Sun Peipei, Xie Mo, Zhang Lin-Mei, Liu Jia-Xing, Wu Jin, Li Dong-Sheng, Yuan Shang-Fu, Wu Tao, Li Dan
College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou, 510632, China.
School of Energy Materials and Chemical Engineering, Hefei University, Hefei, 230601, China.
Angew Chem Int Ed Engl. 2022 Nov 2;61(44):e202209971. doi: 10.1002/anie.202209971. Epub 2022 Sep 29.
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, {Ag (TBI) X } (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".
表面钝化技术为贵金属材料提供了有限的化学稳定性,尤其是在高酸性条件下。为了设计有效的策略来提高贵金属颗粒的稳定性,通过使用二维(2D)贵金属配位聚合物(CP)作为其界面区域的理想模型,在原子水平上理解其表面防腐机制是很有必要的。在2-硫代苯并咪唑(TBI)的保护下,我们分离出了两种基于银的二维CP,{Ag (TBI) X } (S-X,其中S表示片层,X = Cl或Br)。这些化合物在浸入各种常见溶剂、沸水、沸腾乙醇、10%过氧化氢、浓酸(12 M HCl)和浓碱(19 M NaOH)中时表现出优异的化学稳定性。系统表征和DFT分析表明,S-X的卓越稳定性归因于疏水有机壳层和动态质子缓冲层作为双重保护“盾牌”。