谱进行表征(i-PLD)。该技术能够对原始且无污染物的混合导电表面上的氧还原动力学进行量化。测量结果表明,所有原始材料均具有出色的催化性能,其极化电阻比文献中先前报道的低两个数量级。例如,在致密的LaSrCoO薄膜上,在合成空气中600°C时的面积比表面电阻约为0.2Ω·cm,而在传统测量装置中通常测量的值>1Ω·cm。虽然i-PLD测量后的表面非常干净,但常压X射线光电子能谱(AP-XPS)测量发现,在其他装置中测量的所有样品都被硫酸盐吸附物污染。AP-XPS期间的阻抗谱表明,即使在形成SrSO次生相之前,高纯度气体中存在的痕量硫也会迅速在原始表面上积累,并导致表面极化电阻大幅增加。因此,到目前为止,这类重要材料固有的优异催化性能往往难以实现。作为概念验证,在使用气体净化装置的测量中也实现了在无硫酸盐表面上观察到的快速动力学,并进一步降低了高纯度气体中的硫浓度。