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Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
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Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
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Ethers are generally unreactive and unsuitable for direct nucleophilic substitution reactions since the alkoxy groups are strong bases and, therefore, poor leaving groups. However, ethers readily undergo acidic-cleavage reactions. Ethers can be converted to alkyl halides when heated with strong acids such as HBr and HI in a sequence of two substitution reactions.
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Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
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The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
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SN2 substitutions and E2 eliminations of alkyl halides proceed via a concerted pathway. While the nucleophile attacks the alpha carbon in SN2 reactions, it functions as a strong base and abstracts a beta hydrogen in the E2 mechanism. The rate-limiting transition state in E2 elimination reactions is characterized by partially broken carbon–hydrogen and carbon–halogen bonds and a partially formed pi bond between the alpha and beta carbons. The beta hydrogen and halide are eliminated...
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Elementary processes governing V2AlC chemical etching in HF.

Youngsoo Kim1,2, Athanasios Gkountaras2,3, Odette Chaix-Pluchery2

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Chemical exfoliation of V2AlC to MXene occurs through edges, not basal planes. This process is isotropic and slows significantly after ~45 μm, offering insights into MXene synthesis.

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Chemistry

Background:

  • MXenes are a significant class of 2D materials.
  • Understanding MXene chemical exfoliation from MAX phases is crucial.
  • Well-defined structures are needed to study exfoliation mechanisms.

Purpose of the Study:

  • Investigate the chemical exfoliation of V2AlC to MXene.
  • Determine the kinetics and spatial resolution of MXene conversion.
  • Clarify the role of crystal orientation in exfoliation.

Main Methods:

  • Utilized well-defined square pillars of V2AlC (7-500 μm).
  • Employed Raman spectroscopy, scanning electron microscopy, and optical microscopy.
  • Assessed MXene conversion kinetics with μm spatial resolution.

Main Results:

  • HF penetration and Al loss occur primarily through the edges of V2AlC pillars.
  • No significant etching observed through basal planes at room temperature.
  • Etching rate is initially linear (2.2 ± 0.3 μm h⁻¹) and isotropic in defect-free pillars.
  • Etching rate diminishes significantly beyond ~45 μm.

Conclusions:

  • Chemical exfoliation of V2AlC to MXene is predominantly an edge-driven process.
  • Basal plane etching by HF is negligible under studied conditions.
  • The findings provide critical insights into controlling MXene synthesis and properties.