Simultaneous Determination of Nitrophenol Isomers Based on β‐Cyclodextrin Functionalized Reduced Graphene Oxide

β‐CD modified reduced graphene oxide (RGO) sheets have been prepared and characterized by TEM, AFM, IR, EIS and CVs. In comparison with bare glass carbon electrode (GCE) and RGO modified GCE, CD‐RGO/GCE showed much higher peak currents to the reduction of nitrophenol isomers (NPs), attributed to the larger specific surface area of RGO and high quantities of host–guest recognition sites. Three pairs of redox peaks are observed on the CVs of CD‐RGO for p‐NP (0.3 V), o‐NP (?0.2 V) and m‐NP (0.05 V), separating well with each other. Under the optimized condition, the anodic peak currents were linear over ranges around 1–10 mg dm^?3 for p‐NP, 1–9 mg dm^?3 for o‐NP and 1–6 mg dm^?3 for m‐NP, with the detection limits of 0.05 mg dm^?3, 0.02 mg dm^?3 and 0.1 mg dm^?3, respectively. Thus, the CD‐RGO is expected to be a promising sensor material for detecting trace NPs in waste water.     

Sensitive Voltammetric Response of p‐Nitroaniline on Single‐Wall Carbon Nanotube‐Ionic Liquid Gel Modified Glassy Carbon Electrodes

An ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF₆)‐single‐walled carbon nanotube (SWNT) gel modified glassy carbon electrode (BMIMPF₆‐SWNT/GCE) is fabricated. At it the voltammetric behavior and determination of p‐nitroaniline (PNA) is explored. PNA can exhibit a sensitive cathodic peak at ?0.70 V (vs. SCE) in pH 7.0 phosphate buffer solution on the electrode, resulting from the irreversible reduction of PNA. Under the optimized conditions, the peak current is linear to PNA concentration over the range of 1.0×10^?8–7.0×10^?6 M, and the detection limit is 8.0×10^?9 M. The electrode can be regenerated by successive potential scan in a blank solution for about 5 times and exhibits good reproducibility. Meanwhile, the feasibility to determine other nitroaromatic compounds (NACs) with the modified electrode is also tested. It is found that the NACs studied (i.e., p‐nitroaniline, p‐nitrophenol, o‐nitrophenol, m‐nitrophenol, p‐nitrobenzoic acid, and nitrobenzene) can all cause sensitive cathodic peaks under the conditions, but their peak potentials and peak currents are different to some extent. Their peak currents and concentrations show linear relationships in concentration ranges with about 3 orders of magnitude. The detection limits are 8.0×10^?9 M for p‐nitroaniline, 2.0×10^?9 M for p‐nitrophenol, 5.0×10^?9 M for o‐nitrophenol, 5.0×10^?9 M for m‐nitrophenol, 2.0×10^?8 M for p‐nitrobenzoic acid and 8.0×10^?9 M for nitrobenzene respectively. The BMIMPF₆‐SWNT/GCE is applied to the determination of NACs in lake water.     

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au–alkanedithiol–NP–molecule hybrid entity. The NP appears to relay long‐range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface‐confined 6‐(ferrocenyl) hexanethiol molecules and NPs of Au, Pt and Pd to address the dependence of the rate of ET through the hybrid on the particular NP metal. Cyclic voltammograms show an increasing difference in the peak‐to‐peak separation for NPs in the order Au<Pt<Pd, especially when the length of the alkanedithiol increases from octanedithiol to decanedithiol. The corresponding apparent rate constants, k_app, for decanedithiol are 1170, 360 and 14 s^?1 for NPs of Au, Pt and Pd, respectively, indicating that the efficiency of NP mediation of the ET clearly depends on the nature of the NP. Based on a preliminary analysis rooted in interfacial electrochemical ET theory, combined with a simplified two‐step view of the NP coupling to the electrode and the molecule, this observation is referred to the density of electronic states of the NPs, reflected in a broadening of the molecular electron/NP bridge group levels and energy‐gap differences between the Fermi levels of the different metals.     

Electrochemical sensor for detection of p-nitrophenol based on nanoporous gold

Nanoporous gold (NPG) with uniform pore sizes and ligaments was prepared by a simple dealloying method. The as-prepared NPG samples were used as the working electrodes to investigate the redox behavior of p-nitrophenol (p-NP) by cyclic voltammetry (CV). Quite different from the voltammetric behavior of polycrystalline gold electrode, the CV profiles of NPG display a pair of nearly symmetric redox waves which are ascribed to the reaction of 4-(hydroxyamino)phenol/4-nitrosophenol couple. It is interesting that this pair of redox waves are hardly affected by the isomers of p-NP; and moreover, their peak areas are linear with the concentration of p-NP in the range from 0.25 to 10 mg dm^?3. Because of high sensitivity and good selectivity, NPG is expected to act as a promising electrochemical sensor material for detecting trace p-NP in wastewaters.     

Electrochemical Behavior of o‐Nitrophenol at Hexagonal Mesoporous Silica Modified Carbon Paste Electrodes

A hexagonal mesoporous silica (HMS) modified carbon paste electrode (CPE) was fabricated and characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods (ferrocene as a probe). The electrochemical behavior of nitrophenol (o‐NP) at the HMS modified electrode (HMSCPE) was investigated. Compared with CPE, a well‐defined reduction peak and a remarkably peak current response was observed. It is indicated that mesoporous HMS exhibited remarkable enhancement effects on the electrochemical reduction of o‐NP. The electrochemical reduction mechanism was also discussed. Consequently, a simple and sensitive electrochemical method was proposed for the determination of o‐NP, which was used to determine o‐NP in waste water samples.     

Metal‐organic framework ZIF‐8 nanocrystals as pseudostationary phase for capillary electrokinetic chromatography

The outstanding properties such as large surface area, diverse structure, and accessible tunnels and cages make metal organic frameworks (MOFs) attractive as novel separation media in separation sciences. However, the utilization of MOFs in EKC has not been reported before. Here we show the exploration of zeolitic imidazolate framework‐8 (ZIF‐8), one of famous MOFs, as the pseudostationary phase (PSP) in EKC. ZIF‐8 nanocrystals were used as the PSP through dispersing in the running buffer (20 mM phosphate solution containing a 1% v/v methanol (pH 9.2)) to enhance the separation of the phenolic isomers (p‐benzenediol, m‐benzenediol, o‐benzenediol, m‐nitrophenol, p‐nitrophenol, and o‐nitrophenol). ZIF‐8 nanocrystals in the running buffer were negatively charged, and interacted with the phenolic hydroxyl groups of the analytes, and thus greatly improved the separation of the phenolic isomers. Inclusion of 200 mg L?¹ ZIF‐8 in the running buffer as the background electrolyte gave a baseline separation of the phenolic isomers within 4 min. The relative standard deviations for five replicate separations of the phenolic isomers were 0.2–1.1% for migration time and 4.5–9.7% for peak area. The limits of detection varied from 0.44 to 2.0 mg L?¹. The results show that nanosized MOFs are promising for application in EKC.     

Controlling the Selectivity of the Surface Plasmon Resonance Mediated Oxidation of p‐Aminothiophenol on Au Nanoparticles by Charge Transfer from UV‐excited TiO2

Although catalytic processes mediated by surface plasmon resonance (SPR) excitation have emerged as a new frontier in catalysis, the selectivity of these processes remains poorly understood. Here, the selectivity of the SPR‐mediated oxidation of p‐aminothiophenol (PATP) employing Au NPs as catalysts was controlled by the choice of catalysts (Au or TiO₂‐Au NPs) and by the modulation of the charge transfer from UV‐excited TiO₂ to Au. When Au NPs were employed as catalyst, the SPR‐mediated oxidation of PATP yielded p,p‐dimercaptobenzene (DMAB). When TiO₂‐Au NPs were employed as catalysts under both UV illumination and SPR excitation, p‐nitrophenol (PNTP) was formed from PATP in a single step. Interestingly, PNTP molecules were further reduced to DMAB after the UV illumination was removed. Our data show that control over charge‐transfer processes may play an important role to tune activity, product formation, and selectivity in SPR‐mediated catalytic processes.     

Synthesis, Structure and Growth Mechanism of Size and Shape Tunable Au/Ag Bimetallic Nanoparticles

By simply adding ascorbic acid in advance of AgNO₃, the size and shape controllable Au/Ag bimetallic nanoparticles (NP) were prepared in the traditional Au growth solution free of seed at room temperature. The size distribution of NP is well uniform with ca. 10%–15% standard deviation in diameter. By changing CTAB concentration, the size and shape of NPs are tunable. After researching the surface‐enhanced Raman spectroscopy (SERS) behavior of the prepared NPs, an enhancement factor varied from 4.3×10⁴ to 1.1×10⁵ was obtained for the NP centered at ca. (64±8) nm. Electrochemical cyclic voltammetric results revealed that the so formed nanoparticles were Au riched Au/Ag bimetallic NP, and this formation might be due to the disproportionation reaction of Au⁺ prompted by Ag⁺ and the under potential deposition process of Ag⁺ on Au.     

Electrochemical Determination of 2‐Nitrophenol in Water Samples Using Mg‐Al‐SDS Hydrotalcite‐Like Clay Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) modified with Mg‐Al‐SDS hydrotalcite‐like clay (SDS‐HTLC) was used for the sensitive voltammetric determination of 2‐nitrophenol (2‐NP) utilizing the oxidation process. The results indicate the prepared modified electrode has an excellent electrocatalytic activity toward 2‐NP oxidation, lowering the oxidation overpotential and increasing the oxidation current. Under optimal conditions, the oxidation current was proportional to 2‐NP concentration in the range from 1.0×10^?6 to 6.0×10^?4 M with the detection limit of 5.0×10^?7 M by DPV (S/N=3). The fabricated electrode was applied for 2‐NP determination in water samples and the recovery for these samples was from 95.6 to 103.5%.     

Screen‐Printed Disposable Sensors Modified with Bismuth Precursors for Rapid Voltammetric Determination of 3 Ecotoxic Nitrophenols

This work reports the application of screen‐printed electrodes bulk‐modified with bismuth precursors to the voltammetric determination of 2‐nitrophenol (2‐NP), 4‐nitrophenol (4‐NP) and 2,4‐dinitrophenol (2,4‐DNP) in water samples. A bismuth film was formed at the electrode surface via in situ reduction of the precursor compound contained in the electrode matrix by cathodic polarization at ?1.20 V. The formation of bismuth layer at the precursor‐modified electrodes was assessed by cyclic voltammetric (CV) at different pH values and by optical techniques. The target nitrophenols were voltammetrically determined by recording their reduction peaks in the differential pulse (DP) mode. The composition and content of the precursor compounds in the printed ink and the effect of the pH of the supporting electrolyte on the DP reduction currents of the 3 target nitrophenols were studied. The limits of quantification (LOQs) in three water matrices (distilled water, tap water and surface water) were in the range 1.1–2.2 µmol L^?1_. Using a simple solid‐phase extraction (SPE) procedure with Lichrolut EN cartridges and elution with methanol, a preconcentration factor of 100 was achieved; the LOQs were 0.021, 0.027 and 0.025 µmol L^?1 for 2‐NP, 4‐NP and 2,4‐DNP, respectively. The recoveries of samples spiked with the 3 target nitrophenols at two concentration levels (0.04 and 0.1 µmol L^?1) were always >87 %.     

Voltammetric Determination of 4‐Nitrophenol Using a Novel Type of Silver Amalgam Paste Electrode

A differential pulse voltammetric (DPV) method was developed for the determination of 4‐nitrophenol (4‐NP) at a newly developed silver amalgam paste electrode (AgA‐PE) in Britton–Robinson buffer pH 3.0. The electrode is based on a disposable plastic pipette tip filled with paste amalgam based on a mixture of mercury and fine silver powder (9 : 1, w/w). The experimental parameters, such as pH of Britton–Robinson buffer and activation and regeneration potential of the electrode surface were optimized. The reduction peak current dependences were linear for the concentration of 4‐NP from 0.2 to 100 μM. The method showed reproducible results with RSD (n=45) of 1.7%. The limit of determination (LOD) was 0.3 μM. The method was successfully applied for the direct determination of 4‐NP in drinking water.     

Antipassivating Electrochemical Process of Glassy Carbon Electrode (GCE) Dedicated to the Oxidation of Nitrophenol Compounds

We report for the first time a novel electrochemical treatment applied to a glassy carbon electrode (GCE) during p‐nitrophenol (PNP) oxidation and dedicated to the limitation of electrode passivation by nitrophenol compounds oxidation. We propose an electrochemical process of direct phenol oxidation by starting the electrolysis at a very low potential, ?1.2 V/SCE, in order to generate a soluble monomer, p‐aminophenol, on the electrode surface. Then, p‐aminophenol elaborated on the electrode surface in the place of oligomers, gives benzoquinone as a by‐product and no film formation was observed. Furthermore, the presence of a p‐NiTSPc (film of nickel tetrasulfonated phtalocyanine) coating permitted to increase two times the electrode sensitivity without passivation, too.     

Electrocatalytic Oxidation of Folic Acid on Carbon Paste Electrode Modified by Nickel Ions Dispersed into Poly(o‐anisidine) Film

Poly(o‐anisidine) (POA) was formed by successive cyclic voltammetry in monomer solution containing sodium dodecyl sulfate (SDS) at the surface of carbon paste electrode. Then Ni(II) ions were incorporated to electrode by immersion of the polymeric modified electrode having amine group in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode; a good redox behavior of Ni(OH)₂/NiOOH couple at the surface of electrode can be observed. The capability of this modified electrode for catalytic oxidation of folic acid was demonstrated. The amount of α and surface coverage (Γ*) of the redox species and catalytic chemical reaction rate constant (k) for folic acid oxidation were calculated. The catalytic oxidation peak current of folic acid was linearly dependent on its concentration and a linear calibration curve was obtained in the range of 0.1 to 5 mM with a correlation coefficient of 0.9994. The limit of detection (3σ) was determined as 0.091 mM. This electrocatalytic oxidation was used as simple, selective and precise voltammetric method for determination of folic acid in pharmaceutical preparations.     

The influence of aminobenzoic acid on Zn(II) electroreduction on a mercury electrode in water-methanol

Summary The influence of the isomers of aminobenzoic acid on the reaction Zn(II)/Zn(Hg) was studied in water-methanol mixtures. Theo- andm-isomers accelerate this reaction in all investigated solutions. The standard rate constants are similar at the same degree of electrode coverage with these isomers in water and mixed solutions.p-Aminobenzoic acid inhibits the process of Zn(II)/Zn(Hg) electroreduction. The results suggest that the decisive role in the acceleration is played by the formation of the active complex inside the adsorption layer.

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Der Einfluß von Aminobenzoesäure auf die Elektroreduktion von Zn(II) an einer Quecksilberelektrode in Methanol-Wasser

Zusammenfassung Der Einfluß der verschiedenen Isomeren von Aminobenzoesäure auf die Reduktion von Zn(II) an einer Quecksilberelektrode wurde in Methanol-Wasser-Mischungen untersucht. Dieo- undm-Isomeren beschleunigen die Reaktion, und die Reaktionsgeschwindigkeiten sind in Wasser und in Methanol-Wasser gleich. Die Beschleunigung wird wahrscheinlich durch Bildung des aktivierten Komplexes innerhalb der Adsorptionsschicht verursacht.p-Aminobenzoesäure hemmt die Elektroreduktion.

     

QCM and EC-SPR Studies of Cytochrome cSelf-assembled on Au Electrode and Enhancement of SPR Signal by Au Nanoparticles

Quartz crystal microbalance(QCM) and cyclic voltammetry(CV) were used to characterize the monolayer of cytochrome c(Cyt c), which was adsorbed on gold film modified with alkanethiol mixed monolayer. A direct comparison of protein surface coverages calculated from QCM and cyclic voltammetric measurements illustrates that the ratio of the electroactive Cyt c to the total surface-confined Cyt cis 34%, which suggests that the orientation is a main factor affecting the electroactivity of Cyt c. Moreover, surface plasmon resonance(SPR) measurement combined with CV “in situ” was used to investigate the conformational change of Cyt c in the redox process. Besides, Au nanoparticles(Au NPs) were adsorbed on the surface of Cyt c. The result indicates that Au NPs promote electron transfer between Cyt c and the gold electrode, and SPR result suggests Au NPs enhance SPR signal.     

Direct Electroanalysis of p‐Nitrophenol (PNP) in Estuarine and Surface Waters by a High Sensitive Type C/p‐NiTSPc Coating Carbon Fiber Microelectrode (CFME)

We report for the first time on the elaboration of a remarkable sensitivity type C/p‐NiTSPc carbon fiber microelectrode (CFME) for p‐nitrophenol (PNP) pollutant. We observed the best performances using square wave voltammetry (SWV) technique in the place of differential pulse voltammetry (DPV). Also the combination of p‐NiTSPc optimized cycles of electrodeposition and accumulation time, helped us to increase remarkably the sensor slope (320 times) and the limit of detection (LOD) (1000 times), with a final LOD of 0.1 µg/L, the current regulatory limit for drinkable waters. Furthermore the recoveries of the standards added are close to 100 % indicating that the method has some suitability. The proposed voltammetric procedure might be applied for organophosphorus pesticides and their by‐products with a remarkable sensing in natural polluted waters.     

Electrocatalytic Oxidation of Some Carbohydrates by Nickel/Poly(o‐Aminophenol) Modified Carbon Paste Electrode

This study investigates the electrocatalytic oxidation of glucose and some other carbohydrates on nickel/poly(o‐aminophenol) modified carbon paste electrode as an enzyme free electrode in alkaline solution. Poly(o‐aminophenol) was prepared by electropolymerization using a carbon paste electrode bulk modified with o‐aminophenol and continuous cyclic voltammetry in HClO₄ solution. Then Ni(II) ions were incorporated to electrode by immersion of the polymeric modified electrode having amine group in 1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode; a good redox behavior of Ni(OH)₂/NiOOH couple at the surface of electrode can be observed, the capability of this modified electrode for catalytic oxidation of glucose and other carbohydrates was demonstrated. The amount of α and surface coverage (Γ*) of the redox species and catalytic chemical reaction rate constant (k) for each carbohydrate were calculated. Also, the electrocatalytic oxidation peak currents of all tested carbohydrates exhibit a good linear dependence on concentration and their quantification can be done easily.     

Fibrillar Networks of Glycyrrhizic Acid for Hybrid Nanomaterials with Catalytic Features

Self‐assembly of the naturally occurring sweetening agent, glycyrrhizic acid (GA) in water is studied by small‐angle X‐ray scattering and microscopic techniques. Statistical analysis on atomic force microscopy images reveals the formation of ultralong GA fibrils with uniform thickness of 2.5 nm and right‐handed twist with a pitch of 9 nm, independently of GA concentration. Transparent nematic GA hydrogels are exploited to create functional hybrid materials. Two‐fold and three‐fold hybrids are developed by introducing graphene oxide (GO) and in situ‐synthesized gold nanoparticles (Au NPs) in the hydrogel matrix for catalysis applications. In the presence of GO, the catalytic efficiency of Au NPs in the reduction of p‐nitrophenol to p‐aminophenol is enhanced by 2.5 times. Gold microplate single crystals are further synthesized in the GA hydrogel, expanding the scope of these hybrids and demonstrating their versatility in materials design.     

Resolution of a Mononitrophenol Isomers Mixture by Differential Alternative Pulses Voltammetry

The high resolution second order voltammetric technique, Differential Alternative Pulse Voltammetry (DAPV), was applied for the simultaneous quantification of the mononitrophenol (NP) isomers. Complete resolution of the three isomers was achieved at concentration ratios as high as 1 : 5, employing the corresponding anodic and cathodic peaks appeared on the DAPV curve. The working glassy carbon electrode was modified by a nanocomposite of graphite nanopowder and Au nanoparticles to increase the sensitivity. The linear concentration range was found to be extended up to 125 μmol L^?1 for both the m‐NP and p‐NP isomers, while the o‐NP isomer presented calibration plot of two linear sections: up to 100 μmol L^?1 and up to 225 μmol L^?1. The LOD was found to be as low as 1.5 μmol L^?1, 2.5 μmol L^?1, and 0.5 μmol L^?1 for o‐NP, m‐NP, and p‐NP, respectively. The accuracy of the proposed method was evaluated by quantification of spiked tap waters samples. No interference was observed from a range of phenolic compounds such as phenol, 4‐aminophenol, 4‐chlorophenol, 2,4‐dinitrophenol, and resorcinol.     

Electrochemical Designing of Au/Pt Core Shell Nanoparticles as Nanostructured Catalyst with Tunable Activity for Oxygen Reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer‐by‐layer growth of Pt layers on Au NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(II) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air‐saturated 0.1 M H₂SO₄ was used to investigate the electrocatalytic behavior of the as‐prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring‐disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four‐electron reduction on the as‐prepared modified electrode with 5 Pt layers and first charge transfer is the rate‐determining step.