Felio Perez

Flower-shaped cobalt oxide nano-structures as an efficient, flexible and stable electrocatalyst for the oxygen evolution reaction

The industrial application of water splitting for oxygen evolution requires low cost, high performance and stable electrocatalysts which can operate at low overpotential. Here, we develop a high performance and stable electrocatalyst for the oxygen evolution reaction (OER) using earth abundant materials. A binder free approach for the synthesis of flower-shaped cobalt oxide (Co3O4) composed of nanosheets showed high OER catalytic activity. The Co3O4 electrode requires a low overpotential of 356 mV to achieve a current density of 10 mA cm−2 with a low onset potential of 284 mV. The electrode showed outstanding flexibility and stability. The catalytic activity of the Co3O4 electrode was very stable up to the 2000th cycle of the polarization study. The high catalytic activity and structural stability arise due to efficient and fast charge transportation through the nanosheets of Co3O4 which are in direct contact with the conducting nickel of the electrode. The porous structure of Co3O4 allows easy access of the electrolyte and escape of generated oxygen without damaging the structure. Collectively, the flower-shaped nanostructured Co3O4 electrode can be used as a flexible and high performance electrode for the OER in an industrial setup.

PEDOT(PSS) as solid contact for ion-selective electrodes: the influence of the PEDOT(PSS) film thickness on the equilibration times

To understand the rate determining processes during the equilibration of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate-based (PEDOT(PSS)-based) solid contact (SC) ion-selective electrodes (ISEs), the surfaces of Pt, Au, and GC electrodes were coated with 0.1, 1.0, 2.0, and 4.0 μm thick galvanostatically deposited PEDOT(PSS) films. Next, potential vs time transients were recorded with these electrodes, with and without an additional potassium ion-selective membrane (ISM) coating, following their first contact with 0.1 M KCl solutions. The transients were significantly different when the multilayered sensor structures were assembled on Au or GC compared to Pt. The differences in the rate of equilibration were interpreted as a consequence of differences in the hydrophilicity of PEDOT(PSS) in contact with the substrate electrode surfaces based on X-ray photoelectron spectroscopy (XPS) and synchrotron radiation-XPS (SR-XPS) analysis of 10-100 nm thick PEDOT(PSS) films. The influence of the layer thickness of the electrochemically deposited PEDOT(PSS)-films on the hydrophilicity of these films has been documented by contact angle measurements over PEDOT(PSS)-coated Au, GC, and Pt electrode surfaces. This study demonstrates that it is possible to minimize the equilibration (conditioning) time of SC ISEs with aqueous solutions before usage by optimizing the thickness of the SC layer with a controlled ISM thickness. PEDOT(PSS)-coated Au and GC electrodes exhibit a significant negative potential drift during their equilibration in an aqueous solution. By coating the PEDOT(PSS) surface with an ISM, the negative potential drift is compensated by a positive potential drift related to the hydration of the ISM and activity changes at the PEDOT(PSS)|ISM interface. The potential drifts related to activity changes in the ISM have been determined by a novel adaptation of the sandwich membrane method.

Facile displacement of citrate residues from gold nanoparticle surfaces

The stability of citrate-residues on gold nanoparticles (AuNPs) against ligand displacement has been controversial. Using AuNPs synthesized with deuterated citrate in combination with in-situ surface-enhanced Raman spectroscopic (SERS) analysis, we report that both citrate-residues and solution impurities can be simultaneously adsorbed onto citrate-reduced AuNPs in solution. The citrate-residues can be readily displaced from AuNPs by organosulfur such as organothiols (RS-H), organodisuflide (R-S-S-R), and non-specific ligands including halides and adenine. Control experiments conducted on high-purity gold films sputter-coated onto silicone substrates indicate that air-borne and solvent-borne impurities rapidly contaminate the gold surfaces. Head-to-head comparison of ligand-functionalized AuNPs by in-situ SERS measurements verses those from the ex-situ X-ray photoelectron spectroscopic (XPS) measurements reveal that the impurity deposition can compromise the reliability of ex-situ XPS identification of surface adsorbates on AuNPs in solution. These insights are of general significance to nanoscience research given the broad interest in nanoparticle surface chemistry and popularity of XPS for nanomaterial characterizations.