金属原子团簇作为多功能质子传导材料的构建基块：理论和实验表征,Inorganic Chemistry

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金属原子团簇作为多功能质子传导材料的构建基块：理论和实验表征
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-07-30 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00340
Gilles Daigre ₁ , Jérôme Cuny ₂ , Pierric Lemoine ₁ , Maria Amela-Cortes ₁ , Serge Paofai ₁ , Nathalie Audebrand ₁ , Annie Le Gal La Salle ₃ , Eric Quarez ₃ , Olivier Joubert ₃ , Nikolay G. Naumov _{4,

5} , Stéphane Cordier ₁

Affiliation

寻找新的显示质子传导特性的多功能材料对于开发电致变色器件和超级电容器以及能量转换和存储至关重要。在本研究中，首次报道了三种基于钼团簇的材料的质子传导性：（H）₄ [Mo ₆ Br ₆ S ₂（OH）₆ ] -12H ₂ O和（H）₂ [Mo ₆ X ₈（OH）₆ ] -12H ₂ O（X ＝ Cl，Br）。我们证明了发光[Mo ₆ L ₈ⁱ（OH）₆的自组装^a ]^{2– / 4–4}簇单元同时导致发光和质子传导性（σ= 1.4×10^–4 S·cm^–1 in（H）₂ [Mo₆ Cl₈（OH）₆ ] -12H₂O在潮湿条件下）中的三种材料。后者的性质是由在簇和水分子之间形成的强氢键网络产生的，并且由于质子的存在而被放大，质子在统计上被相邻簇之间的顶端羟基共享。从头开始的分子动力学模拟在分子尺度上凸显了它们在质子传导中的作用，证明了通过氢键网络进行协调的质子转移是可能的。此外，热重分析还显示了化合物容纳或多或少的水分子的能力，这突出表明在材料内可能发生了车辆（或扩散）运输。最后，基于理论和实验证据，提出了移动质子的红外指纹图谱。本研究依赖于可扩展到其他质子传导材料的协同计算/实验方法。因此，它为设计和理解新型的质子传导材料（展现原始和令人兴奋的特性）铺平了道路。

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Metal Atom Clusters as Building Blocks for Multifunctional Proton-Conducting Materials: Theoretical and Experimental Characterization

The search for new multifunctional materials displaying proton-conducting properties is of paramount necessity for the development of electrochromic devices and supercapacitors as well as for energy conversion and storage. In the present study, proton conductivity is reported for the first time in three molybdenum cluster-based materials: (H)₄[Mo₆Br₆S₂(OH)₆]-12H₂O and (H)₂[Mo₆X₈(OH)₆]-12H₂O (X = Cl, Br). We show that the self-assembling of the luminescent [Mo₆L₈ⁱ(OH)₆^a]^2–/4– cluster units leads to both luminescence and proton conductivity (σ = 1.4 × 10^–4 S·cm^–1 in (H)₂[Mo₆Cl₈(OH)₆]-12H₂O under wet conditions) in the three materials. The latter property results from the strong hydrogen-bond network that develops between the clusters and the water molecules and is magnified by the presence of protons that are statistically shared by apical hydroxyl groups between adjacent clusters. Their role in the proton conduction is highlighted at the molecular scale by ab initio molecular dynamics simulations that demonstrate that concerted proton transfers through the hydrogen-bond network are possible. Furthermore, thermogravimetric analysis also shows the ability of the compounds to accommodate more or less water molecules, which highlights that vehicular (or diffusion) transport probably occurs within the materials. An infrared fingerprint of the mobile protons is finally proposed based on both theoretical and experimental proofs. The present study relies on a synergic computational/experimental approach that can be extended to other proton-conducting materials. It thus paves the way to the design and understanding of new multifunctional proton-conducting materials displaying original and exciting properties.

更新日期：2018-07-30

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