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Tunable Ti3C2Tx MXene-Derived TiO2 Nanocrystals at Controlled pH and Temperature
Langmuir ( IF 3.7 ) Pub Date : 2022-10-07 , DOI: 10.1021/acs.langmuir.2c02110
Ari Chae 1, 2 , Sehyun Doo 1 , Daesin Kim 1 , Tae Yun Ko 1 , Taegon Oh 1 , Seon Joon Kim 1, 3 , Dong-Yeun Koh 2 , Chong Min Koo 1, 4, 5
Affiliation  

While two-dimensional (2D) Ti3C2Tx MXene in aqueous dispersions spontaneously oxidizes into titanium dioxide (TiO2) nanocrystals, the crystallization mechanism has not been comprehensively understood and the resultant crystal structures are not controlled among three representative polymorphs: anatase, rutile, and brookite. In this study, such control on the lattice structures and domain sizes of the MXene-derived TiO2 crystallites is demonstrated by means of the oxidation conditions, pH, and temperature (3.0–11.0 and 20–100 °C, respectively). It is observed that the formation of anatase phase is preferred against rutile phase in more basic and hotter oxidizing solutions, and even 100% anatase can be obtained at pH 11.0 and 100 °C. At lower pH and temperature, the portion of rutile phase increases such that it reaches ∼70% at pH 3 and 20 °C. Under certain circumstances, small portion of brookite phase is also observed. Smaller domain sizes of both anatase and rutile phases are observed in more basic oxidizing solutions and at lower temperatures. Based on these experimental results, we propose the crystallization mechanism in which the oxidative dissociation of Ti3C2Tx first produces Ti ions as the intermediate state, and they bind to abundant oxygen in the aqueous dispersions, and nucleate and crystallize into TiO2.

中文翻译:

在受控 pH 和温度下可调谐 Ti3C2Tx MXene 衍生的 TiO2 纳米晶体

虽然水分散体中的二维 (2D) Ti 3 C 2 T x MXene 自发氧化成二氧化钛 (TiO 2 ) 纳米晶体,但其结晶机制尚未得到全面了解,并且所得晶体结构在三种代表性多晶型中不受控制:锐钛矿、金红石和板钛矿。在本研究中,这种对 MXene 衍生的 TiO 2的晶格结构和畴尺寸的控制通过氧化条件、pH 和温度(分别为 3.0–11.0 和 20–100 °C)来证明微晶。据观察,在碱性更强和更热的氧化溶液中,锐钛矿相的形成优于金红石相,甚至在 pH 11.0 和 100 °C 下也可以获得 100% 的锐钛矿。在较低的 pH 值和温度下,金红石相的比例增加,在 pH 3 和 20 °C 时达到 70%。在某些情况下,还观察到一小部分板钛矿相。在更碱性的氧化溶液和更低的温度下观察到锐钛矿和金红石相的区域尺寸更小。基于这些实验结果,我们提出了Ti 3 C 2 T x氧化解离的结晶机制。首先产生Ti离子作为中间态,它们与水分散体中丰富的氧结合,成核结晶成TiO 2
更新日期:2022-10-07
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