高等学校化学学报 ›› 2023, Vol. 44 ›› Issue (1): 20220656.doi: 10.7503/cjcu20220656
收稿日期:
2022-10-06
出版日期:
2023-01-10
发布日期:
2022-11-27
基金资助:
Received:
2022-10-06
Online:
2023-01-10
Published:
2022-11-27
Contact:
YIN Yadong
E-mail:yadong.yin@ucr.edu
Supported by:
摘要:
中空纳米材料的可控合成使其在催化、 能量转换与储存、 生物医药等领域具有广阔的应用前景. 本专论旨在揭示刻蚀反应对纳米结构空心过程的关键影响. 讨论了通过增强纳米粒子表面在刻蚀液中的相对稳定性来精确操纵中空化过程的策略, 主要关注3种刻蚀策略, 包括硬模板法、 氧化还原辅助中空法和表面钝化自模板法. 最后, 对基于刻蚀反应的纳米结构空心化可控合成未来的发展方向进行了展望.
中图分类号:
TrendMD:
叶祖洋, 殷亚东. 基于刻蚀反应的纳米结构空心化. 高等学校化学学报, 2023, 44(1): 20220656.
YE Zuyang, YIN Yadong. Etching-based Hollowing of Nanostructures. Chem. J. Chinese Universities, 2023, 44(1): 20220656.
Method | Formation of protective shell | Requirement for dedicated coating steps | Shell resistance to etching | Shell composition | Control over shell thickness |
---|---|---|---|---|---|
Hard templating | Precoating | Yes | High | Same as the coating | By coating |
Redox⁃assisted etching | During etching | No | High | Reaction dependent | By etchant amount |
Surface⁃passivated etching | Precoating | No | Medium | Original composition | By etching time |
Table 1 Summary of etching-based hollowing methods
Method | Formation of protective shell | Requirement for dedicated coating steps | Shell resistance to etching | Shell composition | Control over shell thickness |
---|---|---|---|---|---|
Hard templating | Precoating | Yes | High | Same as the coating | By coating |
Redox⁃assisted etching | During etching | No | High | Reaction dependent | By etchant amount |
Surface⁃passivated etching | Precoating | No | Medium | Original composition | By etching time |
Fig.1 Schematic illustration showing the typical synthesis procedure of the hard templating method(A) and TEM images of the samples at each preparation step(B—D)[19](B) SiO2@TiO2 core⁃shell structures prepared by sol⁃gel coating; (C) SiO2@TiO2 core⁃shell structures after water⁃assisted crystallization; (D) mesoporous TiO2 hollow nanostructures after removing SiO2 cores.(B)—(D) Copyright 2013, the Royal Society of Chemistry.
Fig.2 TEM images of anisotropic hollow nanostructures prepared using the hard templating method[31](A) FeOOH nanorods; (B) FeOOH/Au@RF hybrid rods; (C) Au nanoparticle-decorated RF nanocapsules.
Fig.5 Synthesis of hollow Pd nanocrystals with thin walls by repeating the cavitation process three times[45](A) Schematic illustration showing the evolution of the molar ratio of P to Pd during repeated cavitation cycles; (B—G) high-angle annular dark-field scanning TEM(HAADF-STEM) images(B—D) and high-resolution HAADF-STEM images(E—G) of the obtained hollow nanocrystals after repeated cavitation cycles: H-Pd-1 obtained by one cavitation cycle(B, E), H-Pd-2 achieved by two cavitation cycles(C, F), and H-Pd-3 produced by three cavitation cycles(D, G). Scale bars in (B)—(D) are 50 nm. Scale bars in (E)—(G) are 5 nm.
Fig.6 Hollow SiO2 nanostructures prepared based on the surface⁃protected etching method[53](A)—(D) TEM images of silica nanospheres after being etched in 0.33 mol/L NaOH for 5 h. Before etching, the silica nanospheres were heated at 100 ℃ for 3 h in a PVP solution with different molar ratios of PVP repeating unit to Si: 0(A), 1(B), 5(C), and 10(D). The scale bars are 100 nm. (E) Change of dissolved SiO2 concentration as a function of etching time. The error of each value was calculated by taking the standard deviation of three measurements.
Fig.8 Pd octahedral nanoframes prepared by maneuvering the rates of oxidative etching and regrowth[62](A) Representative TEM image; (B) HAADF⁃STEM images; (C) HRTEM images of Pd octahedral nanoframe projected along (110), (100), and (111) zone axes and the corresponding Fourier transform(FT) patterns, respectively; (D) 3D model of a Pd octahedral nanoframe and its projections along (110), (100), and (111) zone axes.
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