Disentangling Electronic and Geometric Effects in Electrocatalysis through Substitution in Isostructural Intermetallic Compounds.
Disentangling Electronic and Geometric Effects in Electrocatalysis through Substitution in Isostructural Intermetallic Compounds.
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DOI：
10.1021/jacs.2c03348
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发表时间：
2022-04
影响因子：
15
通讯作者：
R. Zerdoumi;O. Matselko;L. Rößner;B. Sarkar;Y. Grin;M. Armbrüster
中科院分区：
文献类型：
--
作者：
R. Zerdoumi;O. Matselko;L. Rößner;B. Sarkar;Y. Grin;M. Armbrüster
催化材料的有效开发需要了解定义催化性能的决定性参数。在多组分金属催化剂中，这些效应被归类为电子效应和几何效应，但它们之间有很强的相关性。系统的解缠结可以通过固定一个参数同时改变另一个参数来实现，这通过在同构金属间化合物中的取代而成为可能。这种方法使电子或几何的贡献，单独和组合的评估。这里，这是通过在系列In 1-xSnxPd 2中用锡（四价电子）取代铟（三价电子）来实现的，这允许每个单元电池的电子总数的系统变化，而单元电池参数仅发生微小变化，从而允许电子效应的评估。几何效应进行了评估，通过取代铟与镓的Ga 1-xInxPd 2系列，这使得一个系统的原子间距离的变化，同时保持相同数量的价电子每单位电池和密切的原子坐标。通过在Ga 1-xSnxPd 2系列中用锡取代镓，这两种效应被结合并同时解决。甲醇氧化反应在Ga_（1-x）Sn_xPd_（2-x）系列催化剂上的催化活性增强是由于上述综合效应的协同作用。
Efficient development of catalytic materials requires knowledge of the decisive parameters defining the catalytic properties. In multicomponent metallic catalysts, these are categorized as electronic and geometric effects, yet they are strongly interrelated. A systematic disentanglement can be achieved by fixing one parameter while altering the other, which becomes possible through the substitution in isostructural intermetallic compounds. This approach enables the evaluation of electronic or geometric contributions both individually and combined. Herein, this is achieved by substitution of indium (three valence electrons) with tin (four valence electrons) in the series In1-xSnxPd2, which allows for a systematic variation of the total number of electrons per unit cell with only a minor variation of the unit cell parameters and thus the evaluation of the electronic effect. Geometric effects were evaluated by substitution of indium with gallium in the Ga1-xInxPd2 series, which allows for a systematic variation of the interatomic distances while maintaining the same number of valence electrons per unit cell and close atomic coordinates. By substituting gallium with tin in the Ga1-xSnxPd2 series, both effects are combined and addressed simultaneously. The activity enhancement of the methanol oxidation reaction on the Ga1-xSnxPd2 series is attributed to the synergy of the combined effects.