PKU-3: An HCl-Inclusive Aluminoborate for Strecker Reaction Solved by Combining RED and PXRD

Chen, Hong; Ju, Jing; Meng, Qingpeng; Su, Jie; Lin, Cong; Zhou, Zhengyang; Li, Guobao; Wang, Weilu; Gao, Wenliang; Zeng, Chong; Tang, Chiu C.; Lin, Jianhua; Yang, Tao; Sun, Junliang

doi:10.1021/jacs.5b03685

Cited by 34 publications

(12 citation statements)

References 46 publications

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“…In satimolite and PKU-8 these fundamental building units consist of one M -centred octahedron, one BO 3 triangle and one BO 4 tetrahedron. The same configuration was described recently in the structure of another synthetic borate PKU-3 (Chen et al ., 2015). The remarkable feature of the aluminoborate frameworks of satimolite and PKU-8 is the presence of large ellipsoidal cages with an approximate size of 12 Å x 8.6 Å (Fig.…”

Section: Discussionmentioning

confidence: 99%

Redefinition of satimolite

et al. 2018

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The borate mineral satimolite, which was first described in 1969 and remained poorly-studied until now, has been re-investigated (electron microprobe analysis, single-crystal and powder X-ray diffraction studies, crystal-structure determination, infrared spectroscopy) and redefined based on the novel data obtained for the holotype material from the Satimola salt dome and a recently found sample from the Chelkar salt dome, both in North Caspian Region, Western Kazakhstan. The revised idealized formula of satimolite is KNa2(Al5Mg2)[B12O18(OH)12](OH)6Cl4·4H2O (Z = 3). The mineral is trigonal, space group R$\bar{3}$m, unit-cell parameters are: a = 15.1431(8), c = 14.4558(14) Å and V = 2870.8(4) Å3 (Satimola) and a = 15.1406(4), c = 14.3794(9) Å and V = 2854.7(2) Å3 (Chelkar). The crystal system and unit-cell parameters are quite different from those reported previously. The crystal structure of the sample from Chelkar was solved based on single-crystal data (direct methods, R = 0.0814) and the structure of the holotype from Satimola was refined on a powder sample by the Rietveld method (Rp = 0.0563, Rwp = 0.0761 and Rall = 0.0667). The structure of satimolite is unique for minerals. It contains 12-membered borate rings [B12O18(OH)12] in which BO3 triangles alternate with BO2(OH)2 tetrahedra sharing common vertices, and octahedral clusters [M7O6(OH)18] with M = Al5Mg2 in the ideal case, with sharing of corners between rings and clusters to form a three-dimensional heteropolyhedral framework. Each borate ring is connected with six octahedral clusters: three under the ring and three over the ring. Large ellipsoidal cages in the framework host Na and K cations, Cl anions and H2O molecules.

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Section: Discussionmentioning

confidence: 99%

Redefinition of satimolite

et al. 2018

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“…表 1 几种电子衍射方法的比较 [47] (网络版彩图) 图 4 (a~c) IM-5在三个主轴方向的HRTEM照片; (d) 不同角度的选区电子衍射图像; (e) 三维电势分布图 [46] (网络版彩图) [49] (图7). [48] (网络版彩图) d, e) 结构示意图 [49] (网络版彩图) 图 8 PKU-3 [50] (a)和KCu 4 Se 8 [51] (b)的结构示意图(网络版彩图)…”

Section: 连续旋转电子衍射(Cred)unclassified

“…Figure 8 Structure model of PKU-3 (a) [50] and KCu 4 Se 8 (b) [51]. Adapted with permission from Refs.…”

Section: 旋转电子衍射(Red)mentioning

confidence: 99%

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Research progress on the crystal structure determination using electron diffraction

Qiu¹,

Zhou²,

Sun³

2020

Sci. Sin.-Chim

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Electron diffraction is one of the basic techniques to study crystal structures. With the improvement of the transmission electron microscope hardware facilities and the development of structural analysis methods, electron diffraction plays an increasingly important role in exploring the relationship between the material structures and their physical properties. In this review, the progress of crystal structure determination using electron diffraction was mainly discussed. Our group has analyzed many complex crystal structures including inorganic functional materials, zeolites and covalent organic framework materials, utilizing selected area electron diffraction and three-dimensional electron diffraction technology combined with powder X-ray diffraction, single crystal X-ray diffraction, high-resolution electron microscopy and other characterization methods.

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“…The catalytic activity was quite different when Fe(III) species were supported or anchored in a different matrix, which hints at the existing states of Fe species, e.g., the surface distributions, matrix choice, and apparent valence state will bring a great disparity in the catalytic activity. As an excellent dopant matrix, octahedra-based molecular sieves PKU-n (aluminoborates) have received much attention recently. − In PKU-n, 6-coordinated Al 3+ in the framework can be isomorphously replaced by other 6-coordinated metal cations (i.e., Fe 3+ , Cr 3+ ), and their flexible octahedra-based backbone can accommodate specific transition metals with a relatively high concentration, thus making M-incorporated PKU-n a good candidate for some redox- or acid–base-catalyzed reactions. − In this regard, a Fe-incorporated solid acid catalyst with an octahedra-based framework (named as Fe–PKU-1) was developed through the boric acid molten method and was evaluated in the ring-opening hydration reaction of epoxides under ambient pressure. The current focus is to better understand the structure–activity relationship between the Fe sites and epoxide activation.…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Hydration of Epoxides into Diols with a Low Water–Epoxide Ratio Catalyzed by a Fe-Incorporated Octahedra-Based Molecular Sieve

et al. 2021

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1,2-Diols are important organic intermediates in the production of a variety of organic chemicals, and their eco-friendly production has attracted much attention, especially from epoxide hydration using solid-acid catalysts. Herein, Fe 3+incorporated PKU-1 molecular sieve (Fe−PKU-1), an open-framework and octahedra-based aluminoborate with 18-membered-ring channels, was successfully synthesized and behaved as a solid Lewis acid to catalyze the ring-opening hydration of epoxides. The as-synthesized Fe−PKU-1 catalyst has a high catalytic efficiency at a low water−epoxide ratio and better structural stability. The comparative tests indicated that some other Fe-containing catalysts only had a very low catalytic activity, which confirmed the structure-sensitive role of Fe 3+ doped in the PKU-1 framework. Reaction kinetics analyses showed that the hydration reaction is a firstorder reaction and has a lower apparent activation energy (∼30 kJ•mol −1 ). Further investigations discovered that trans-1,2-cyclohexanediol was exclusively formed through a nucleophilic addition when using cyclohexene oxide as substrate molecule, and the adsorption experiment indicated an extremely high amount of epoxide was accumulated in the solid/liquid interface of Fe− PKU-1, which is nearly 100 times higher than that of Fe-free PKU-1. On the basis of the above results, a plausible catalytic mechanism was proposed to elucidate the epoxide hydration process.

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PKU-3: An HCl-Inclusive Aluminoborate for Strecker Reaction Solved by Combining RED and PXRD

Cited by 34 publications

References 46 publications

Redefinition of satimolite

Redefinition of satimolite

Research progress on the crystal structure determination using electron diffraction

Ring-Opening Hydration of Epoxides into Diols with a Low Water–Epoxide Ratio Catalyzed by a Fe-Incorporated Octahedra-Based Molecular Sieve

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