Optimal thermodynamic conditions to minimize kinetic byproducts in aqueous materials synthesis

Wang, Zheren; Sun, Yingzhi; Cruse, Kevin; Zeng, Yan; Fei, Yuxing; Liu, Zexuan; Shangguan, Junyi; Byeon, Young‐Woon; Jun, KyuJung; He, Tanjin; Sun, Wenhao; Ceder, Gerbrand

doi:10.21203/rs.3.rs-2398824/v1

Cited by 3 publications

(3 citation statements)

References 45 publications

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“…However, these diagrams are often constructed by solving the Nernst equation to draw phase boundaries between competing phases, an approach that cannot consider the free energy or concentration of each species individually. In contrast, our computational Pourbaix diagrams are derived using a grand thermodynamic potential for each species, which enables us to consider the energy contributions of both ion concentration and chemical potential for all elements. , To the best of our knowledge, this work represents the first time this method has been applied to quaternary oxynitride systems.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, our computational Pourbaix diagrams are derived using a grand thermodynamic potential for each species, which enables us to consider the energy contributions of both ion concentration and chemical potential for all elements. 28,54 To the best of our knowledge, this work represents the first time this method has been applied to quaternary oxynitride systems.…”

Section: Chemistry Of Materialsmentioning

confidence: 97%

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Thermodynamic Stability and Anion Ordering of Perovskite Oxynitrides

et al. 2023

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Perovskite oxynitrides (PONs) are a promising class of materials for applications ranging from catalysis to photovoltaics. However, the vast space of single PON materials (ABO3–x N x ) has yet to be fully explored. Additionally, the community needs guidelines that relate PON chemistry and anion ordering to stability to better understand how to design PON materials that resist corrosion and decomposition under operating conditions. Screening this materials space requires identifying candidate PON materials that will be stable under operating conditions, which in turn requires methods to evaluate each material’s stability. Here, we predict the stability of single PON materials using a four-step approach based on density functional theory modeling: (i) enumerate viable cation pairs, (ii) select an energetically favorable prototypical anion ordering, (iii) compute each PON’s energy above the thermodynamic convex hull, and (iv) generate computational Pourbaix diagrams to determine allowable ranges of electrochemical operating conditions. A critical part of our approach is determining a prototypical stable anion ordering for both ABO2N and ABON2 stoichiometries across a variety of A- and B-site cations. We demonstrate a stable anion ordering containing a high degree of cis ordering between B cations and minority-composition anions. We predict 85 stable and 109 metastable PON compounds, with A ∈ {La, Pb, Nd, Sr, Ba, Ca} and B ∈ {Re, Os, Nb, Ta} forming cation pairs that lead to stable PONs less than 10 meV/atom above the thermodynamic convex hull. Computational Pourbaix diagrams for two stable candidates, CaReO2N and LaTaON2, suggest that not all compounds with zero energy above the thermodynamic convex hull can be easily synthesized.

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Section: Resultsmentioning

confidence: 99%

Section: Chemistry Of Materialsmentioning

confidence: 97%

Thermodynamic Stability and Anion Ordering of Perovskite Oxynitrides

et al. 2023

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“…All relevant data are provided within this paper and are available at https://doi.org/10.6084/m9.figshare.23902362 ref. 61,42.…”

Section: Data Availabilitymentioning

confidence: 99%

Optimal thermodynamic conditions to minimize kinetic by-products in aqueous materials synthesis

Wang,

Sun,

Cruse

et al. 2024

Nat. Synth

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Phase diagrams offer substantial predictive power for materials synthesis by identifying the stability regions of target phases. However, thermodynamic phase diagrams do not offer explicit information regarding the kinetic competitiveness of undesired by-product phases. Here we propose a quantitative and computable thermodynamic metric to identify synthesis conditions under which the propensity to form kinetically competing by-products is minimized. We hypothesize that thermodynamic competition is minimized when the difference in free energy between a target phase and the minimal energy of all other competing phases is maximized. We validate this hypothesis for aqueous materials synthesis through two empirical approaches: first, by analysing 331 aqueous synthesis recipes text-mined from the literature; and second, by systematic experimental synthesis of LiIn(IO3)4 and LiFePO4 across a wide range of aqueous electrochemical conditions. Our results show that even for synthesis conditions that are within the stability region of a thermodynamic Pourbaix diagram, phase-pure synthesis occurs only when thermodynamic competition with undesired phases is minimized.

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