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Related Concept Videos

Photochemical Electrocyclic Reactions: Stereochemistry01:26

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Two-Dimensional Functionalized Germananes as Photoelectrocatalysts.

Siowwoon Ng1, Jiri Sturala2, Jan Vyskocil3

  • 1Future Energy and Innovation Laboratory, Central European Institute of Technology, Brno University of Technology, Purkyňova 123, 61200 Brno, Czech Republic.

ACS Nano
|June 14, 2021
PubMed
Summary
This summary is machine-generated.

Organic functionalization of 2D germananes enhances their performance in energy conversion. Specific functional groups on germanane materials optimize hydrogen evolution and water oxidation reactions for catalysis.

Keywords:
band gapcovalent functionalizationdensity functional theoryformation energygroup 14layered materialsphotoelectrochemistry

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Catalysis

Background:

  • Monoelemental two-dimensional (2D) materials, or 'Xenes' like germanene, are gaining interest.
  • Germanane (GeH), hydrogen-terminated germanene, offers tunable properties via covalent functionalization.
  • Applications of germananes in energy conversion catalysis remain largely unexplored.

Purpose of the Study:

  • To synthesize and investigate functionalized germananes for photo- and electrocatalysis.
  • To explore the impact of organic functionalization on germanane properties for energy applications.
  • To evaluate germananes in hydrogen evolution and water oxidation reactions.

Main Methods:

  • Synthesis of germanane and its derivatives with various alkyl chains.
  • Density functional theory (DFT) calculations for structural, energetic, and electronic properties.
  • Electrochemical testing of functionalized germananes as photoelectrocatalysts.

Main Results:

  • Functionalization significantly influences the properties and catalytic performance of germananes.
  • Germanane with a hydroxypropyl (-CH2CH2CH2OH) termination showed the lowest overpotentials for hydrogen evolution.
  • Germanane with hydrogen (-H) termination achieved the highest photocurrent densities for visible-light water oxidation.

Conclusions:

  • Organic functionalization is a viable strategy to tune 2D germananes for enhanced photo- and electrochemical energy conversion.
  • Specific functional groups can be tailored to optimize catalytic activity for hydrogen evolution and water oxidation.
  • This approach can be extended to other 'Xenes' for advanced energy applications.