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

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

doi:10.1021/acs.jpcc.2c08217

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

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

Nanomaterials Chemistry Group

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	3760-3768
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	127
Issue number	7
DOIs	https://doi.org/10.1021/acs.jpcc.2c08217
State	Published - Feb 23 2023

Funding

This work was supported by the US Department of Energy Critical Materials Institute (CMI) Hub under the Subaward Number DE-AC02-07CH11358. This manuscript has been authored by UT-Battelle, LLC under Contract no. DEAC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

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title = "Role of Anions in Stabilizing the [Zn-Al] Layered Double Hydroxides: A Thermodynamic Study",

abstract = "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-, CO32-, and SO42-). 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.",

author = "K. Jayanthi and Grace Neilsen and Alexis Gibson and Alexandra Navrotsky and Woodfield, \{Brian F.\}",

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AU - Neilsen, Grace

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AU - Navrotsky, Alexandra

AU - Woodfield, Brian F.

PY - 2023/2/23

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N2 - 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-, CO32-, and SO42-). 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.

AB - 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-, CO32-, and SO42-). 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.

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

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