Gold Nanoparticles/Carbon Nanotubes and Gold Nanoporous as Novel Electrochemical Platforms for L-Ascorbic Acid Detection: Comparative Performance and Application

Herein, the effects of nanostructured modifications of a gold electrode surface in the development of electrochemical sensors for L-ascorbic acid detection have been investigated. In particular, a bare gold electrode has been modified by electrodeposition of gold single-walled carbon nanotubes (Au/SWCNTs) and by the formation of a highly nanoporous gold (h-nPG) film. The procedure has been realized by sweeping the potential between +0.8 V and 0 V vs. Ag/AgCl for 25 scans in a suspension containing 5 mg/mL of SWCNTs in 10 mM HAuCl4 and 2.5 M NH4Cl solution for Au/SWCNTs modified gold electrode. A similar procedure was applied for a h-nPG electrode in a 10 mM HAuCl4 solution containing 2.5 M NH4Cl, followed by applying a fixed potential of −4 V vs. Ag/AgCl for 60 s. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the properties of the modified electrodes. The developed sensors showed strong electrocatalytic activity towards ascorbic acid oxidation with enhanced sensitivities of 1.7 × 10−2 μA μM−1cm−2 and 2.5 × 10−2 μA μM−1cm−2 for Au/SWCNTs and h-nPG modified electrode, respectively, compared to bare gold electrode (1.0 × 10−2 μA μM−1cm−2). The detection limits were estimated to be 3.1 and 1.8 μM, respectively. The h-nPG electrode was successfully used to determine ascorbic acid in human urine with no significant interference and with satisfactory recovery levels.

OPTIMISATION OF AN ELECTROCHEMICAL SENSOR BASED ON BARE GOLD ELECTRODE FOR DETECTION OF ALUMINIUM ION

In this work, an electrochemical method for detection of trace amount of aluminium (Al3+), a heavy metal ion, based on a bare gold electrode (AuE) was developed. Current responses of the AuE under various type of electrolytes, redox indicators, pH, scan rate and accumulation time were investigated using cyclic voltammetry (CV) method to obtain the optimum conditions for Al3+ detection. The sensing properties of the AuE towards the target ion with different concentrations were investigated using differential pulse voltammetry (DPV) method. From the CV results, the optimalconditions for the detection of Al3+ were Tris-HCl buffer (0.1 M, pH 2) supported by 5 mM Prussian blue with scan rate and accumulation time respectively of 100 mVs−1 and 15 s. Under the optimum conditions, the DPV method was detected with different concentrations of aluminium ion ranging from 0.2 to 1.0 ppm resulted in a good linear regression r² = 0.9806. This result suggests that the optimisation of the basic parameters in electrochemical detection using AuE is crucial before further modification of the Au-electrode to improve the sensitivity and selectivity especially for the low concentration of ion detection. The developed method has a great potential for rapid detection of heavy metal ion (Al3+) in drinking water samples.

Ion-specific Adsorption on Bare Gold (Au) Nanoparticles in aqueous Solution: Double-Layer Structure and Surface Potentials

We study the solvation and electrostatic properties of bare gold (Au) nanoparticles (NPs) of 1-2 nm in size in aqueous electrolyte solutions of sodium salts of various anions with large physicochemical diversity (Cl^-, BF₄^-, PF₆^-, Nip^-(nitrophenolate), 3- and 4-valent hexacyanoferrate (HCF)) using nonpolarizable, classical molecular dynamics computer simulations. We find a substantial facet selectivity in the adsorption structure and spatial distribution of the ions at the Au-NPs: while sodium and some of the anions (e.g., Cl^-, HCF^3-) adsorb more at the `edgy' (100) and (110) facets of the NPs, where the water hydration structure is more disordered, other ions (e.g., BF₄^-, PF₆^-, Nip^-) prefer to adsorb strongly on the extended and rather flat (111) facets. In particular, Nip^-, which features an aromatic ring in its chemical structure, adsorbs strongly and perturbs the first water monolayer structure on the NP (111) facets substantially. Moreover, we calculate adsorptions, radially-resolved electrostatic potentials, as well as the far-field <i>effective</i> electrostatic surface charges and potentials by mapping the long-range decay of the calculated electrostatic potential distribution onto the standard Debye-Hückel form. We show how the extrapolation of these values to other ionic strengths can be performed by an analytical Adsorption-Grahame relation between effective surface charge and potential. We find for all salts negative effective surface potentials in the range from -10 mV for NaCl down to about -80 mV for NaNip, consistent with typical experimental ranges for the zeta-potential. We discuss how these values depend on the surface definition and compare them to the explicitly calculated electrostatic potentials near the NP surface, which are highly oscillatory in the ± 0.5 V range. <br>

Ion-specific Adsorption on Bare Gold (Au) Nanoparticles in aqueous Solution: Double-Layer Structure and Surface Potentials

We study the solvation and electrostatic properties of bare gold (Au) nanoparticles (NPs) of 1-2 nm in size in aqueous electrolyte solutions of sodium salts of various anions with large physicochemical diversity (Cl^-, BF₄^-, PF₆^-, Nip^-(nitrophenolate), 3- and 4-valent hexacyanoferrate (HCF)) using nonpolarizable, classical molecular dynamics computer simulations. We find a substantial facet selectivity in the adsorption structure and spatial distribution of the ions at the Au-NPs: while sodium and some of the anions (e.g., Cl^-, HCF^3-) adsorb more at the `edgy' (100) and (110) facets of the NPs, where the water hydration structure is more disordered, other ions (e.g., BF₄^-, PF₆^-, Nip^-) prefer to adsorb strongly on the extended and rather flat (111) facets. In particular, Nip^-, which features an aromatic ring in its chemical structure, adsorbs strongly and perturbs the first water monolayer structure on the NP (111) facets substantially. Moreover, we calculate adsorptions, radially-resolved electrostatic potentials, as well as the far-field <i>effective</i> electrostatic surface charges and potentials by mapping the long-range decay of the calculated electrostatic potential distribution onto the standard Debye-Hückel form. We show how the extrapolation of these values to other ionic strengths can be performed by an analytical Adsorption-Grahame relation between effective surface charge and potential. We find for all salts negative effective surface potentials in the range from -10 mV for NaCl down to about -80 mV for NaNip, consistent with typical experimental ranges for the zeta-potential. We discuss how these values depend on the surface definition and compare them to the explicitly calculated electrostatic potentials near the NP surface, which are highly oscillatory in the ± 0.5 V range. <br>

Ion-specific Adsorption on Bare Gold (Au) Nanoparticles in aqueous Solution: Double-Layer Structure and Surface Potentials

We study the solvation and electrostatic properties of bare gold (Au) nanoparticles (NPs) of 1-2 nm in size in aqueous electrolyte solutions of sodium salts of various anions with large physicochemical diversity (Cl^-, BF₄^-, PF₆^-, Nip^-(nitrophenolate), 3- and 4-valent hexacyanoferrate (HCF)) using nonpolarizable, classical molecular dynamics computer simulations. We find a substantial facet selectivity in the adsorption structure and spatial distribution of the ions at the Au-NPs: while sodium and some of the anions (e.g., Cl^-, HCF^3-) adsorb more at the `edgy' (100) and (110) facets of the NPs, where the water hydration structure is more disordered, other ions (e.g., BF₄^-, PF₆^-, Nip^-) prefer to adsorb strongly on the extended and rather flat (111) facets. In particular, Nip^-, which features an aromatic ring in its chemical structure, adsorbs strongly and perturbs the first water monolayer structure on the NP (111) facets substantially. Moreover, we calculate adsorptions, radially-resolved electrostatic potentials, as well as the far-field <i>effective</i> electrostatic surface charges and potentials by mapping the long-range decay of the calculated electrostatic potential distribution onto the standard Debye-Hückel form. We show how the extrapolation of these values to other ionic strengths can be performed by an analytical Adsorption-Grahame relation between effective surface charge and potential. We find for all salts negative effective surface potentials in the range from -10 mV for NaCl down to about -80 mV for NaNip, consistent with typical experimental ranges for the zeta-potential. We discuss how these values depend on the surface definition and compare them to the explicitly calculated electrostatic potentials near the NP surface, which are highly oscillatory in the ± 0.5 V range. <br>