Thermodynamic Descriptors to Predict Oxide Formation in Aqueous Solutions

Walters, Lauren N.; Wang, Emily L.; Rondinelli, James M.

doi:10.1021/acs.jpclett.2c01173

Cited by 9 publications

(5 citation statements)

References 37 publications

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“…Importantly, this identifies a unique point in thermodynamic space for optimal materials synthesis-in contrast with a stability region from the thermodynamic phase diagram. We note here that a similar concept based on "maximum driving force" was recently proposed by Walters and Rondinelli for determination of which oxide phases form to protect against metal corrosion [20].…”

Section: Introductionmentioning

confidence: 69%

Optimal thermodynamic conditions to minimize kinetic byproducts in aqueous materials synthesis

Wang

Sun

Cruse

et al. 2023

Preprint

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Thermodynamics has strong predictive power for materials synthesis by identifying the stability region of target phases, but does not give explicit information about the relative competitiveness of undesired byproduct phases in synthesis. In this work, we propose a quantitative and computable measure to guide the selection of synthesis conditions. Defining thermodynamic competition as the difference in driving force between a target phase and its competing phases, we hypothesize that phase-pure synthesis becomes more likely when this thermodynamic competition is minimized. We systematically validate this hypothesis with two approaches: (1) we analyze large-scale solution synthesis procedures as text-mined from the literature, and show that experimentally-optimized synthesis conditions are near the predicted thermodynamic optimum point, and (2) direct experimental evaluation of synthesis in LiIn(IO3)4 and LiFePO4, which show that phase-pure synthesis occurs only when thermodynamic competition is minimized. Our work demonstrates that a quantitative assessment of thermodynamic competition is an effective descriptor for synthesis optimization and a promising tool for optimizing aqueous solution-based experimental synthesis conditions.

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Section: Introductionmentioning

confidence: 69%

Optimal thermodynamic conditions to minimize kinetic byproducts in aqueous materials synthesis

Wang

Sun

Cruse

et al. 2023

Preprint

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“…1b-in contrast with a stability region from the thermodynamic phase diagram. A similar concept based on maximum driving force was recently proposed by Walters and Rondinelli for determination of which oxide phases form to protect against metal corrosion 20 .…”

Section: Thermodynamic Competition In Aqueous-solution-based Systemsmentioning

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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“…Importantly, the oxide boundary can be shifted because of the re-actions, but the key factor of the actual oxide layer growth is the diffusion of copper atoms from the top of the Cu 2 O oxide surface to the top surface of CuO oxide, where the generation of a new CuO oxide layer occurs (Figure 2). [47,48] This key process was modeled in three stages: i) dissociation of the cuprous oxide, ii) jump of the released copper atom into the neighboring node occupied by the cupric oxide, and iii) the generation of the cuprous oxide in the new location of the copper atom (see details in the Supporting Information).…”

Section: General Description Of the Modelmentioning

confidence: 99%

Hierarchical Nanomaterials by Selective Deposition of Noble Metal Nanoparticles: Insight into Control and Growth Processes

Baranov

Belmonte

Levchenko

et al. 2023

Advcd Theory and Sims

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Complex hierarchical metamaterials are currently the focus of many cutting‐edge studies due to their potential to advance such critically important areas of technology as energy storage and transformation, sensing, photovoltaics, nano‐medicine, antibacterial and self‐regenerating materials. However, the deterministic design of novel hierarchical metamaterials remains problematic due to the lack of efficient, highly reliable methods for controlling the internal structure and architecture of materials. A comprehensive advanced model is proposed to simulate the formation of complex hierarchical metamaterials with a controllable structure. The control is achieved via selective deposition of noble metal nanoparticles (Au, Au, Pd, Pt). Moreover, the novel method for the nanofabrication is theoretically examined and experimentally verified. This approach allows for the sophisticated spatiotemporal control of growth conditions and, as a result, achieving the targeted internal structure of metamaterials. This opens a way to the deterministic design and formation of complex multi‐material metamaterials on the basis of metal oxides and noble metal nanoparticles. Moreover, a fundamental insight related to the longstanding question about the prevalence of bottom‐up versus top‐down growth for various materials and systemswhich is challenging to directly verify experimentally is presented.

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Thermodynamic Descriptors to Predict Oxide Formation in Aqueous Solutions

Cited by 9 publications

References 37 publications

Optimal thermodynamic conditions to minimize kinetic byproducts in aqueous materials synthesis

Optimal thermodynamic conditions to minimize kinetic byproducts in aqueous materials synthesis

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

Hierarchical Nanomaterials by Selective Deposition of Noble Metal Nanoparticles: Insight into Control and Growth Processes

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