In situ identification of kinetic factors that expedite inorganic crystal formation and discovery

Jiang, Zhelong; Ramanathan, Arun; Shoemaker, Daniel P.

doi:10.1039/c6tc04931a

Cited by 34 publications

(39 citation statements)

References 57 publications

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“…However, high temperatures also lead to the ripening of large particles, which eliminates interfaces and thereby reduces reaction kinetics. 3 Because of these often conflicting constraints, solid-state synthesis occasionally proceeds with slow reaction kinetics, non-equilibrium intermediates, or impurities, [4][5][6] which hinder the phase-pure synthesis of a desired target material.…”

Section: Introductionmentioning

confidence: 99%

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces

et al. 2020

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“…Solid-state reactions involve coupled transformations of chemistry and structure that can be complex to disentangle. Insight into the mechanism and pathway for such reactions can be obtained by characterizing how the structure, chemistry and abundance of the multiple crystalline reagents, intermediates, products, impurities and polymorphs thereof evolve as a function of time and reaction temperature using in situ X-ray scattering (Jiang et al, 2017;Martinolich & Neilson, 2017;Shoemaker et al, 2012;Todd et al, 2019).…”

Section: Solid-state Reaction: Metathesismentioning

confidence: 99%

A thermal-gradient approach to variable-temperature measurements resolved in space

et al. 2020

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Temperature is a ubiquitous environmental variable used to explore materials structure, properties and reactivity. This article reports a new paradigm for variable-temperature measurements that varies the temperature continuously across a sample such that temperature is measured as a function of sample position and not time. The gradient approach offers advantages over conventional variable-temperature studies, in which temperature is scanned during a series measurement, in that it improves the efficiency with which a series of temperatures can be probed and it allows the sample evolution at multiple temperatures to be measured in parallel to resolve kinetic and thermodynamic effects. Applied to treat samples at a continuum of temperatures prior to measurements at ambient temperature, the gradient approach enables parametric studies of recovered systems, eliminating temperaturedependent structural and chemical variations to simplify interpretation of the data. The implementation of spatially resolved variable-temperature measurements presented here is based on a gradient-heater design that uses a 3Dprinted ceramic template to guide the variable pitch of the wire in a resistively heated wire-wound heater element. The configuration of the gradient heater was refined on the basis of thermal modelling. Applications of the gradient heater to quantify thermal-expansion behaviour, to map metastable polymorphs recovered to ambient temperature, and to monitor the time-and temperaturedependent phase evolution in a complex solid-state reaction are demonstrated.

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Section: Introductionmentioning

confidence: 99%

Selective Metathesis Synthesis of MgCr2S4 by Control of Thermodynamic Driving Forces

Miura

Ito

Bartel

et al. 2019

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MgCr2S4 thiospinel is predicted to be a compelling Mg-cathode material, but its preparation via traditional solid-state synthesis methods has proven challenging. Wustrow et al. [Inorg. Chem. 57, 14 (2018)] found that the formation of MgCr2S4 from MgS + Cr2S3 binaries requires weeks of annealing at 800 ℃ with numerous intermediate regrinds. The slow reaction kinetics of MgS + Cr2S3 à MgCr2S4 can be attributed to a miniscule thermodynamic driving force of ΔH = -2 kJ/mol. Here, we demonstrate that the double ion-exchange metathesis reaction, MgCl2 + 2 NaCrS2 à MgCr2S4 + 2 NaCl, has a reaction enthalpy of ΔH = -47 kJ/mol, which is thermodynamically driven by the large exothermicity of NaCl formation. Using this metathesis reaction, we successfully synthesized MgCr2S4 nanoparticles (< 200 nm) from MgCl2 and NaCrS2 precursors in a KCl flux at 500 °C in only 30 minutes. NaCl and other metathesis byproducts are then easily washed away by water. We rationalize the selectivity of MgCr2S4 in the metathesis reaction from the topology of the DFT-calculated pseudo-ternary MgCl2-CrCl3-Na2S phase diagram. Our work helps to establish metathesis reactions as a powerful alternative synthesis route to inorganic materials that have otherwise small reaction energies from conventional precursors.

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In situ identification of kinetic factors that expedite inorganic crystal formation and discovery

Abstract: In situ X-ray diffraction reveals key processes that can be utilized to direct the synthesis of complex inorganic crystals.

Cited by 34 publications

References 57 publications

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces

A thermal-gradient approach to variable-temperature measurements resolved in space

Selective Metathesis Synthesis of MgCr2S4 by Control of Thermodynamic Driving Forces

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In situ identification of kinetic factors that expedite inorganic crystal formation and discovery

Abstract: In situ X-ray diffraction reveals key processes that can be utilized to direct the synthesis of complex inorganic crystals.

Cited by 34 publications

References 57 publications

Selective metathesis synthesis of MgCr2S4 by control of thermodynamic driving forces

Selective metathesis synthesis of MgCr2S4 by control of thermodynamic driving forces

A thermal-gradient approach to variable-temperature measurements resolved in space

Selective Metathesis Synthesis of MgCr2S4 by Control of Thermodynamic Driving Forces

Contact Info

Product

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About

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces

Selective metathesis synthesis of MgCr₂S₄ by control of thermodynamic driving forces