Journal article
Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(11), pp.2754-2767
03/20/2025
DOI: 10.1021/acs.jpca.5c00390
PMID: 40048634
Abstract
Despite decades of work on aqueous lead (Pb) adsorption on α-Fe2O3 (hematite) and α-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experiment for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001), (012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parameterized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experimental insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).
Details
- Title: Subtitle
- Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights
- Creators
- Jennifer L Bjorklund - University of IowaLogan J Augustine - University of IowaAli Abbaspour Tamijani - University of IowaThomas P Trainor - University of Alaska FairbanksAnne M Chaka - Pacific Northwest National LaboratorySara E Mason - University of Iowa
- Resource Type
- Journal article
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(11), pp.2754-2767
- DOI
- 10.1021/acs.jpca.5c00390
- PMID
- 40048634
- NLM abbreviation
- J Phys Chem A
- ISSN
- 1520-5215
- eISSN
- 1520-5215
- Publisher
- AMER CHEMICAL SOC
- Grant note
- U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory: DE-SC0012704 U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division through its Geosciences program: FWP 56674 Battelle Memorial Institute: DE-AC05-76RL01830
This research was supported in part through high-performance computational resources provided by The University of Iowa, Iowa City, Iowa. This research also used the Theory and Computation facility of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. Anne Chaka's time was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division through its Geosciences program (FWP 56674) at Pacific Northwest National Laboratory (PNNL). PNNL is operated for DOE by the Battelle Memorial Institute under contract DE-AC05-76RL01830.
- Language
- English
- Electronic publication date
- 03/06/2025
- Date published
- 03/20/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984798362102771
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