振动和频率产生光谱揭示了氧化铬(001)表面的惰性。

IF 9.7 1区 化学 Q1 CHEMISTRY, PHYSICAL
Journal of Colloid and Interface Science Pub Date : 2026-01-01 Epub Date: 2025-08-06 DOI:10.1016/j.jcis.2025.138631
Mavis D Boamah, Tiffany Kaspar, Yatong Zhao, Tim Droubay, Mark Bowden, Zheming Wang, Kevin M Rosso
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引用次数: 0

摘要

纳米工程金属氧化物如Cr(III)-氧化物(chromia)薄膜在缓蚀、修复、能源生成、催化、数据存储以及生物和环境系统中具有多种潜在的应用。考虑到材料降解或氧化成有毒的铬酸盐,必须了解铬/水界面,从它们的羟基化和水化行为开始。振动和频率产生光谱(vSFG)提供了特定的分子水平的信息,水在氧化物/水结具有高的表面选择性。为了克服非线性光学研究中某些金属氧化物在紫外可见范围内典型的强吸收问题,我们采用分子束外延技术在蓝宝石(Al2O3(001))衬底上沉积具有(001)晶体取向的Cr2O3透明外延纳米膜,原子力显微镜和x射线衍射证实了这一点。Cr2O3(001)膜的空气和水界面的vSFG光谱显示了表面上与解离水和分子水相对应的羟基特征。与裸露的Al2O3(001)衬底上的悬空羟基相反,沉积的Cr2O3(001)纳米膜上的羟基在暴露于环境条件下不同形式的D2O时不易发生同位素H/D交换。当考虑水溶液中相应的三价阳离子的化学性质时,这一发现与它们相似的酸度和质子交换动力学不同,但与六水Cr3+的球内水配体交换明显较慢一致。这一发现挑战了水/Cr₂O₃(001)界面上的质子和水的交换是完全相关的,由金属桥接氧键的强度和表面羟基分布驱动,没有直接的因果关系。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Vibrational sum frequency generation spectroscopy reveals the inertness of chromium oxide (001) surfaces.

Nanoengineered metal oxides such as Cr(III)-oxide (chromia) films have diverse potential applications in corrosion inhibition, remediation, energy generation, catalysis, data storage, and biological and environmental systems. Concerns about material degradation or oxidation to toxic chromate necessitate an understanding of chromia/aqueous interfaces, beginning with their hydroxylation and hydration behavior. Vibrational sum-frequency generation spectroscopy (vSFG) provides specific molecular-level information about water at the oxide/aqueous junction with high surface selectivity. To overcome the strong absorber problem typical of certain metal oxides in the UV-visible range during nonlinear optical studies, we employed molecular beam epitaxy to deposit transparent, epitaxial nanofilms of Cr2O3 with (001) crystalline orientation on sapphire (Al2O3 (001)) substrates, as confirmed by atomic force microscopy and X-ray diffraction. vSFG spectra of the air and water interfaces of the Cr2O3 (001) films reveal hydroxyl features corresponding to both dissociated and molecular water on the surface. In contrast to the dangling hydroxyls found on the bare Al2O3 (001) substrate, the hydroxyl groups on the deposited Cr2O3 (001) nanofilm do not readily undergo isotopic H/D exchange when exposed to varying forms of D2O under ambient conditions. When considering the chemistries of the corresponding trivalent cations in aqueous solution, the finding is at variance with their similar acidities and proton exchange dynamics but consistent with markedly slower inner-sphere water ligand exchange of hexaquo Cr3+. This finding challenges the idea that proton and water exchange at the water/Cr₂O₃(001) interface are solely correlated, driven by the strength of metal-bridging oxygen bonds and surface hydroxyl distribution, without direct causation.

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来源期刊
CiteScore
16.10
自引率
7.10%
发文量
2568
审稿时长
2 months
期刊介绍: The Journal of Colloid and Interface Science publishes original research findings on the fundamental principles of colloid and interface science, as well as innovative applications in various fields. The criteria for publication include impact, quality, novelty, and originality. Emphasis: The journal emphasizes fundamental scientific innovation within the following categories: A.Colloidal Materials and Nanomaterials B.Soft Colloidal and Self-Assembly Systems C.Adsorption, Catalysis, and Electrochemistry D.Interfacial Processes, Capillarity, and Wetting E.Biomaterials and Nanomedicine F.Energy Conversion and Storage, and Environmental Technologies
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