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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.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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Heterogeneous Catalysis

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Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
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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.
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Catalysis

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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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Introduction
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Optimizing conditions for utilization of an H2 oxidation catalyst with outer coordination sphere functionalities.

Arnab Dutta1, Bojana Ginovska1, Simone Raugei1

  • 1Pacific Northwest National Laboratory, Richland, WA 99352, USA. Wendy.shaw@pnnl.gov.

Dalton Transactions (Cambridge, England : 2003)
|February 25, 2016
PubMed
Summary
This summary is machine-generated.

This study introduces a nickel-based hydrogen oxidation complex (CyArg) that achieves record-breaking speed for homogeneous electrocatalysis. Optimal conditions in acidic water demonstrate its potential for fuel cell technologies.

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Materials Science

Background:

  • Hydrogen oxidation is crucial for energy conversion.
  • Developing efficient homogeneous electrocatalysts is key for renewable energy applications.
  • Nickel-based complexes offer potential for cost-effective catalysis.

Purpose of the Study:

  • To investigate an efficient and reversible Ni-based H2 oxidation and production complex, [Ni(P(Cy)2N(Arginine)2)2](7+) (CyArg).
  • To evaluate the complex's performance under varying conditions (pressure, temperature, solvent).
  • To identify optimal conditions for simultaneous improvements in rate and overpotential for H2 oxidation.

Main Methods:

  • Electrochemical testing of the CyArg complex.
  • Systematic variation of temperature, pressure, and solvent (methanol, water).
  • Kinetic analysis and comparison with a control complex ([Ni(P(Cy)2N(Benzyl)2)2](2+), CyBn).

Main Results:

  • Optimal performance achieved at 72 °C and 100 atm H2 in acidic aqueous solution (pH = 1).
  • Record turnover frequency (TOF) of 1.1 × 10^6 s^-1 at 240 mV overpotential for H2 oxidation.
  • Significantly lower TOF (280 s^-1) and higher overpotential (750 mV) observed in methanol, suggesting a change in the rate-limiting step.

Conclusions:

  • The CyArg complex demonstrates exceptional catalytic activity for H2 oxidation under specific conditions.
  • Optimal conditions (elevated temperature, acidic aqueous solution) are compatible with fuel cell technologies.
  • This work advances the implementation of homogeneous synthetic catalysts for renewable energy.