Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study

Jayanthi, Kumar; Neilsen, Grace; Gibson, Alexis; Navrotsky, Alexandra; Woodfield, Brian F.

doi:10.1021/acs.jpcc.2c08217

Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study

Journal Article · Mon Feb 13 23:00:00 EST 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c08217· OSTI ID:1959588

^[1]; Neilsen, Grace ^[2]; Gibson, Alexis ^[2]; ^[3]; ^[2]

Arizona State Univ., Tempe, AZ (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Brigham Young Univ., Provo, UT (United States)
Arizona State Univ., Tempe, AZ (United States)

Here, room-temperature acid solution calorimetry, high-temperature oxide melt solution calorimetry, and low-temperature heat capacity measurements were employed to calculate the thermodynamic stabilities of the [Zn–Al–X] layered double hydroxides (LDH) containing different anions (X = Cl^–, CO₃^2–, and SO₄^2–). Cryogenic heat capacity measurements demonstrated a Schottky-type anomaly in the heat capacity of all three LDHs below 11 K. This anomaly is attributed to the tunneling of protons between adjacent oxygen atoms in the LDH interlayer as this creates an energy system similar to a two-level system modeled with a Schottky term. These heat capacity measurements were also used to determine vibrational entropies which, when combined with configurational entropies, provide standard entropies of these LDHs. Enthalpies of formation of LDHs from binary components were determined and combined with the entropies of formation to calculate Gibbs free energies. Based on these values, the order of stability is [Zn–Al–SO₄] > [Zn–Al–CO₃] > [Zn–Al–Cl]. This trend results from a combination of the interlayer spacing, amount of water in the interlayer, interactions among the interlayer species, and interactions between the metal hydroxide layer and the interlayer.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725; AC02-07CH11358

OSTI ID:: 1959588

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 7 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study

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