Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.
Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.
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溶剂对己硫醇单层保护的金纳米团簇氧化还原性能的影响。
DOI：
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发表时间：
2006
影响因子：
3.3
通讯作者：
H. Girault
中科院分区：
文献类型：
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作者：
B. Su;Meiqi Zhang;Y. Shao;H. Girault
从静电学的角度重新考虑了单层保护的金纳米团簇（MPC）在溶液中的电容C（MPC），其中MPC被认为是两个电介质层（本征涂层单层和本体溶剂）内的孤立带电球体。该模型预测，本体溶剂提供了一个重要的贡献C（MPC）和影响MPC的氧化还原性能。然后通过比较MPC在四种有机溶剂中的氧化还原性质来实验研究这一理论预测：1，2-二氯乙烷（DCE），二氯甲烷（DCM），氯苯（CB）和甲苯（TOL），在所有这些MPC都具有良好的溶解性。此外，这组有机溶剂的特征在于介电常数在10.37（DCE）至2.38（TOL）的范围内，这足够宽以探测溶剂效应。在这些有机溶剂中，使用四己基铵双（三氟甲基磺酰基）酰亚胺（THATf 2N）作为支持电解质。循环和差分脉冲伏安法的结果提供了具体的证据，尽管单层保护，溶剂发挥了显着的影响，在溶液中的MPC的性能。
The capacitance of monolayer-protected gold nanoclusters (MPCs), C(MPC), in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to C(MPC) and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparing the redox properties of MPCs in four organic solvents: 1,2-dichloroethane (DCE), dichloromethane (DCM), chlorobenzene (CB), and toluene (TOL), in all of which MPCs have excellent solubility. Furthermore, this set of organic solvents features a dielectric constant in a range from 10.37 (DCE) to 2.38 (TOL), which is wide enough to probe the solvent effect. In these organic solvents, tetrahexylammonium bis(trifluoromethylsulfonyl)imide (THATf2N) is used as the supporting electrolyte. Cyclic and differential pulse voltammetric results provide concrete evidence that, despite the monolayer protection, the solvent plays a significant effect on the properties of MPCs in solution.