Covalent attachment of [Ni(alkynyl-cyclam)]2+ catalysts to glassy carbon electrodes.

@article{Zhanaidarova2018CovalentAO,
  title={Covalent attachment of [Ni(alkynyl-cyclam)]2+ catalysts to glassy carbon electrodes.},
  author={Almagul Zhanaidarova and Curtis E. Moore and Milan Gembicky and Clifford P. Kubiak},
  journal={Chemical communications},
  year={2018},
  volume={54 33},
  pages={
          4116-4119
        }
}
Surface modification of glassy carbon electrodes (GCEs) with molecular electrocatalysts is an important step towards developing more efficient heterogeneous CO2 reduction materials. Here, we report direct anodic electrografting of [Ni(alkynyl-cyclam)]2+ catalysts to the surface of GCEs in one simple step using inexpensive earth-abundant chemicals. When modified, these electrodes show reversible electrochemistry in organic solvents with zero peak-to-peak separations (ΔE = 0) and non-diffusive I… 
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22 Citations

22 Citations

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Citation Type

Noncovalent Immobilization of a Nickel Cyclam Catalyst on Carbon Electrodes for CO2 Reduction Using Aqueous Electrolyte
Functionalization of Carbon Nanotubes with Nickel Cyclam for the Electrochemical Reduction of CO2.
TLDR
A Ni-cyclam complex, with a cyclam derivative functionalized with a pyrene moiety, was synthesized, shown to be a selective catalyst for CO 2 electroreduction to CO and immobilized on a carbon nanotube-coated gas diffusion electrode by using a non-covalent binding strategy.
Anodic Oxidation of Ethynylferrocene Derivatives in Homogeneous Solution and Following Anodic Deposition onto Glassy Carbon Electrodes
Eight ferrocene derivatives linked by either an ether, amine, or phenylacetylene moiety to a terminal ethynyl group were covalently deposited on glassy carbon electrodes by anodic electrochemical…
The effect of extended conjugation on electrocatalytic CO2 reduction by molecular catalysts and macromolecular structures
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Electrocatalytic CO2 reduction by heterogeneous molecular catalysts is emerging as an important area for CO2 utilization. Unlike commonly used solid heterogeneous catalysts, molecular catalysts…
Design of robust 2,2'-bipyridine ligand linkers for the stable immobilization of molecular catalysts on silicon(111) surfaces.
TLDR
The results suggest that use of reductively stable linkers can enable robust attachment of catalysts while maintaining chemical behavior on the electrode similar to that exhibited in homogeneous solution.
Re(tBu-bpy)(CO)3Cl supported on multi-walled carbon nanotubes selectively reduces CO2 in water.
TLDR
Supporting Re(tBu-bpy)(CO)3Cl on MWCNTs increases current den-sities, decreases overpotential, retains selectivity for reduction of CO2 to CO, and allows operation in water at pH = 7.3 compared to the molecular catalyst in acetonitrile solution.
Heterogeneous electrocatalytic reduction of carbon dioxide with transition metal complexes
Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials.
TLDR
The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO2 reduction.
Electrochemical reduction of CO2 to CO and HCOO- using metal-cyclam complex catalysts: predicting selectivity and limiting potential from DFT.
TLDR
This work computed the reaction free energies of electrocatalytic reduction of CO2 to CO and HCOO- using the density functional theory method and screened transition metal(M)-cyclam(L) complexes as molecular catalysts for CO2 reduction to show that pKa of the proton adduct can be used as a descriptor to select the operating pH of the solution to steer the reaction toward either the CO or hydride cycle.
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