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New Phosphorus‐Doped Perovskite Oxide as an Oxygen Reduction Reaction Electrocatalyst in an Alkaline Solution
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2018-03-26 , DOI: 10.1002/chem.201705675
Yujuan Shen 1, 2, 3 , Yinlong Zhu 1, 2, 3 , Jaka Sunarso 4 , Daqin Guan 1, 2, 3 , Bo Liu 1, 2, 3 , Hong Liu 1, 2, 3 , Wei Zhou 1, 2, 3 , Zongping Shao 1, 2, 3, 5
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Because of their structural and compositional flexibility, perovskite oxides represent an attractive alternative electrocatalyst class to precious metals for the oxygen reduction reaction (ORR); an important reaction in fuel cells and metal–air batteries. Partial replacement of the original metal cation with another cation, namely, doping, can be used to tailor the ORR activity of perovskite, for which a metal has been exclusively used as the dopant component in the past. Herein, phosphorus is proposed as a non‐metal dopant for the cation site to develop a new perovskite family with the formula of La0.8Sr0.2Mn1−xPxO3−δ (x=0, 0.02, 0.05, and 0.1; denoted as LSM, LSMP0.02, LSMP0.05, and LSMP0.1, respectively). Powder XRD patterns reveal that the solubility of phosphorus in the perovskite structure is around 0.05. Rotating ring‐disk electrode experiments in the form of linear‐sweep voltammetry scans demonstrated the best ORR performance for LSMP0.05, and also revealed close to a four‐electron ORR pathway for all four compositions. A chronoamperometric test (9000 s) and 500 cycle accelerated durability test demonstrated higher durability for LSMP0.05 relative to that of LSM and the commercial 20 wt % Pt/C catalyst. The higher ORR activity for LSMP0.05 is attributed to the optimised average valence of Mn, as evidenced by combined X‐ray photoelectron spectroscopy and soft X‐ray absorption spectroscopy data. Doping phosphorus into perovskites is an effective way to develop high‐performance electrocatalysts for ORR.

中文翻译:

新型磷掺杂钙钛矿氧化物在碱性溶液中作为氧还原反应电催化剂

由于其结构和组成的灵活性,钙钛矿氧化物代表了用于氧气还原反应(ORR)的,有吸引力的替代贵金属的电催化剂。在燃料电池和金属空气电池中的重要反应。可以用另一种阳离子(即掺杂​​)部分代替原始金属阳离子,以调整钙钛矿的ORR活性,过去,钙钛矿仅将金属用作掺杂剂。在此,磷被提出作为阳离子部位的非金属掺杂剂,以开发一种新的钙钛矿家庭用的La的式0.80.2的Mn 1- X P X ø 3- δX =0、0.02、0.05和0.1;分别表示为LSM,LSMP0.02,LSMP0.05和LSMP0.1)。粉末XRD图谱表明磷在钙钛矿结构中的溶解度约为0.05。以线性扫描伏安法扫描的形式进行的环形盘电极实验证明了LSMP0.05的最佳ORR性能,并且还揭示了所有四种成分的接近四电子ORR途径。计时电流测试(9000 s)和500周期加速耐久性测试表明,相对于LSM和市售20 wt%Pt / C催化剂,LSMP0.05具有更高的耐久性。LSMP0.05的较高ORR活性归因于Mn的优化平均价,这通过X射线光电子能谱和软X射线吸收光谱数据的组合得到证明。
更新日期:2018-03-26
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