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Binding dynamics of carboxylate to amorphous aluminum oxides as studied by flow-adsorption microcalorimetry
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2025-12-05
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Flow-adsorption microcalorimetry was used to investigate the dynamics, energetics, and kinetics of mono- and dicarboxylate sorption onto a series of aluminum (hydr)oxides, conducted at the mineral-water interface at pH 5. A synthetic boehmite-bayerite series and γ-Al2O3 were characterized to quantify variations in hydroxyl speciation and structural order and examine surface heterogeneity effects on sorption. This work demonstrates that variations in structural hydroxyl chemistry among aluminum (hydr)oxides produce measurable and systematic effects on the energetics and kinetics of carboxylate sorption. It also highlights the dominance of outer-sphere interactions in sorption and desorption mechanics that largely depend on carboxylate pKa. A multi-step sorption/desorption framework proposed here, consisting of electrostatic and hydrogen-bonding interactions, offers a transferable model for interpreting carboxylate-mineral interactions across heterogeneous aluminum (hydr)oxide systems.
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PayblasCaitlin_thesis.pdf
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- Embargoed until 2027-12-05
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Geology