Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates†

doi:10.7503/cjcu20170590

Abstract

Abstract:

By heating the initial mixture with the molar composition of n(Al₂O₃):n(P₂O₅):n(R):n(H₂O)=1:1:1:277(R=methylamine or dimethylamine) at 200 ℃, highly crystalline three-dimensional anionic open-framework aluminophosphate of AlPO₄-53 or AlPO₄-21 was obtained. Protonated methylamine and dimethylamine were located in the framework of AlPO₄-53 and AlPO₄-21 to balance the negative charge of the framework, respectively. The crystallization processes of both initial mixtures were investigated by X-ray diffraction analysis(XRD), elemental analysis and pH measurement. Theoretical calculation shows that the charge on the N atom of protonated methylamine and dimethylamine is -0.263 and -0.558 e(Mulliken), respectively. The corresponding formal charge density is 22.3 and 16.0 e/nm³, respectively. The framework charge density of AlPO₄-53 and AlPO₄-21 is -3.3 and -3.1 e/nm³, respectively. These results indicate that the environment change around N atom can affect the amount of charge on it, which accordingly affects its structure-directing ability. A charge matching between the formal charge density of organic amines and the framework charge density was observed.

Key words: Zeolite, Aluminophosphate, Structure-directing effect, Template effect, Formal charge density, Framework charge density

CLC Number:

O611.4

TrendMD:

CHANG Xiaowen, YAN Wenfu, SHI Wei, XU Ruren. Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^†[J]. Chem. J. Chinese Universities, 2018, 39(1): 12.

Figures/Tables 4

Fig.1 Summary of the crystallization of the initial mixtures with the molar composition of n(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277(R=CH3NH2 and CH3NHCH3)

Fig.2 Simulated XRD patterns of AlPO4-53, AlPO4-21 and the experimental powder XRD patterns of solid samples isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277. (A) R=CH3NH2. Hydrothermal treatment period/h: a. 0; b. 3; c. 4; d. 72; e. simulated AlPO4-53. (B) R=CH3NHCH3. Hydrothermal treatment period/h: a. 0; b. 2.5; c. 4; d. 16; e. 96; f. simulated AlPO4-21.

Fig.3 Evolution of the concentrations of Al(a) and P(b) in the liquid phase of the samples isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(R):n(H2O)=1:1:1:277. (A) R=CH3NH2; (B) R=CH3NHCH3.

Fig.4 Evolution of the pH of the liquid phase in the products isolated throughout the hydrothermal treatment period of the initial mixturen(Al2O3):n(P2O5):n(CH3NH2):n(H2O)=1:1:1:277. (A) CH3NH2; (B) R=CH3OHCH3.

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