The effects of graphene and other nanomaterials on the electrocatalytic behaviour of phthalocyanines

Carbon based nanomaterials, gold nanorods and metallophthalocyanine nanoconjugates have been developed for electrocatalysis. Carbon based nanomaterials used are multiwalled carbon nanotubes, pristine graphene oxide nanosheets, nitrogen, boron, sulphur, phosphorus doped graphene oxide nanosheets. Cobalt phthalocyanine (CoPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPhPc), cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhPc) are the phthalocyanines employed in this work. Metallophthalocyanines were employed either in their bulk form or in their nanosized form. Electrode modification by these nanomaterials was either done sequentially, premixed or linked nanoconjugates. In all sequential modification, phthalocyanines were employed on top of other nanomaterials. Sequentially modified electrodes gave higher detection currents than both premixed and covalently bonded nanoconjugates. The nanomaterials reported here were characterised by transmission electron microscopy, Raman spectroscopy, time of flight secondary ion mass spectrometry, and X-ray diffraction among other techniques. The modified electrodes were further characterised by scanning electron microscopy, scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry, while square wave, linear scan and cyclic voltammetry, rotating disc electrode and chronoamperometry have been used to evaluate the electrocatalytic behaviour of the previously mentioned towards either oxidation or reduction of L-cysteine and/or hydrogen peroxide respectively. Generally, the nanoconjugates resulted in superior catalytic performance compared to the performance of individual nanomaterials. Zinc octacarboxy phthalocyanine (ZnOCPc) conjugated to either GONS or rGONS were employed to compare electrocatalytic detection of hydrogen peroxide to its luminescence sensing

The effects of graphene and other nanomaterials on the electrocatalytic behaviour of phthalocyanines

Carbon based nanomaterials, gold nanorods and metallophthalocyanine nanoconjugates have been developed for electrocatalysis. Carbon based nanomaterials used are multiwalled carbon nanotubes, pristine graphene oxide nanosheets, nitrogen, boron, sulphur, phosphorus doped graphene oxide nanosheets. Cobalt phthalocyanine (CoPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPhPc), cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhPc) are the phthalocyanines employed in this work. Metallophthalocyanines were employed either in their bulk form or in their nanosized form. Electrode modification by these nanomaterials was either done sequentially, premixed or linked nanoconjugates. In all sequential modification, phthalocyanines were employed on top of other nanomaterials. Sequentially modified electrodes gave higher detection currents than both premixed and covalently bonded nanoconjugates. The nanomaterials reported here were characterised by transmission electron microscopy, Raman spectroscopy, time of flight secondary ion mass spectrometry, and X-ray diffraction among other techniques. The modified electrodes were further characterised by scanning electron microscopy, scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry, while square wave, linear scan and cyclic voltammetry, rotating disc electrode and chronoamperometry have been used to evaluate the electrocatalytic behaviour of the previously mentioned towards either oxidation or reduction of L-cysteine and/or hydrogen peroxide respectively. Generally, the nanoconjugates resulted in superior catalytic performance compared to the performance of individual nanomaterials. Zinc octacarboxy phthalocyanine (ZnOCPc) conjugated to either GONS or rGONS were employed to compare electrocatalytic detection of hydrogen peroxide to its luminescence sensing

Electrode modification using nanocomposites of boron or nitrogen doped graphene oxide and cobalt (II) tetra aminophenoxy phthalocyanine nanoparticles

Reduced graphene oxide nanosheets (rGONS), reduced boron doped graphene oxide nanosheets (rBDGONS) and reduced nitrogen doped graphene oxide nanosheets (rNDGONS) and their composites with cobalt tetra aminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP) were employed towards the detection of hydrogen peroxide. The nanomaterials were characterized by absorption spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear sweep voltammetry and cyclic voltammetry. rNDGONS showed excellent electrooxidation and electroreduction of hydrogen peroxide supported by superior surface coverage values. The inclusion of nanosized Pc significantly lowered the reduction overpotential. CoTAPhPcNP-rNDGONS-GCE gave a sensitivity of 39.30 mA/M, catalytic rate constant of 1 × 103 M−1 s−1 and a detection limit of 8.2 nM. An adsorption equilibrium constant and Gibbs free energy of 1.26 × 103 M−1 and −17.69 kJ mol−1 respectively were observed

Electrocatalytic application for gold nanoparticles decorated sulfur-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt tetra aminophenoxy phthalocyanine conjugates

Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively

“Turn on” fluorescence enhancement of Zn octacarboxyphthaloyanine-graphene oxide conjugates by hydrogen peroxide

Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyaninereduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences

Nanocomposites of sulphur-nitrogen co-doped graphene oxide nanosheets and cobalt mono carboxyphenoxy phthalocyanines for facile electrocatalysis

Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode

Nanocomposites of sulphur-nitrogen co-doped graphene oxide nanosheets and cobalt mono carboxyphenoxy phthalocyanines for facile electrocatalysis

Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode

Electrocatalytic detection of l-cysteine using molybdenum POM doped-HKUST-1 metal organic frameworks

Glass carbon electrodes (GCE) were modified with metal organic frameworks (MOFs) containing molybdenum polyoxometallates (Mo POMs) in a copper benzene tricarboxylate framework (HKUST-1). The Mo POMs were introduced via one-pot synthesis (Mo2) and post-synthetic modification (Mo1) techniques. The electrode modifiers were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal analysis. The modified electrodes’ oxidation capacity toward L-cysteine was studied. Mo POMs significantly improved electron transfer kinetics compared to the bare GCE. The best Mo POM doped electrode (Mo1-GCE) had a catalytic rate constant of 2.2 × 104 M−1 s−1 and a limit of detection of 3.07 × 10−7 M. Under the employed experimental conditions, the detection response for L-cysteine was very fast (within 0.1 s) for all the modified electrodes and selective toward L-cysteine in the presence of other amino acids

Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine, Multi‐walled Carbon Nanotubes and Gold Nanoparticles

Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP), multi‐walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPcNP‐MWCNT‐GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×103 M−1 s−1 and a detection limit of 1.61×10−7 M. Adsorption Gibbs free energy ΔGo was found to be −19.22 kJ mol−1 for CoTAPhPcNP‐MWCNT‐GCE

Electrode modification using nanocomposites of boron or nitrogen doped graphene oxide and cobalt (II) tetra aminophenoxy phthalocyanine nanoparticles

Reduced graphene oxide nanosheets (rGONS), reduced boron doped graphene oxide nanosheets (rBDGONS) and reduced nitrogen doped graphene oxide nanosheets (rNDGONS) and their composites with cobalt tetra aminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP) were employed towards the detection of hydrogen peroxide. The nanomaterials were characterized by absorption spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear sweep voltammetry and cyclic voltammetry. rNDGONS showed excellent electrooxidation and electroreduction of hydrogen peroxide supported by superior surface coverage values. The inclusion of nanosized Pc significantly lowered the reduction overpotential. CoTAPhPcNP-rNDGONS-GCE gave a sensitivity of 39.30 mA/M, catalytic rate constant of 1 × 103 M−1 s−1 and a detection limit of 8.2 nM. An adsorption equilibrium constant and Gibbs free energy of 1.26 × 103 M−1 and −17.69 kJ mol−1 respectively were observed