Ionic-Liquid-Modified Hybrid Materials Prepared by Physical Vapor Codeposition: Cobalt and Cobalt Oxide Nanoparticles in [C1C2Im][OTf] Monitored by In Situ IR Spectroscopy

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• 作者：Sascha Mehl ; Tanja Bauer ; Olaf Brummel ; Kaija Pohako-Esko ; Peter Schulz ; Peter Wasserscheid ; Jörg Libuda
• 刊名：Langmuir
• 出版年：2016
• 出版时间：August 30, 2016
• 年：2016
• 卷：32
• 期：34
• 页码：8613-8622
• 全文大小：659K
• 年卷期：0
• ISSN：1520-5827

文摘

The synthesis of ionic-liquid-modified nanomaterials has attracted much attention recently. In this study we explore the potential to prepare such systems in an ultraclean fashion by physical vapor codeposition (PVCD). We codeposit metallic cobalt and the room-temperature ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [C₁C₂Im][OTf] simultaneously onto a Pd(111) surface at 100 K. This process is performed under ultrahigh-vacuum (UHV) conditions in the presence of CO, or in the presence of O₂ and CO. We use time-resolved (TR) and temperature-programmed (TP) infrared reflection absorption spectroscopy (IRAS) to investigate the formation and stability of the IL-modified Co deposits in situ during the PVD-based synthesis. CO is used as a probe molecule to monitor the growth. After initial growth of flat Co films on Pd(111), multilayers of Co nanoparticles (NPs) are formed. Characteristic shifts and intensity changes are observed in the vibrational bands of both CO and the IL, which originate from the electric field at the IL/Co interface (Stark effect) and from specific adsorption of the [OTf]⁻ anion. These observations indicate that the Co aggregates are stabilized by mixed adsorbate shells consisting of CO and [OTf]⁻. The CO coverage on the Co particle decreases with increasing temperature, but some CO is preserved up to the desorption temperature of the IL (370 K). Further, the IL shell suppresses the oxidation of the Co NPs if oxygen is introduced in the PVCD process. Only chemisorbed oxygen is formed at oxygen partial pressures that swiftly lead to formation of Co₃O₄ in the absence of the IL (5 × 10^–6 mbar O₂). This chemisorbed oxygen is found to destabilize the CO ligand shell. The oxidation of Co is not suppressed if IL and Co are deposited sequentially under otherwise identical conditions. In this case we observe the formation of fully oxidized cobalt oxide particles.