Dimensionality Dependent Water Splitting Mechanisms on Free Manganese Oxide Clusters
Dimensionality Dependent Water Splitting Mechanisms on Free Manganese Oxide Clusters
复制标题
DOI：
10.1021/nl4031456
复制
发表时间：
2013-11-01
期刊：
影响因子：
10.8
通讯作者：
Landman, Uzi
中科院分区：
文献类型：
--
作者：
Lang, Sandra M.;Fleischer, Irene;Landman, Uzi
研究了无配体的氧化锰纳米团簇与水的相互作用，旨在揭示一些现象，为设计人工水裂解分子催化剂提供帮助。在离子阱中的气相测量结合第一性原理计算提供了新的机理洞察介导的水裂解过程由双和四nudear单电荷锰氧化物簇，Mn2O2+和Mn4O4+。特别是，水引起的维数变化的Mn4O4+的预测，需要从一个二维的环状基态结构的裸簇的立方体的八羟基复合物的水合一个变换。进一步预测，簇维数交叉促进了水裂解过程。振动光谱计算的物种发生沿着预测的途径Mn4O4+与水的反应提供了动力，为未来的探索，包括振动光谱实验。
The interaction of ligand-free manganese oxide nanoclusters with water is investigated, aiming at uncovering phenomena which could aid the design of artificial water-splitting molecular catalysts. Gas phase measurements in an ion trap in conjunction with first-principles calculations provide new mechanistic insight into the water splitting process mediated by bi- and tetra-nudear singly charged manganese oxide clusters, Mn2O2+ and Mn4O4+. In particular, a water-induced dimensionality change of Mn4O4+ is predicted, entailing transformation from a two-dimensional ring-like ground state structure of the bare cluster to a cuboidal octa-hydroxy-complex for the hydrated one. It is further predicted that the water splitting process is facilitated by the cluster dimensionality crossover. The vibrational spectra calculated for species occurring along the predicted pathways of the reaction of Mn4O4+ with water provide the impetus for future explorations, including vibrational spectroscopic experiments.