Electrophoretic Deposition of Hybrid Calcium Alginate-Gold Nanoparticle Hydrogel Films via Catalyzed Electrooxidation of Hydroquinone

Abstract

The electrophoretic deposition (EPD) of hybrid alginate (Alg)-Au nanoparticle (NP) films results from the localized pH drop at the electrode surface due to oxidation of hydroquinone (HQ) catalyzed by 4 and 15 nm diameter citrate-coated gold NPs (cit-Au NPs). The localized pH drop at the electrode leads to neutralization of both Alg and cit, leading to EPD of both Alg and cit-Au NPs simultaneously. Post-treatment of the film with Ca2+ solution leads to hybrid Ca-Alg-Au NP hydrogel films. The EPD of Alg in the presence of 4 nm cit-Au NPs occurs at ∼0.8 V (vs Ag/AgCl) as compared to ∼1.0 V in the presence of 15 nm cit-Au NPs and ∼1.4 V in the absence of cit-Au NPs. This is due to the higher catalytic activity of 4 nm cit-Au NPs compared to 15 nm cit-Au NPs for the oxidation of HQ. UV-vis spectra of Ca-Alg-Au NP hydrogel films show absorbance features for both Ca-Alg and Au NPs entrapped within the hydrogel. As the concentration of Au NPs in the EPD solution increases, the Ca-Alg absorbance and localized surface plasmon resonance (LSPR) peak of the Au NPs increases, confirming the role of the Au NPs as a catalyst for EPD of Alg. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of the Ca-Alg-Au NP hydrogel films show characteristic peaks for Ca-Alg and protonated alginic acid groups. The hydrogel thickness is greater with cit-Au NPs compared to without cit-Au NPs at constant EPD potential and time. Forming Ca-Alg and hybrid Ca-Alg-Au NP hydrogel films at low potentials has potential applications in electrochemical and optical sensor development, catalysis, and biological studies.