Reaction Mechanism of Active Groups in Geopolymers: A DFT Study
Publication: Journal of Materials in Civil Engineering
Volume 36, Issue 12
Abstract
Although the concept of geopolymers was proposed over 40 years ago, there still remains a lack of clarity regarding their atomic-level structure and formation. In this study, the quantum chemistry calculation program, based on density functional theory (DFT), was used to determine a range of electronic structural properties associated with the initial, intermediate (IM), transition (TS), and final states of conversion reactions in the alkali-activator. The properties analyzed included total energy, Gibbs free energy, electrostatic potential (ESP), Fukui functions, and frontier orbitals, comprising the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO). The simulation results indicated that electrons were transferred from the HOMO of O in and to the LUMO of Al in or , leading to an increase in the LUMO energy level of Al and a reduction in the chemical reactivity of the newly formed Al monomers. The transformation processes from to involved varying numbers of steps, energy release, and energy barriers. Notably, during the transition state conversion process, the breaking and reformation of O─ H bonds often occurred as necessary conditions for the formation of transition states. These findings have significant implications for the advancement of new technologies based on geopolymer conversion processes.
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Data Availability Statement
Some or all data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
Acknowledgments
This work was supported by the Joint Funds of the National Natural Science Foundation of China (U20A20324), the National Natural Science Foundation of China (52272016), Youth Fund Project of National Natural Science Foundation of China (52308235), and the Dalian Science and Technology Innovation Fund Project (2023JJ12SN036).
Author contributions: Jiazhi Huang: Conceptualization, Methodology, Investigation, Validation, Formal analysis, Visualization, Writing–original draft, Writing–review and editing. Baomin Wang: Project administration, Funding acquisition, Writing–review and editing. Shipeng Zhang: Formal analysis, Writing–review and editing. Chengcheng Fan: Funding acquisition, Writing–review and editing.
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© 2024 American Society of Civil Engineers.
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Received: May 24, 2023
Accepted: Apr 9, 2024
Published online: Sep 17, 2024
Published in print: Dec 1, 2024
Discussion open until: Feb 17, 2025
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