In-situ Raman spectroscopic insight into charge delocalization-improved electrical conductivity in metal–cyanide frameworks,Nanoscale

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In-situ Raman spectroscopic insight into charge delocalization-improved electrical conductivity in metal–cyanide frameworks
Nanoscale ( IF 5.8 ) Pub Date : 2022-11-28 , DOI: 10.1039/d2nr05285g
Zhixuan Lu _{1,

2} , Yajun Huang ₁ , Liting Shao ₁ , Maofeng Cao ₁ , Shu Hu ₁ , Chuan Liu ₁ , Xiang Wang ₁ , Bin Ren _{1,

3}

Affiliation

Porous crystalline materials (PCMs) have attracted widespread attention due to their high porosity and chemical tunability. To solve the problem of the low electrical conductivity of traditional PCMs, a guest-promoted approach has been developed to impart electrical conductivity, whereas microscopic understanding of this process from experiments is largely lacking. Here we use in-situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) to investigate the microscopic mechanism of the enhanced electrical conductivity in metal–cyanide frameworks, in Prussian Blue (PB), induced by alkali metal ions. The EC-SERS result demonstrates that the charge is localized around the iron atom in PB and becomes delocalized on the CN bond after insertion of the alkali metal ions, verified by density functional theory (DFT) calculations. The enhanced electrical conductivity of PCMs promoted by the guest via the through-bond mechanism instead of the through-space hopping mechanism in pristine PB, offers a new approach to develop conductive PCMs.

中文翻译：

原位拉曼光谱洞察金属氰化物骨架中电荷离域改善的导电性

多孔晶体材料（PCM）由于其高孔隙率和化学可调性而受到广泛关注。为了解决传统 PCM 的低电导率问题，已经开发了一种客体促进方法来赋予电导率，而从实验中对该过程的微观理解在很大程度上是缺乏的。这里我们使用原位电化学表面增强拉曼光谱 (EC-SERS) 研究碱金属离子诱导的普鲁士蓝 (PB) 中金属氰化物骨架导电性增强的微观机制。EC-SERS 结果表明，电荷位于 PB 中的铁原子周围，并在插入碱金属离子后在 CN 键上离域，这已通过密度泛函理论 (DFT) 计算得到验证。客体通过键合机制而不是原始 PB 中的空间跳跃机制促进了 PCM 的导电性增强，为开发导电 PCM 提供了一种新方法。

更新日期：2022-12-01

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