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利用MFI型沸石作为纳米反应容器合成一种意想不到的[Zn₂]²⁺物种及其光热调控

Synthesis of an unexpected [Zn2](2+) species utilizing an MFI-type zeolite as a nano-reaction pot and its manipulation with light and heat.

作者信息

Oda Akira, Ohkubo Takahiro, Yumura Takashi, Kobayashi Hisayoshi, Kuroda Yasushige

机构信息

Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima, Kita-ku, Okayama 700-8530, Japan.

出版信息

Dalton Trans. 2015 Jun 7;44(21):10038-47. doi: 10.1039/c5dt01088h.

Abstract

Compared with mercury, the existence of Zn2 species is rare. We succeeded in preparing a stable Zn2 species by utilizing an MFI-type zeolite as a nano-reaction pot, which was confirmed using XAFS spectroscopy: the bands at R = 2.35 Å due to the Zn(+)-Zn(+) scattering and at 9660.7 eV due to the 1s-σ* (the anti-bonding orbital comprised of the 4s-4s orbital) transition of the Zn2 species. This species also gives the characteristic band around 42 000 cm(-1) due to its σ-σ* transition. Furthermore, UV-irradiation corresponding to the σ-σ* transition causes the bond dissociation, forming two unprecedented Zn(+) ions, and detached Zn(+) ions were recombined through heat-treatment at 573 K: [Zn(+)-Zn(+)] ⇄ 2Zn(+). These processes were reproduced by applying the DFT calculation method to the assumed triplet, σ(α)-σ*(α), structure formed on the M7-S2 site with the specific Al array in the MFI-type zeolite. Research into the specific field using zeolites to synthesize "ultra-state ions" is very promising.

摘要

与汞相比,Zn2物种的存在较为罕见。我们通过利用MFI型沸石作为纳米反应容器成功制备了一种稳定的Zn2物种,这一点通过XAFS光谱得以证实:由于Zn(+)-Zn(+)散射,在R = 2.35 Å处出现谱带,由于Zn2物种的1s-σ*(由4s-4s轨道组成的反键轨道)跃迁,在9660.7 eV处出现谱带。该物种由于其σ-σ跃迁,在42000 cm(-1)左右也给出特征谱带。此外,对应于σ-σ跃迁的紫外线照射会导致键解离,形成两个前所未有的Zn(+)离子,并且通过在573 K下进行热处理,分离出的Zn(+)离子会重新结合:[Zn(+)-Zn(+)] ⇄ 2Zn(+)。通过将DFT计算方法应用于在MFI型沸石中具有特定Al排列的M7-S2位点上形成的假定三重态σ(α)-σ*(α)结构,再现了这些过程。利用沸石合成“超态离子”的特定领域研究非常有前景。

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