Surface transformation thermodynamics of alkaline earth carbonates using first-principles calculations

Grimes, Ryan T.; Bennett, Joseph W.

doi:10.1016/j.susc.2022.122165

Cited by 6 publications

(5 citation statements)

References 79 publications

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“…The first step starts with an A-terminated ABX surface, and the alkali metal A is exchanged with a proton to simulate reactivity in a humid environment or saturated interface. This A/H exchange was previously shown to be favorable for oxide-based materials such as LiCoO 2 , PbO, and PbCO 3 ; ,,,, however, this is the first time that both cation exchange and monolayer formation have been studied for pnictides using the DFT + Solvent Ion method.…”

Section: Methodsmentioning

confidence: 88%

“…The first step starts with an Aterminated ABX surface, and the alkali metal A is exchanged with a proton to simulate reactivity in a humid environment or saturated interface. This A/H exchange was previously shown to be favorable for oxide-based materials such as LiCoO 2 , PbO, and PbCO 3 ; 39,41,62,65,66 however, this is the first time that both cation exchange and monolayer formation have been studied for pnictides using the DFT + Solvent Ion method. Prior computational work on the liquid phase exfoliation of 2D materials such as boron nitride, graphene, phosphorene, and molybdenum disulfide, using molecular dynamics simulations, showed that experimentally controllable parameters such as relative surface and solvent polarities, solvent size, and diffusion coefficients resulted in (a) different types of solvent layering effects, (b) adjusted electrostatic interactions, and (c) distinct preferences for exfoliation mechanisms (e.g., shearing vs pulling).…”

Section: ■ Introductionmentioning

confidence: 86%

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Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Layegh

Bennett

2023

J. Phys. Chem. C

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During the past decade, two-dimensional (2D) nanomaterials have provided a broad platform for a wide variety of applications and have been the focus of numerous studies due to their unique properties. The most common 2D materials are of hexagonal or trigonal symmetry, with structures that can be grown on inexpensive substrates like Si and sapphire. The ability to grow 2D materials on additional substrates with a larger variety of symmetries and surface terminations, such as metals, glass, and complex metal oxides, can be regarded as a big and necessary step in the design of new functional materials. However, there is a dearth of knowledge on 2D materials beyond hexagonal and trigonal symmetries, their synthesis, and epitaxy. Here, we present a procedure to rationalize the aqueous exfoliation of known 3D materials as a route to create stable tetragonal 2D materials with tunable lattice parameters and electronic structures. We develop a model using first-principles density functional theory plus thermodynamics to propose an ecofriendly synthesis of 2D materials using aqueous media and use it to investigate a class of previously synthesized tetragonal ABX compounds. Then, we predict the thermodynamics of their exfoliation in water by combining surface slab models, their subsequent surface transformations, and experimentally determined changes in free energy. The atomistic results obtained here are correlated to periodic properties and are used to elucidate trends in electronic structure and the thermodynamics of aqueous exfoliation.

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Section: Methodsmentioning

confidence: 88%

Section: ■ Introductionmentioning

confidence: 86%

Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Layegh

Bennett

2023

J. Phys. Chem. C

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“…The gas-phase catalytic dehydrochlorination of 1,1,2-TCE was carried out in the temperature range of 200–260 °C . The results are shown in Table and Figure a,b.…”

Section: Resultsmentioning

confidence: 99%

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

Ge,

Zhao,

Yuan

et al. 2024

Ind. Eng. Chem. Res.

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The heterogeneous catalytic splitting reaction of 1,1,2trichloroethane (1,1,2-TCE) was designed to study the process of catalyst deactivation. The results showed that the conversion of 1,1,2-TCE decreased from 51.34 to 44.01%, while the selectivity of vinylidene chloride decreased from 65.12 to 61.77% (260 °C, 8h), which indicated a decrease in catalyst activity. Solid-phase microextraction gas chromatography−mass spectrometry characterization was performed to confirm species on the surface of the spent catalyst. Density functional theory calculations revealed the essence of 1,1,2-TCE splitting to produce different products, and then a possible reaction network was proposed. Tandem side reactions occurred to generate chloroacetylene, which was an unstable species. Chloroacetylene selfpolymerized to form dichlorobutadiene and further polymerized to form aromatic compounds. The coke deposition precursors agglomerated on the surface of the active component, leading to catalyst deactivation. These conclusions explained the deactivation of the catalyst during 1,1,2-TCE dehydrochlorination, thus providing a theoretical basis for further research on methods to inhibit deactivation. Breaking through the key problem of catalyst deactivation would make it possible to replace the saponification reaction with catalytic dehydrochlorination in industry.

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“…In a study focused on LCO, DFT + solvent ion methodology was benchmarked using numerous DFT exchange–correlation functionals and in-plane surface supercell sizes . The methodology has been extended to newly proposed formulations of the cathode, lithiation states, and nanomaterials used in agriculture. − …”

Section: Introductionmentioning

confidence: 99%

Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni_1/3Mn_1/3Co_1/3)O₂: Insights from First-Principles

Hudson,

Jones,

Rivera Bustillo

et al. 2023

J. Phys. Chem. C

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The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(Ni x Mn y Co1‑x‑y)O2 (NMC), the mechanisms of chemical processes at the solid–water interface are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. The study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn.

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Surface transformation thermodynamics of alkaline earth carbonates using first-principles calculations

Cited by 6 publications

References 79 publications

Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni_1/3Mn_1/3Co_1/3)O₂: Insights from First-Principles

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Surface transformation thermodynamics of alkaline earth carbonates using first-principles calculations

Cited by 6 publications

References 79 publications

Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Density Functional Theory Combined with Thermodynamics Exploration of Novel 2D Materials Created Using Aqueous Exfoliation

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni1/3Mn1/3Co1/3)O2: Insights from First-Principles

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Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni_1/3Mn_1/3Co_1/3)O₂: Insights from First-Principles