化学
多金属氧酸盐
水溶液
氧化还原
星团(航天器)
质子化
电子
电子顺磁共振
溶剂化电子
化学物理
过渡金属
无机化学
结晶学
物理化学
离子
核磁共振
放射分析
有机化学
催化作用
计算机科学
物理
程序设计语言
量子力学
作者
Jiajia Chen,Laia Vilà‐Nadal,Albert Solé‐Daura,Greig Chisholm,Takuo Minato,Christoph Busche,Tingting Zhao,Balamurugan Kandasamy,Alexey Y. Ganin,Rachelle M. Smith,Ian Colliard,Jorge J. Carbó,Josep M. Poblet,May Nyman,Leroy Cronin
摘要
Aqueous solutions of polyoxometalates (POMs) have been shown to have potential as high-capacity energy storage materials due to their potential for multi-electron redox processes, yet the mechanism of reduction and practical limits are currently unknown. Herein, we explore the mechanism of multi-electron redox processes that allow the highly reduced POM clusters of the form {MO3}y to absorb y electrons in aqueous solution, focusing mechanistically on the Wells-Dawson structure X6[P2W18O62], which comprises 18 metal centers and can uptake up to 18 electrons reversibly (y = 18) per cluster in aqueous solution when the countercations are lithium. This unconventional redox activity is rationalized by density functional theory, molecular dynamics simulations, UV-vis, electron paramagnetic resonance spectroscopy, and small-angle X-ray scattering spectra. These data point to a new phenomenon showing that cluster protonation and aggregation allow the formation of highly electron-rich meta-stable systems in aqueous solution, which produce H2 when the solution is diluted. Finally, we show that this understanding is transferrable to other salts of [P5W30O110]15- and [P8W48O184]40- anions, which can be charged to 23 and 27 electrons per cluster, respectively.
科研通智能强力驱动
Strongly Powered by AbleSci AI