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Reduction of Alkenes: Catalytic Hydrogenation02:13

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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.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
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In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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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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Hydrogen Bonds01:04

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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Stacking Fault-Enriched MoNi4/MoO2 Enables High-Performance Hydrogen Evolution.

Yuan Wang1, Hamidreza Arandiyan2,3, Sajjad S Mofarah4

  • 1Department of Chemical Engineering, The University of Melbourne, Parkville, VIC, 3010, Australia.

Advanced Materials (Deerfield Beach, Fla.)
|June 13, 2024
PubMed
Summary
This summary is machine-generated.

Researchers developed a novel non-platinum catalyst (d-MoNi) using stacking fault defects for efficient green hydrogen production via water electrolysis. This breakthrough offers a cost-effective and sustainable alternative to platinum catalysts for the hydrogen economy.

Keywords:
MoNi alloydefecthigh current densityhydrogen evolution reactionstacking fault

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Green Chemistry

Background:

  • Cost-effective green hydrogen production via water electrolysis is crucial for a sustainable hydrogen economy.
  • Platinum-based catalysts, while effective for the hydrogen evolution reaction (HER), are limited by high cost and scarcity.
  • Developing non-precious metal catalysts is essential for economic viability.

Purpose of the Study:

  • To engineer a high-performance, non-platinum electrocatalyst for the hydrogen evolution reaction (HER).
  • To investigate the role of stacking fault (SF) defects in enhancing HER activity.
  • To provide a new synthetic strategy for defective metal alloy electrocatalysts.

Main Methods:

  • A combined chemical and thermal reduction strategy was employed to create MoNi4/MoO2 nanosheets with high fractions of stacking fault (SF) defects (d-MoNi).
  • Electrochemical performance for HER was evaluated using overpotentials at various current densities in 1 M KOH.
  • Catalyst activity and durability were compared against a benchmark platinum catalyst (20% Pt/C).
  • Density Functional Theory (DFT) calculations were used to understand the mechanism of defect-enhanced HER activity.

Main Results:

  • The d-MoNi catalyst demonstrated ultralow overpotentials for HER (78 mV at 500 mA cm-2 and 121 mV at 1000 mA cm-2).
  • The defect-rich catalyst exhibited four times higher turnover frequency than 20% Pt/C.
  • Excellent durability (> 100 hours) was observed, positioning d-MoNi as a leading non-Pt HER catalyst.
  • Abundant SFs were found to induce compressive strain, optimizing proton adsorption and hydrogen desorption.

Conclusions:

  • Engineered stacking fault defects in MoNi4/MoO2 nanosheets create a highly active and durable non-platinum catalyst for the hydrogen evolution reaction.
  • The d-MoNi catalyst presents a promising, cost-effective alternative to platinum for green hydrogen production.
  • This work offers a viable synthetic route for developing advanced electrocatalysts for energy conversion applications.