Zinc phthalocyanine and silver/gold nanoparticles incorporated MCM-41 type materials as electrode modifiers

Manas Pal, Vellaichamy Ganesan
Langmuir: the ACS Journal of Surfaces and Colloids 2009 November 17, 25 (22): 13264-72
Mercaptopropyl functionalized ordered mesoporous silica spheres were prepared (MPS). Ag or Au nanoparticles (NPs) were anchored onto the MPS materials (Ag-MPS or Au-MPS). Further, zinc phthalocyanine (ZnPc) was adsorbed into the channels and surface (MPS-ZnPc, Ag-MPS-ZnPc, Au-MPS-ZnPc). Diffuse reflectance studies revealed the successful incorporation of Ag or Au NPs inside the silica spheres with and without ZnPc. TEM images showed the uniform distribution of Ag or Au NPs in the silica spheres of different size ranging from 4 to 22 nm or 6 to 31 nm, respectively. XRD pattern showed average crystallite particle size of 18 or 28 nm for Ag or Au NPs respectively which were reduced to 14 or 16 nm on introduction of ZnPc which oxidizes the metal NPs partially. Chemically modified electrodes were prepared by coating the colloidal solutions of the silica materials on the glassy carbon (GC) electrodes. Electrocatalytic reductions of O(2) and CO(2) at the modified electrodes were studied. The presence of Ag or Au NPs was found to increase the electrocatalytic efficiency of ZnPc toward O(2) reduction by 290% or 70% based on the current density measured at -0.35 V and toward CO(2) reduction by 150% or 120% based on the current density measured at -0.60 V respectively. Catalytic rate constants were increased 2-fold for O(2) reduction and 8-fold for CO(2) reduction due to Ag or Au NPs, respectively, which act as nanoelectrode ensembles. The synergic effect of ZnPc and metal NPs on the electrocatalytic reduction of O(2) is presented.

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