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Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
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Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
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Catalysis02:50

Catalysis

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The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
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Introduction
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Simple aryl halides do not react with nucleophiles under normal conditions. However, the reaction can proceed under drastic conditions involving high temperatures and high pressure to give the substituted products. For example, chlorobenzene is converted to phenol using aqueous sodium hydroxide at 350 °C under high pressure by the Dow process. The reaction follows an elimination-addition mechanism involving a benzyne intermediate. Here, the chloride ion is...
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Defective Biphenylene as High-Efficiency Hydrogen Evolution Catalysts.

Yi Luo1,2, Yiqiang He1, Yunfei Ding1

  • 1School of Mechanical Engineering, Jiangsu Ocean University, Lianyungang 222005, China.

Inorganic Chemistry
|December 31, 2023
PubMed
Summary
This summary is machine-generated.

Defective biphenylenes show great promise as metal-free electrocatalysts for water splitting. Engineered defects significantly boost hydrogen evolution reaction efficiency, outperforming platinum in key metrics for sustainable hydrogen production.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Sustainable Energy

Background:

  • Electrocatalysts are crucial for efficient water splitting and hydrogen production.
  • Developing cost-effective, high-performance catalysts is essential for sustainable energy solutions.
  • Metal-free catalysts offer an alternative to precious metal-based materials.

Purpose of the Study:

  • To investigate the potential of defective biphenylenes as electrocatalysts for the hydrogen evolution reaction (HER).
  • To evaluate the impact of defect engineering on the catalytic activity and stability of biphenylene-based materials.
  • To explore novel, earth-abundant carbon-based catalysts for sustainable hydrogen production.

Main Methods:

  • First-principles simulations were employed to systematically study the structure, stability, and electronic properties of defective biphenylenes.
  • Calculations assessed the Gibbs free energy and exchange current density for the hydrogen evolution reaction.
  • The preferred reaction mechanism (Volmer-Heyrovsky) and its energy barrier were determined.

Main Results:

  • Biphenylene with a double-vacancy defect demonstrated superior electrocatalytic activity for HER compared to platinum.
  • The defective biphenylene exhibited a Gibbs free energy of -0.08 eV and an exchange current density of -3.08 A cm⁻².
  • A low energy barrier of 0.80 eV was identified for the Volmer-Heyrovsky mechanism in the hydrogen evolution reaction.

Conclusions:

  • Defect engineering in biphenylenes significantly enhances electrocatalytic performance for hydrogen evolution.
  • Defective biphenylenes represent a promising class of metal-free, carbon-based electrocatalysts.
  • This research offers a viable pathway towards sustainable and cost-effective hydrogen production via water splitting.