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Published December 11, 2013 | Supplemental Material
Journal Article Open

Noncovalent Immobilization of Electrocatalysts on Carbon Electrodes for Fuel Production


We show that molecular catalysts for fuel-forming reactions can be immobilized on graphitic carbon electrode surfaces via noncovalent interactions. A pyrene-appended bipyridine ligand (P) serves as the linker between each complex and the surface. Immobilization of a rhodium proton-reduction catalyst, [Cp*Rh(P)Cl]Cl (1), and a rhenium CO_2-reduction catalyst, Re(P)(CO)_3Cl (2), afford electrocatalytically active assemblies. X-ray photoelectron spectroscopy and electrochemistry confirm catalyst immobilization. Reduction of 1 in the presence of p-toluenesulfonic acid results in catalytic H_2 production, while reduction of 2 in the presence of CO_2 results in catalytic CO production.

Additional Information

© 2013 American Chemical Society. Received: September 26, 2013. Publication Date (Web): November 18, 2013. The authors thank Peter Agbo for helpful discussions regarding surface preparation and David Lacy for assistance with the GC product analysis. Research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and a CCI Postdoctoral Fellowship to J.D.B.

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