Mechanisms of Zn removal from water by amorphous geopolymer: Molecular-level insights from X-ray absorption spectroscopy, isotope fractionation, and surface complexation modeling

Tang, Jinping; Sun, Guangyi; Feng, Xinbin; Liu, Dongdong; Fei, Yingxiang; Shang, Jing; Finfrock, Y. Zou; Liu, Peng

doi:10.1016/j.cej.2023.147175

Title: Mechanisms of Zn removal from water by amorphous geopolymer: Molecular-level insights from X-ray absorption spectroscopy, isotope fractionation, and surface complexation modeling

Journal Article · 07 November 2023 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2023.147175 · OSTI ID:2329521

Tang, Jinping ^[1]; Sun, Guangyi ^[2]; Feng, Xinbin ^[2]; Liu, Dongdong ^[3]; Fei, Yingxiang ^[4]; Shang, Jing ^[4]; Finfrock, Y. Zou ^[5];

^[4]

China University of Geosciences, Wuhan (China); Weizmann Institute of Science, Rehovot (Israel)
Chinese Academy of Sciences (CAS), Guiyang (China). Institute of Geochemistry
Guizhou University, Guiyang (China)
China University of Geosciences, Wuhan (China)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Porous geopolymers have attracted widespread attention as promising heavy metal adsorbents that can be synthesized from aluminosilicate solid wastes. However, the precise microstructural evidence for adsorbed heavy metals on geopolymers remains unclear due to the insensitivity of conventional characterization techniques on minerals with amorphous structure and surface disorder. Batch adsorption and column experiments coupled with X-ray absorption spectroscopy (XAS), Zn stable isotope, and surface complexation model (SCM) were employed to reveal the Zn removal mechanisms with coal fly ash porous geopolymer (CFAPG) at a molecular scale. The macroscopic kinetic and isothermal adsorption of Zn on CFAPG were well described by the pseudo-second-order model and Bi_Langmuir equation, respectively, indicating the presence of abundant heterogeneous active sites on the CFAPG surface. Further, two types of active sites on the CFAPG surface were identified by XAS coupled with Zn isotopes in batch experiments at pH <= 6.0: one is pH-dependent and associated with tetrahedral zinc coordi-nation, and the other is pH-insensitive and associated with octahedral zinc coordination; these sites were confirmed by the bidentate SCM as the variable charge site (surface complexation, >S-OH) and the permanent negative charge site (cation exchange, >X^-), respectively. Furthermore, the important contribution of surface co -precipitation besides surface complexation and cation exchange to the Zn adsorption on CFAPG was identified by XAS coupled with SCM in a flow-through column experiment at pH >6.0. These investigations provide a systemic understanding of the Zn adsorption mechanisms on CFAPG and an SCM reference for the application and prediction of geopolymers in heavy metal-contaminated water remediations.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; National Key Research and Development Program of China; China Scholarship Council

Grant/Contract Number:: AC02-06CH11357; 2019YFC1803600; 202206410083

OSTI ID:: 2329521

Journal Information:: Chemical Engineering Journal, Vol. 477; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanisms of Zn removal from water by amorphous geopolymer: Molecular-level insights from X-ray absorption spectroscopy, isotope fractionation, and surface complexation modeling

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