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.
References
Bagheri, A., A. Nazari, J. G. Sanjayan, P. Rajeev, and W. Duan. 2016. “Fly ash-based boroaluminosilicate geopolymers: Experimental and molecular simulations.” Ceram. Int. 43 (5): 4119–4126. https://doi.org/10.1016/j.ceramint.2016.12.020.
Bagheri, A. A. J. G. 2018. “Molecular simulation of water and chloride ion diffusion in nanopores of alkali-activated aluminosilicate structures.” Ceram. Int. 44 (17): 20723–20731. https://doi.org/10.1016/j.ceramint.2018.08.067.
Carr, J. M., S. A. Trygubenko, and D. J. Wales. 2005. “Finding pathways between distant local minima.” J. Chem. Phys. 122 (23): 234903. https://doi.org/10.1063/1.1931587.
Davidovits, J. 1994. “Properties of geopolymer cements alkaline cements and concretes.” In Proc., 1st Int. Conf. on Alkaline Cements and Concretes. Kiev, Ukraine: VIPOL Stock Company.
Delley, B. 1990. “An all-electron numerical method for solving the local density functional for polyatomic molecules.” J. Chem. Phys. 92 (1): 508–517. https://doi.org/10.1063/1.458452.
Delley, B. 2000. “From molecules to solids with the DMol3 approach.” J. Chem. Phys. 113 (18): 7756–7764. https://doi.org/10.1063/1.1316015.
Dicks, O. A., and A. L. Shluger. 2017. “Theoretical modeling of charge trapping in crystalline and amorphous .” J. Phys.: Condens. Matter 29 (31): 314005. https://doi.org/10.1088/1361-648X/aa7767.
Du, M. H., L. L. Wang, A. Kolchin, and H. P. Cheng. 2003. “Water-silica interaction in clusters.” Eur. Phys. J. D 24 (1–3): 323–326. https://doi.org/10.1140/epjd/e2003-00177-6.
Fernández, E. M., R. I. Eglitis, G. Borstel, and L. C. Balbás. 2007. “Ab initio calculations of H2O and adsorption on substrates.” Comput. Mater. Sci. 39 (3): 587–592. https://doi.org/10.1016/j.commatsci.2006.08.010.
Gao, Y., T. Guo, Z. Li, Z. Zhou, and J. Zhang. 2022. “Mechanism of retarder on hydration process and mechanical properties of red mud-based geopolymer cementitious materials.” Constr. Build. Mater. 356 (Sep): 129306. https://doi.org/10.1016/j.conbuildmat.2022.129306.
Grimme, S. 2004. “Accurate description of van der Waals complexes by density functional theory including empirical corrections.” J. Comput. Chem. 25 (12): 1463–1473. https://doi.org/10.1002/jcc.20078.
Huang, J. Q., and J. G. Dai. 2020. “Flexural performance of precast geopolymer concrete sandwich panel enabled by FRP connector.” Compos. Struct. 248 (Sep): 112563. https://doi.org/10.1016/j.compstruct.2020.112563.
Juenger, M., F. Winnefeld, J. L. Provis, and J. H. Ideker. 2011. “Advances in alternative cementitious binders.” Cem. Concr. Res. 41 (12): 1232–1243. https://doi.org/10.1016/j.cemconres.2010.11.012.
Koch, U., and P. Popelier. 1995. “Characterization of C-h-o Hydrogen-bonds on the Basis of the Charge-density.” J. Phys. Chem. 99 (24): 9747–9754. https://doi.org/10.1021/j100024a016.
Li, J., W. Zhang, K. Garbev, G. Beuchle, and P. Monteiro. 2020. “Influences of cross-linking and Al incorporation on the intrinsic mechanical properties of tobermorite.” Cem. Concr. Res. 136 (Apr): 106170. https://doi.org/10.1016/j.cemconres.2020.106170.
Li, Y., H. Pan, and Z. Li. 2022. “Ab initio metadynamics simulations on the formation of calcium silicate aqua complexes prior to the nuleation of calcium silicate hydrate.” Cem. Concr. Res. 156 (Feb): 106767. https://doi.org/10.1016/j.cemconres.2022.106767.
Lu, Q., X. Y. Zhou, Y. W. Wu, T. G. Mi, J. Liu, B. Hu, and L. Zhao. 2021. “Interaction mechanism between cadmium species and of municipal solid waste incineration fly ash: Effect of HCl.” Chem. Eng. J. 425 (Dec): 130604. https://doi.org/10.1016/j.cej.2021.130604.
Merlino, S., E. Bonaccorsi, and T. Armbruster. 1999. “Tobermorites: Their real structure and order-disorder (OD) character.” Am. Miner. 84 (10): 1613–1621. https://doi.org/10.2138/am-1999-1015.
Ogundiran, M. B., and S. Kumar. 2015. “Synthesis and characterisation of geopolymer from Nigerian Clay.” Appl. Clay Sci. 108 (Feb): 173–181. https://doi.org/10.1016/j.clay.2015.02.022.
Perdew, J. P., K. Burke, and M. Ernzerhof. 1996. “Generalized Gradient Approximation Made Simple.” Phys. Rev. Lett. 77 (18): 3865. https://doi.org/10.1103/PhysRevLett.77.3865.
Prasanphan, S., A. Wannagon, T. Kobayashi, and S. Jiemsirilers. 2019. “Reaction mechanisms of calcined kaolin processing waste-based geopolymers in the presence of low alkali activator solution.” Constr. Build. Mater. 221 (Dec): 409–420. https://doi.org/10.1016/j.conbuildmat.2019.06.116.
Qu, W., H. Zu, J. Yang, Z. Yang, and H. Li. 2021. “The influences of selenium species on mercury removal over pyrite surface: A density functional theory study.” Fuel 292 (Jun): 120284. https://doi.org/10.1016/j.fuel.2021.120284.
Richardson, I. G. 2004. “Tobermorite/jennite- and tobermorite/calcium hydroxide-based models for the structure of C-S-H: Applicability to hardened pastes of tricalcium silicate, -dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaol.” Cem. Concr. Res. 34 (9): 1733–1777. https://doi.org/10.1016/j.cemconres.2004.05.034.
Richardson, I. G. 2015. “Model structures for C-(A)-S-H(I).” Acta Crystallogr. 70 (6): 903–923.
Roy, R. K. 2003. “Stockholders charge partitioning technique. A reliable electron population analysis scheme to predict intramolecular reactivity sequence.” J. Phys. Chem. A 107 (48): 10428–10434. https://doi.org/10.1021/jp035848z.
Shi, Y., Q. Zhao, C. Xue, Y. Jia, W. Guo, Y. Zhang, and Y. Qiu. 2023. “Preparation and curing method of red mud-calcium carbide slag synergistically activated fly ash-ground granulated blast furnace slag based eco-friendly geopolymer.” Cem. Concr. Compos. 139 (Jan): 104999. https://doi.org/10.1016/j.cemconcomp.2023.104999.
Silva, P. D., K. Sagoe-Crenstil, and V. Sirivivatnanon. 2007. “Kinetics of geopolymerization: Role of and SiO2.” Cem. Concr. Res. 37 (4): 512–518. https://doi.org/10.1016/j.cemconres.2007.01.003.
Singh, P. S., M. Trigg, I. Burgar, and T. Bastow. 2005. “Geopolymer formation processes at room temperature studied by 29Si and 27Al MAS-NMR.” Mater. Sci. Eng., A 396 (1–2): 392–402. https://doi.org/10.1016/j.msea.2005.02.002.
Svenum, I. I. G. B. 2020. “Structure, hydration, and chloride ingress in C-S-H: Insight from DFT calculations.” Cem. Concr. Res. 129 (Mar): 105965. https://doi.org/10.1016/j.cemconres.2019.105965.
Trygubenko, S. A., and D. J. Wales. 2004. “A doubly nudged elastic band method for finding transition states.” J. Chem. Phys. 120 (5): 2082–2094. https://doi.org/10.1063/1.1636455.
Tse, W. H. 2017. “The design, fabrication, and characterization of nanoparticle-protein interactions for theranostic applications.” Doctoral dissertation, Univ. of Western Ontario. https://core.ac.uk/download/pdf/129543694.pdf.
Wan, Q., F. Rao, S. Song, R. E. García, R. M. Estrella, C. L. Patiño, and Y. Zhang. 2017. “Geopolymerization reaction, microstructure and simulation of metakaolin-based geopolymers at extended ratios.” Cem. Concr. Compos. 79 (May): 45–52. https://doi.org/10.1016/j.cemconcomp.2017.01.014.
Weng, L., and K. Sagoe-Crentsil. 2007. “Dissolution processes, hydrolysis and condensation reactions during geopolymer synthesis: Part I—Low Si/Al ratio systems.” J. Mater. Sci. 42 (9): 2997–3006. https://doi.org/10.1007/s10853-006-0820-2.
Wynne-Jones, W. F. K., and H. Eyring. 1935. “The absolute rate of reactions in condensed phases.” J. Chem. Phys. 3 (8): 492–502. https://doi.org/10.1063/1.1749713.
Yang, Y., J. Liu, Z. Wang, and Y. Yu. 2020. “Reaction mechanism of elemental mercury oxidation to during SO2/SO3 conversion over V2O5/TiO2 catalyst.” Proc. Combust. Inst. 38 (3): 4317–4325. https://doi.org/10.1016/j.proci.2020.10.007.
Zhang, A., J. Liu, Y. Yang, Y. Yu, and J. Zhang. 2022. “Reaction chemistry of formation over sorbent.” Fuel 310 (Apr): 122407. https://doi.org/10.1016/j.fuel.2021.122407.
Zhou, S., C. Lu, X. Zhu, and F. Li. 2021. “Upcycling of natural volcanic resources for geopolymer: Comparative study on synthesis, reaction mechanism and rheological behavior.” Constr. Build. Mater. 268 (Mar): 121184. https://doi.org/10.1016/j.conbuildmat.2020.121184.
Zhuang, X. Y., L. Chen, S. Komarneni, C. H. Zhou, D. S. Tong, H. M. Yang, W. H. Yu, and H. Wang. 2016. “Fly ash-based geopolymer: Clean production, properties and applications.” J. Cleaner Prod. 125 (Jun): 253–267. https://doi.org/10.1016/j.jclepro.2016.03.019.
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Published In
Journal of Materials in Civil Engineering
Volume 36 • Issue 12 • December 2024
Copyright
© 2024 American Society of Civil Engineers.
History
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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