Ultrastable Anti‐Acid “Shield” in Layered Silver Coordination Polymers

Surface passivation technology provides noble‐metal materials with limited chemical stability, especially under highly acidic condition. To design effective strategy to enhance stability of noble‐metal particles, an understanding of their surface anticorrosion mechanism at the atomic level is desira...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-11, Vol.61 (44), p.e202209971-n/a
Main Authors: Sun, Peipei, Xie, Mo, Zhang, Lin‐Mei, Liu, Jia‐Xing, Wu, Jin, Li, Dong‐Sheng, Yuan, Shang‐Fu, Wu, Tao, Li, Dan
Format: Article
Language:English
Subjects:
2D Coordination Polymers
Anti-Acid
Boiling
Buffer layers
Chemical compounds
Coordination polymers
Corrosion prevention
Corrosion resistance
Ethanol
Hydrogen peroxide
Hydrophobicity
Interfacial Structures
Metal Nanomaterials
Metal particles
Polymers
Silver
Sodium hydroxide
Stability analysis
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Summary:Surface passivation technology provides noble‐metal materials with limited chemical stability, especially under highly acidic condition. To design effective strategy to enhance stability of noble‐metal particles, an understanding of their surface anticorrosion mechanism at the atomic level is desirable by using two‐dimensional (2D) noble‐metal coordination polymer (CP) as an ideal model for their interfacial region. With the protection of 2‐thiobenzimidazole (TBI), we isolated two Ag‐based 2D CPs, {Ag14(TBI)12X2}n (S−X, where S denotes sheet and X=Cl or Br). These compounds exhibited excellent chemical stability upon immersion in various common solvents, boiling water, boiling ethanol, 10 % hydrogen peroxide, concentrated acid (12 M HCl), and concentrated alkali (19 M NaOH). Systematic characterization and DFT analyses demonstrate that the superior stability of S−X was attributed to the hydrophobic organic shell and dynamic proton buffer layer acting as a double protective “shield”. Acid resistance (12 M HCl) was made possible for two isomorphic two‐dimensional silver‐based coordination polymers. Protection is provided by a hydrophobic organic shell and a dynamic proton buffer layer via a thiolate‐thione tautomerism of 2‐thiobenzimidazole ligands. Thus, these ligands are promising surface inhibitors, acting as a dual protective shield against metal corrosion.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202209971