A study of adsorption kinetics and thermodynamics of ω-mercaptoalkylhydroquinone self-assembled monolayer on a gold electrode

The adsorption kinetics and thermodynamics for the formation of redox active self-assembled monolayer (SAM) of 2-(n-mercaptoalkyl)hydroquinone (abbreviated as H₂Q(CH₂)_nSH, where n = 4, 6, 8, 10, and 12) on gold electrode has been investigated by cyclic voltammetry to study the effects of concentration and alkyl chain length. The time dependence of surface coverage, differential capacitance, and formal potential of electroactive hydroquinone(H₂Q) moiety supports that the adsorption of H₂Q(CH₂)_nSH molecules typically processes with a two-step adsorption consisted of a fast initial adsorption and a slowly following reorganization. The adsorption processes can be satisfactorily described by simple Langmuir adsorption kinetics, irrespective of concentration and alkyl chain length of adsorbate molecule. Based on Langmuir kinetics, the adsorption rate constant was determined at the initial step for the formation of all H₂Q(CH₂)_nSH-SAMs studied in this work. The rate constant value was found to be decreased with increasing alkyl chain length and decreasing bulk solution concentration (≤10 μM). The dependence of a surface coverage (Γ_e) at adsorption equilibrium on the bulk concentration is accurately described by the Langmuir isotherm at several concentrations ranging from 8 × 10⁻⁶ to 1 × 10⁻⁵ M for all H₂Q(CH₂)_nSH molecules. Parameters characterizing the adsorption thermodynamics, such as Γ_s, adsorption coefficient (β), and adsorption free energy (ΔG_ads) were determined from this isotherm.     

Electrochemical characterization of a 1,8-octanedithiol self-assembled monolayer (ODT-SAM) on a Au(1 1 1) single crystal electrode

Recently, it has becoming increasingly important to control the organization of self-assembled monolayers (SAMs) of ω-functionalized thiols for its potential applications in the construction of more complex molecular architectures. In this paper, we report on the spontaneous formation of a SAM of octanedithiol (ODT) as a function of the modification time. Electrochemical techniques such as cyclic voltammetry, double layer capacitance and electrochemical impedance spectroscopy are used for the characterization of this monolayer. The increase in modification time brings about changes in the octanedithiol self-assembled monolayer (ODT-SAM) reductive desorption voltammograms that indicate an evolution toward a more ordered and compact monolayer. This trend has also been found by following the changes in the electron transfer processes of the redox probe K₃Fe(CN)₆. In fact, the ODT-SAM formed at low-modification time does not significantly perturb the electrochemical response as it is typical of either a low coverage or of the presence of large defects in the layer. Upon increasing the modification time, the voltammograms of the redox probe adopt a sigmoidal shape indicating the existence of pinholes in the monolayer distributed as an array of microelectrodes. The surface coverage as well as the size and distribution of these pinholes have been determined by the impedance technique that gives a more reliable evaluation of these monolayer structural parameters.     

Effect of electrolyte on the supercapacitive behaviour of copper oxide/reduced graphene oxide nanocomposite

Cupric oxide/reduced graphene oxide (CuO/rGO) nanocomposites were synthesized through a chemical reduction method using hydrazine hydrate as the reducing agent. The morphology, elemental composition, and bonding network of the CuO/rGOnanocomposites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy respectively. The XRD results reveal lattice spacing and lattice strain from 3.371 to 3.428 Å and 1.05 × 10⁻³to 5.44 × 10⁻³ respectively, with the increasing ratio of rGO: CuO from 1:1 to 1:5. The cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS)and galvanostatic charge-discharge (GCD) studyofCuO/rGOas the electrode material showed excellent super-capacitive behavior in H₂SO₄ over Na₂SO₄ electrolytes. Moreover CuO/rGO nanocomposites exhibited better capacitance retention in H₂SO₄(75.69%) compared to Na₂SO₄(12.06%).     

Comparative electrochemical study of self-assembled monolayers of 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole formed on polycrystalline gold electrode

Comparative electrochemical behavior of self-assembled monolayers (SAMs) of three heteroaromatic thiols, 2-mercaptobenzoxazole (MBO), 2-mercaptobenzothiazole (MBT), and 2-mercaptobenzimidazole (MBI) are investigated by means of cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The electrochemical characteristics of the electrode/solution interface are considerably and differently affected by thiols constructing the SAMs. The consumed charges for reductive desorption of SAMs, which is criterion for the amount of chemically adsorbed thiol, are significantly different for these three SAMs, specially for MBT, implying that SAM of MBT is formed through both sulfur atoms; the thiol sulfur and skeleton sulfur of the thiazole ring. Desorption potentials of the SAMs have shown the following order for strength of gold-sulfur bond: MBT > MBO > MBI. Activity of the three SAMs as pH-sensitive interfaces was also investigated and their surface-pK_a values derived from the EIS measurements showed this order for acidic strength of SAMs: MBO > MBT > MBI. This is the same order expected due to the difference in electronegativity of the O, S, and N heteroatoms, and confirms that the most electron-rich ring imidazole is attached to the benzene ring of MBI. A comparison of the interfacial charge transfer resistance variation as a function of gold immersion time in thiols solution reveals that kinetics of Au-MBT assembly is different from those of two others and confirms formation of Au-MBT SAM via both sulfur atoms of MBT.     

Solid acidity of metal oxide monolayer and its role in catalytic reactions

Such metal oxide as SO₄²⁻, MoO₃, WO₃, and V₂O₅ spread readily on supports like SnO₂, ZrO₂, and TiO₂ due to the different properties between acid and base oxides to generate the acid site on the monolayer. Number, strength, and structure of the acid site were characterized by temperature-programmed desorption (TPD) of ammonia principally, together with various physico-chemical techniques, and its role for catalytic reactions was studied. Approximately, one to two acid sites were stabilized on 1 nm² of the surface, which consisted of four to eight metal atoms. The limit in surface acid site density was estimated on the monolayer based on the concept of solid acidity on zeolites. Sequence of the metal oxide to show the strong acidity was, SO₄²⁻>WO₃>MoO₃>V₂O₅, and for the support oxide to accommodate the monolayer, SnO₂>ZrO₂>TiO₂>Al₂O₃. From these combinations, the metal oxide monolayer to show the adequate strength of acid site could be selected. Brønsted acidity was observed often, however, the Lewis acidity was prevailing on the reduced vanadium oxide. The structure of acid site, Brønsted or Lewis acid site, thus depended on the oxidation state. Relationship of the profile of solid acidity with various catalytic activities was explained. The solid acid site on the monolayer will possibly be applied to environment friendly technologies.     

The influence of gold nanoparticle modified electrode on the structure of mercaptopropionic acid self-assembly monolayer

The comparison of assembly structure and property of mercaptopropionic acid (MPA) self-assembled monolayers (SAMs) on gold nanoparticle modified electrode (nanogold electrode) with that on planar gold electrode was studied by cyclic voltammetry (CV). The electron transfer of through the MPA SAMs and Cu underpotential deposition (UPD) on MPA-covered electrode indicated that MPA molecules assemblied on the planar gold electrode could form a very compact layer, which could surpass the electron transfer K₃Fe(CN)₆ greatly, whereas on the surface on the nanogold, which curvature make the compact packing loose. The reductive desorption in 0.5 M KOH and oxidative desorption in phosphate buffer solution (PBS) (pH 6.8) showed that gold nanoparticles could enhance the Au-S bond and stabilize the MPA molecules.     

The role of platinum oxide in the electrode system Pt(O2)/yttria-stabilized zirconia

The existence and role of platinum oxide in the solid state electrode system Pt(O₂)/yttria-stabilized zirconia is discussed. Covering and porous model-type Pt film electrodes on YSZ single crystals are investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and in situ scanning photoelectron microscopy. The formation of Pt oxide and its amount strongly depend on the experimental conditions, such as temperature, oxygen partial pressure, and oxygen flux towards the electrode during anodic polarization. Electrode activation and deactivation processes can be explained by formation and decomposition of Pt oxide, which is reducing or inhibiting the oxygen exchange rate.     

Supramolecular assembly of porphyrin bound DNA and its catalytic behavior for nitric oxide reduction

A stable Fe(4-TMPyP)-DNA-PADDA (FePyDP) film was prepared on pyrolytic graphite electrode (PGE) through the supramolecular interaction between water-soluble iron(III) meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(4-TMPyP)) and DNA template, where PADDA (poly(acrylamide-co-diallyldimethylammonium chloride)) is employed as a co-immobilizing polymer. Electronic absorption spectral and quartz crystal microbalance measurements revealed that Fe(4-TMPyP) interacted with DNA to generate a species with the molar ratio of 1:5 for Fe(4-TMPyP):DNA phosphate. Cyclic voltammetry of FePyDP film showed a pair of stable and reversible peaks corresponding to Fe^III/Fe^II redox potential of −0.13 V versus Ag|AgCl in pH 7.4 PBS. The electron transfer was expected across the double-strand of DNA by an “electron tunneling” mechanism. The modified electrode displayed an excellent catalytic activity for NO reduction at −0.61 V versus Ag|AgCl. The catalytic current was enhanced at lower pH. Chronoamperometric experiments demonstrated a rapid response to the reduction of NO with a linear range from 0.1 to 90 μM. The detection limit was 30 nM at a signal-to-noise ratio of 3.     

Special titanium dioxide layers and their electrochemical behaviour

This text describes the production of polycrystalline titanium dioxide layers by anodic spark deposition (ASD). These deposits show an interesting electrochemical and electrocatalytic behaviour. A reversible electrochemical transformation of the crystalline phases could be proved. Furthermore, the TiO₂-layers were used as electrode material for the cathodic reduction of molecular oxygen. In this process, cyclic voltammetry was employed, and the reduction of oxygen was successfully examined in dependence on surface-determining parameters such as layer thickness and pH value.     

Redox behaviour of cerium oxychloride in molten MgCl2-NaCl-KCl eutectic

The electrochemical behaviour of cerium oxychloride in MgCl₂-NaCl-KCl ternary eutectic was investigated by cyclic voltammetry at 823 K. The cyclic voltammogram of UO₂Cl₂-CeOCl in MgCl₂-NaCl-KCl eutectic shows two peaks during the cathodic sweep as well as anodic sweep. The reduction of UO₂²⁺ is by a single step two-electron transfer and that of CeO⁺ is by a single step one-electron transfer. The reduction of CeO⁺ was found to be quasi-reversible.The reduction potentials of UO₂²⁺/UO₂ and CeO⁺/CeO versus Ag(I)/Ag reference electrode at 823 K are 0.103 and −0.299 V, respectively. The diffusion coefficient of CeO⁺ at 823 K is in the range of (1.7-1.9) × 10⁻⁵ cm² s⁻¹. The cyclic voltammogram for 0.015 mol% CeOCl shows an additional peak during the anodic sweep at −0.056 V, which is being attributed to monolayer dissolution of CeO at the glassy carbon working electrode. Electrochemical impedance data of 0.015 mol% CeOCl in MgCl₂-NaCl-KCl eutectic at the open circuit potential was fitted to a Randles cell from which the heterogeneous rate constant was estimated. X-ray photoelectron spectroscopy was used to confirm that the oxidation state of cerium in the eutectic is +3.     

Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards l-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for l-cysteine at potentials where metal oxidation (M^III/M^II) takes place and this metal oxidation mediates the catalytic oxidation of l-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards l-cysteine at potentials where Mn^IV/Mn^III redox peak occurs and this redox peak mediates l-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10⁻⁷ mol L⁻¹ and good linearity for a studied concentration range up to 60 μmol L⁻¹.     

Electrochemical detection of Cd ions by a self-assembled monolayer of 1,9-nonanedithiol on gold

The application of 1,9-nonanedithiol (NDT) self-assembled monolayer (SAM) on gold for the electrochemical determination of Cd²⁺ was studied. Interestingly, we found that a NDT SAM strongly affects the stripping wave of Cd, resulting in a sharp peak that was used for electroanalytical determination of Cd²⁺ in aqueous solutions. The different parameters, such as potential and time of deposition of Cd, were examined. Furthermore, polarization-modulated infrared reflection absorption spectroscopy (PM IRRAS) and X-ray photoelectron spectroscopy (XPS) were used for exploring the interaction between the deposited Cd and the thiol groups on Au. FTIR measurements clearly indicate that NDT is assembled in a disordered liquid type monolayer interacting with the Au electrode via both thiol moieties. XPS reveals that Cd is stripped at two different potentials and that the signal of sulfur is almost unchanged by deposition and desorption of Cd. All these finding allude to the interesting conclusion that Cd is deposited on Au lifting to some extent the thiol groups.     

Study of a gold electrode modified by trans-[Ru(NH3)4(Ist)SO4] to produce an electrochemical sensor for nitric oxide

The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH₃)₄(Ist)SO₄]⁺ to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH₃)₄(Ist)SO₄]⁺ complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO.     

DC and AC voltammetry of a free-base porphyrin adsorbed onto basal-plane graphite under acidic conditions: An example of a close to ideal reversible two-electron surface-confined redox process at sub-monolayer coverages

The free-base porphyrin, 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine (H₂TMPyP), adsorbs onto a basal-plane graphite electrode. Under DC cyclic voltammetric conditions, the fully protonated dication, [H₄TMPyP(0)]²⁺, undergoes an apparently close to ideal surface-confined two-electron reduction to the neutral [H₄TMPyP(-II)] species when the supporting electrolyte consists of aqueous 1 M HCl and 1 M NaCl and coverages are sub-monolayer. The reversible potential calculated from the average of the oxidation and reduction peak potentials is 0.138 ± 0.002 V (vs Ag/AgCl, 3 M NaCl) whilst their separation ΔE_p, approaches 0 mV at slow scan rates, as expected theoretically for an ideal surface-confined electron transfer process. Comparisons of simulated and experimental data imply that the increase in ΔE_p observed at scan rates above 10 V s⁻¹ is consistent with uncompensated Ohmic IR_u drop effects, and not limitations imposed by electron transfer kinetics. Analysis of fundamental and higher harmonic components derived from large-amplitude sine-wave AC voltammetry is consistent with a very fast electron transfer rate constant, k⁰, in excess of 10⁶ s⁻¹ for the overall two-electron process. However, careful comparison with AC theory highlights minor levels of non-ideality not attributable to purely capacitative background or uncompensated resistance effects. These are particularly evident when greater than monolayer surface coverages are employed. It is likely that subtle contributions from heterogeneity in the adsorbed layer and complexities in the reaction mechanism are present in this close to ideal surface-confined process, but they are more readily detected under conditions of large-amplitude Fourier transformed AC cyclic voltammetry than with the conventionally used DC cyclic format.     

The electrochemical behavior of erythromycin A on a gold electrode

The reactivity of erythromycin (pure) was investigated on a gold electrode in neutral electrolyte by cyclic voltammetry. The resulting structural changes were observed with HPLC and FTIR spectroscopy by analyzing the bulk electrolyte after the electrochemical reactions. The results were compared with those previously obtained for azithromycin and clarithromycin under the same experimental conditions. It was found that the electrochemical behavior of erythromycin A differs from that of azithromycin dihydrate. Comparison with the electrochemical activity of basic clarithromycin suggests that the electrochemical activity of erythromycin is similar but more pronounced than that of clarithromycin.HPLC analysis confirmed these observations and showed that during the electrochemical oxidation of erythromycin A, the amount of starting macrolide decreased while the amount of starting impurities increased. Also some new products were observed. FTIR spectroscopy confirmed that erythromycin A is more reactive than clarithromycin, although similar changes in their molecular structures were observed.     

Anodically formed oxide films and oxygen reduction on electrodeposited ruthenium in acid solution

The impedance of the anodically formed hydrous Ru oxide in the system Ru|oxide film|1 M HClO₄ solution has been studied in the range of potentials where the electrode process occurs by a double electron and proton exchange between the oxide film and the solution. The results allowed us to clearly distinguish between the surface process at higher frequency and the bulk process at lower frequency. The high-frequency charging is found to be coupled to Faradaic charging at the film/solution interface. Evaluation of the impedance data at lower frequency, using diffusion equations for the finite boundary conditions, yields an effective proton diffusion coefficient to be 10⁻¹⁰ to 10⁻¹¹ cm² s⁻¹.Oxygen reduction on the spontaneously oxidized ruthenium electrode was discussed on the basis of a rotating ring-disk voltammetry.     

Investigation of the electrochemical behavior of multilayers film assembled porphyrin/gold nanoparticles on gold electrode

Multilayers film of nanostructured gold nanoparticles (AuNPs) has been fabricated based on the layer-by-layer (LBL) technique using a self-assembled monolayer of 5,15-di-[p-(6-mercaptohexyl)-phenyl]-10,20-diphenylporphyrin (trans-PPS₂). AuNPs act as physical cross-link points in the multilayers. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) are applied to study the formation of the organic-inorganic multilayers film and have determined the electrochemical parameters, i.e., the heterogeneous electron transfer rate constant (K_et). The observed phenomena indicate that the electron transfer (ET) process is affected by material properties and the molecular structure of self-assembled monolayers (SAMs). Using the high sensitivity of ET of ferricyanide to the modification of the gold surface with multilayers film, we select this reaction as a probe to study the different modification stages at this modified electrode. ET is retarded on the trans-PPS₂ alternative deposition of layers on the electrode surface and is accelerated on the AuNPs’ layers. SECM images are used to collect surface information in the course of the successive modification process. SECM images obtained from bare and different modification stages show very high resolution with different topographies.     

Voltammetric characterization of the self-assembled monolayer (SAM) of octabutylthiophthalocyaninatoiron(II): a potential electrochemical sensor

The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBu)₈] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH₄)(SO₄)₂ in HClO₄. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)₈ can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This ‘activation’ process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about −57 mV per pH in the pH range of 2-9. A preliminary investigation indicates that FePc(SBu)₈-SAM modified gold electrode shows electrocatalytic activity toward the oxidation of l-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments.     

Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes

Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to Mn^IIIPc²⁻/Mn^IIPc²⁻ and Mn^IIPc³⁻/Mn^IIPc²⁻ processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.     

Application of elimination voltammetry in the study of electroplating processes on the graphite electrode

The electrode reaction mechanism of electrolytical coating by nickel on paraffin impregnated graphite electrode (PIGE) was investigated by cyclic voltammetry (CV) and elimination voltammetry with linear scan (EVLS). The EVLS, a relatively new method of processing electrochemical signals obtained by voltammetry, is able to eliminate some individual chosen currents from total voltammetric currents measured at different scan rates. During the electrodeposition of metals on the graphite electrode, hydrogen evolved from aqueous acidic solutions interferes with the plating process. The elimination of kinetic current arising due to hydrogen evolution enables one to study other processes proceeding at the electrode. Cyclic voltammograms for metal coating deposition/dissolution on the graphite electrode were measured at three scan rates (12.5, 25 and 50 mV/s) and the EVLS functions were calculated for one or two eliminated currents. The results indicate the occurrence of surface reactions with the adsorption of intermediates on graphite. The application of EVLS provides deeper insight into the mechanism of electrode reaction during metal deposition.