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In-situ Raman spectroscopic insight into charge delocalization-improved electrical conductivity in metal-cyanide
Zhixuan Lu1,2, Yajun Huang1, Liting Shao1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (i-ChEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. bren@xmu.edu.cn.
Alkali metal ions enhance electrical conductivity in porous crystalline materials like Prussian Blue by delocalizing charge. This guest-promoted through-bond mechanism offers a new route for developing conductive porous materials.
Area of Science:
- Materials Science
- Electrochemistry
- Nanotechnology
Background:
- Porous crystalline materials (PCMs) offer high porosity and tunable properties.
- Traditional PCMs suffer from low electrical conductivity, limiting their applications.
- A guest-promoted approach can enhance conductivity, but the microscopic mechanism is unclear.
Purpose of the Study:
- To investigate the microscopic mechanism of enhanced electrical conductivity in Prussian Blue (PB) induced by alkali metal ions.
- To understand how guest ions influence charge delocalization in PCMs.
Main Methods:
- In-situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) was employed.
- Density functional theory (DFT) calculations were used for verification.
Main Results:
- EC-SERS revealed charge localization around iron atoms in pristine PB.
- Alkali metal ion insertion led to charge delocalization onto the CN bond.
- A through-bond charge transfer mechanism was identified, contrasting with the through-space hopping in pristine PB.
Conclusions:
- Alkali metal ions promote electrical conductivity in PCMs through a through-bond mechanism.
- This study provides a microscopic understanding of guest-promoted conductivity in PCMs.
- The findings offer a novel strategy for designing conductive porous crystalline materials.
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