Coordination variation of hydrated Cu2+/Br1- ions traversing the interfacial water in mesopores
Coordination variation of hydrated Cu2+/Br1- ions traversing the interfacial water in mesopores
复制标题
水合Cu2/Br1-离子穿过介孔界面水的配位变化
DOI：
10.1063/1.4704545
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发表时间：
2012-04
期刊：
影响因子：
1.6
通讯作者：
Cao, Z. X.
中科院分区：
文献类型：
--
作者：
Wang, Q.;Sun, G.;Lu, K. Q.;Huang, X. F.;Li, C. X.;Pan, L. Q.;Wu, Z. H.;Hu, T. D.;Jiang, Z.;Huang, Y. Y.;Cao, Z. X.
Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (phi = 7.6 nm) by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of similar to 35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110 degrees C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4704545]
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通过介电测量观察多孔 Vycor 上水吸附和解吸的分层
影响因子：
3.7
作者：
Wang, Q;Li, CX;Sun, G;Wang, LW;Lu, KQ;Niu, XJ
通讯作者：
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DOI：
10.1021/j100026a028
发表时间：
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期刊：
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影响因子：
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