金属取代对氧化钌结构和析氧活性及稳定性的影响

Luis A Albiter, Kathleen O. Bailey, Jose Fernando Godinez Salomon, Christopher P. Rhodes
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摘要

质子交换膜水电解槽(PEMWEs)的开发和利用受到析氧反应(OER)电催化剂的成本、活性和稳定性等因素的制约。氧化铱(IrO x)是目前首选的OER电催化剂,因为与其他OER活性催化剂相比,它已被证明具有相对较高的活性和稳定性。然而,铱是地壳中最稀有的元素之一,因此成本是基于铱的电催化剂的主要限制。氧化钌(ruo2)比氧化铱成本低,活性高;然而,若o2在酸性介质中是不稳定的,并且会随着时间的推移而降解。我们研究了将OER稳定金属铌、钽和锆取代到若o2中以提高OER稳定性。我们的研究探讨了不同金属和不同浓度的ruo2 (Ru 1-x M x o2, M = Nb, Ta和Zr)对结构,形态,OER活性和稳定性的影响。采用x射线衍射(XRD)、x射线光电子能谱和扫描电镜对其结构和形貌进行了表征。XRD初步结果表明,在Nb、Ta和Zr浓度较高时可观察到相分离,而在Nb和Ta浓度较低时相分离较少。Zr在较低浓度下无相分离现象。XRD峰移表明金属离子进入了金红石ruo2的晶体结构。采用旋转圆盘电极结构测量了Ru 1-x M x o2的OER活性和稳定性,并与合成的ruo2进行了比较。我们的初步结果表明,OER活性和稳定性受到不同金属的加入的强烈影响,这可能归因于形貌和结构的变化。我们的发现有助于进一步开发成本更低、活性更高、稳定性更高的OER电催化剂,这对大规模采用PEMWE至关重要。
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Effect of Metal-Substitution within Ruthenium Oxide on Structure and Oxygen Evolution Activity and Stability
The development and utilization of proton exchange membrane water electrolyzers (PEMWEs) is hindered by the cost, activity, and stability of the oxygen evolution reaction (OER) electrocatalyst. Iridium oxide (IrO x ) is currently the go-to OER electrocatalyst, as it has been shown to have relative high activity and stability when compared to other OER active catalysts. However, iridium is one of the rarest elements in the Earth’s crust, and therefore cost is a major limitation of iridium-based electrocatalysts. Ruthenium oxide (RuO 2 ) is much lower cost and more active than iridium oxide; however, RuO 2 it is unstable in acidic media and undergoes degradation over time. We investigated substituting niobium, tantalum, and zirconium, which are OER-stable metals, into RuO 2 to improve the OER stability. Our study explored the effects of different metals and varied concentrations within RuO 2 (Ru 1-x M x O 2 , M = Nb, Ta, and Zr) on the structure, morphology, OER activity, and stability. The structure and morphology were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy, and scanning electron microscopy. Preliminary results from XRD showed observable phase separation at higher concentrations of Nb, Ta, and Zr and less phase separation at lower concentrations for Nb and Ta. There was no observable phase separation for Zr at lower concentrations. XRD peak shifts were observed and indicate the incorporation of the metal ions into the crystal structure of rutile RuO 2 . The OER activities and stabilities of Ru 1-x M x O 2 were measured using a rotating disk electrode configuration and compared with synthesized RuO 2 . Our preliminary results show that the OER activity and stability are strongly affected by the addition of the different metals and could be attributed to morphology and structural changes. Our findings help to further the development of lower cost, high activity, and increased stability OER electrocatalysts, which are crucial to the large-scale adoption of PEMWE’s.
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