Biomimetic versus enzymatic high-potential electrocatalytic reduction of hydrogen peroxide on a functionalized carbon nanotube electrode† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc01473e Click here for additional data file.

We report the non-covalent functionalization of a multi-walled carbon nanotube (MWCNT) electrode with a biomimetic model of the horseradish peroxidase (HRP) active site. By modifying the MWCNT electrode surface with imidazole-modified polypyrrole, a new biomimetic complex of HRP was synthesized on the MWCNT sidewalls via the coordination of imidazole (Im) to the metal centre of iron protoporphyrin IX, affording (Im)(PP)Fe. Compared to the pi-stacking of non-coordinated (PP)Fe on a MWCNT electrode, the (Im)(PP)Fe-modified MWCNT electrode exhibits higher electrocatalytic activity with an Imax 1⁄4 0.52 mA cm 2 for the reduction of H2O2, accompanied by a high onset potential of 0.43 V vs. Ag/AgCl. The performances of these novel surface-confined HRP mimics were compared to those of a MWCNT electrode modified by HRP. Although the enzyme electrode displays a higher electrocatalytic activity towards H2O2 reduction, the (Im)(PP)Fe -modified MWCNT electrode exhibits a markedly higher operational stability, retaining 63% of its initial activity after one month.