催化作用
离子
价(化学)
电子转移
金属
电子组态
密度泛函理论
水溶液中的金属离子
氧化态
过渡金属
材料科学
价电子
无机化学
化学物理
物理化学
物理
化学
电子
计算化学
冶金
量子力学
生物化学
有机化学
作者
Chanseok Kim,Dasom Jeon,Nayeong Kim,Jungki Ryu,JunHee Lee
出处
期刊:Small
[Wiley]
日期:2024-03-28
标识
DOI:10.1002/smll.202400114
摘要
Electrocatalytic activity of multi-valence metal oxides for oxygen evolution reaction (OER) arises from various interactions among the constituent metal elements. Although the high-valence metal ions attract recent attentions due to the interactions with their neighboring 3d transition metal catalytic center, atomic-scale explanations for the catalytic efficiencies are still lacking. Here, by employing density functional theory predictions and experimental verifications, unprecedented electronic isolation of the catalytic 3d center (M2+) induced by the surrounding high-valence ions such as W6+ is discovered in multivalent oxides MWO4 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn). Due to W6+'s extremely high oxidation state with the minimum electron occupations (d0), the surrounding W6+ blocks electron transfer toward the catalytic M2+ ions and completely isolates the ions electronically. Now, the isolated M2+ ions solely perform OER without any assistant electron flow from the adjacent metal ions, and thus the original strong binding energies of Cr with OER intermediates are effectively moderated. Through exploiting "electron isolators" such as W6+ surrounding the catalytic ion, exploring can be done beyond the conventional materials such as Ni- or Co-oxides into new candidate groups such as Cr and Mn on the left side of the periodic table for ideal OER.
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