The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study

Thuat T. Trinh; Xavier Rozanska; Francoise Delbecq; Alain Tuel; Philippe Sautet

doi:10.1039/c6cp01223j

The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study

Thuat T. Trinh, Xavier Rozanska, Francoise Delbecq, Alain Tuel, Philippe Sautet

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The condensation reactions between Ge(OH)4 and Si(OH)4 units in solution are studied to understand the mechanism and stable species during the initial steps of the formation process of Ge containing zeolites under basic conditions. The free energy of formation of (OH)3Ge–O–Ge–(OH)2O−, (OH)3Si–O–Si–(OH)2O−, (OH)3Ge–O–Si–(OH)2O− and (OH)3Si–O–Ge–(OH)2O− dimers is calculated with ab initio molecular dynamics and thermodynamic integration, including an explicit description of the water solvent molecules. Calculations show that the attack of the conjugated base (Ge(OH)3O− and Si(OH)3O−) proceeds with a smaller barrier at the Ge center. In addition, the formation of the pure germanate dimer is more favorable than that of the germano-silicate structure. These results explain the experimental observation of Ge–Ge and Si-Ge dimer species in solutions, with a few Si–Si ones.

Original language	English (US)
Pages (from-to)	14419-14425
Number of pages	7
Journal	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume	18
Issue number	21
DOIs	https://doi.org/10.1039/c6cp01223j
State	Published - Apr 28 2016
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2022-06-01
Acknowledged KAUST grant number(s): CADENCED UK-C0017
Acknowledgements: This work was funded by King Abdullah University of Science and Technology (KAUST), within the framework of the Special Academic Partnership Program (CADENCED UK-C0017). The computational issue was supported by KAUST Supercomputing Laboratory (Noor machine).
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1039/c6cp01223j

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title = "The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study",

abstract = "The condensation reactions between Ge(OH)4 and Si(OH)4 units in solution are studied to understand the mechanism and stable species during the initial steps of the formation process of Ge containing zeolites under basic conditions. The free energy of formation of (OH)3Ge–O–Ge–(OH)2O−, (OH)3Si–O–Si–(OH)2O−, (OH)3Ge–O–Si–(OH)2O− and (OH)3Si–O–Ge–(OH)2O− dimers is calculated with ab initio molecular dynamics and thermodynamic integration, including an explicit description of the water solvent molecules. Calculations show that the attack of the conjugated base (Ge(OH)3O− and Si(OH)3O−) proceeds with a smaller barrier at the Ge center. In addition, the formation of the pure germanate dimer is more favorable than that of the germano-silicate structure. These results explain the experimental observation of Ge–Ge and Si-Ge dimer species in solutions, with a few Si–Si ones.",

author = "Trinh, {Thuat T.} and Xavier Rozanska and Francoise Delbecq and Alain Tuel and Philippe Sautet",

note = "KAUST Repository Item: Exported on 2022-06-01 Acknowledged KAUST grant number(s): CADENCED UK-C0017 Acknowledgements: This work was funded by King Abdullah University of Science and Technology (KAUST), within the framework of the Special Academic Partnership Program (CADENCED UK-C0017). The computational issue was supported by KAUST Supercomputing Laboratory (Noor machine). This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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doi = "10.1039/c6cp01223j",

language = "English (US)",

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publisher = "Royal Society of Chemistry",

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T1 - The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study

AU - Trinh, Thuat T.

AU - Rozanska, Xavier

AU - Delbecq, Francoise

AU - Tuel, Alain

AU - Sautet, Philippe

N1 - KAUST Repository Item: Exported on 2022-06-01 Acknowledged KAUST grant number(s): CADENCED UK-C0017 Acknowledgements: This work was funded by King Abdullah University of Science and Technology (KAUST), within the framework of the Special Academic Partnership Program (CADENCED UK-C0017). The computational issue was supported by KAUST Supercomputing Laboratory (Noor machine). This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2016/4/28

Y1 - 2016/4/28

N2 - The condensation reactions between Ge(OH)4 and Si(OH)4 units in solution are studied to understand the mechanism and stable species during the initial steps of the formation process of Ge containing zeolites under basic conditions. The free energy of formation of (OH)3Ge–O–Ge–(OH)2O−, (OH)3Si–O–Si–(OH)2O−, (OH)3Ge–O–Si–(OH)2O− and (OH)3Si–O–Ge–(OH)2O− dimers is calculated with ab initio molecular dynamics and thermodynamic integration, including an explicit description of the water solvent molecules. Calculations show that the attack of the conjugated base (Ge(OH)3O− and Si(OH)3O−) proceeds with a smaller barrier at the Ge center. In addition, the formation of the pure germanate dimer is more favorable than that of the germano-silicate structure. These results explain the experimental observation of Ge–Ge and Si-Ge dimer species in solutions, with a few Si–Si ones.

AB - The condensation reactions between Ge(OH)4 and Si(OH)4 units in solution are studied to understand the mechanism and stable species during the initial steps of the formation process of Ge containing zeolites under basic conditions. The free energy of formation of (OH)3Ge–O–Ge–(OH)2O−, (OH)3Si–O–Si–(OH)2O−, (OH)3Ge–O–Si–(OH)2O− and (OH)3Si–O–Ge–(OH)2O− dimers is calculated with ab initio molecular dynamics and thermodynamic integration, including an explicit description of the water solvent molecules. Calculations show that the attack of the conjugated base (Ge(OH)3O− and Si(OH)3O−) proceeds with a smaller barrier at the Ge center. In addition, the formation of the pure germanate dimer is more favorable than that of the germano-silicate structure. These results explain the experimental observation of Ge–Ge and Si-Ge dimer species in solutions, with a few Si–Si ones.

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The mechanism of the initial step of germanosilicate formation in solution: a first-principles molecular dynamics study

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