Electrocatalytic activity of nanocomposites of sulphur doped graphene oxide and nanosized cobalt phthalocyanines
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
Electrode modification using alkyne manganese phthalocyanine and click chemistry for electrocatalysis
- O'Donoghue, Charles St John Nqwabuko, Fomo, Gertrude, Nyokong, Tebello
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
Effects of the invasive shrub, Lantana camara, on soil properties in the Eastern Cape, South Africa
- Ruwanza, Sheunesu, Shackleton, Charlie M
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180459 , vital:43391 , xlink:href="https://doi.org/10.1111/wbm.12094"
- Description: Lantana camara L. is an invasive alien shrub of worldwide significance due to its impacts on biodiversity. It can alter the soil properties of invaded ecosystems and, as a result, affect management outcomes. However, knowledge on the impacts of L. camara on soil properties is scanty, especially in South Africa, despite the pervasive presence of the plant in the country. In this comparative study, the soils underneath L. camara were assessed in order to determine if they had different properties (soil physico-chemical properties, penetration resistance, infiltration, hydraulic conductivity and water repellency) in comparison to the soils in adjacent natural sites in the Eastern Cape, South Africa. Soil samples were collected from the top soil beneath the canopy of both L. camara-invaded and adjacent natural sites in five different locations over three summer months. The soils that were collected from underneath L. camara had a significantly higher total C, total P, gravimetric soil moisture (in November and December) and were repellent, compared to the soils in the adjacent natural sites. Soil penetration resistance was significantly higher in the natural sites than in the L. camara-invaded sites. The soil hydraulic conductivity, soil infiltration rate, soil pH, exchangeable cations and total N showed no significant difference between the invaded and the natural sites. It appears that the soils underneath L. camara have a high total C and total P, soil moisture and are repellent, thus influencing nutrient cycling, potentially making the soil properties underneath it ideal for its own growth. This could contribute to the success of L. camara as an invasive species.
- Full Text:
- Date Issued: 2016
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180459 , vital:43391 , xlink:href="https://doi.org/10.1111/wbm.12094"
- Description: Lantana camara L. is an invasive alien shrub of worldwide significance due to its impacts on biodiversity. It can alter the soil properties of invaded ecosystems and, as a result, affect management outcomes. However, knowledge on the impacts of L. camara on soil properties is scanty, especially in South Africa, despite the pervasive presence of the plant in the country. In this comparative study, the soils underneath L. camara were assessed in order to determine if they had different properties (soil physico-chemical properties, penetration resistance, infiltration, hydraulic conductivity and water repellency) in comparison to the soils in adjacent natural sites in the Eastern Cape, South Africa. Soil samples were collected from the top soil beneath the canopy of both L. camara-invaded and adjacent natural sites in five different locations over three summer months. The soils that were collected from underneath L. camara had a significantly higher total C, total P, gravimetric soil moisture (in November and December) and were repellent, compared to the soils in the adjacent natural sites. Soil penetration resistance was significantly higher in the natural sites than in the L. camara-invaded sites. The soil hydraulic conductivity, soil infiltration rate, soil pH, exchangeable cations and total N showed no significant difference between the invaded and the natural sites. It appears that the soils underneath L. camara have a high total C and total P, soil moisture and are repellent, thus influencing nutrient cycling, potentially making the soil properties underneath it ideal for its own growth. This could contribute to the success of L. camara as an invasive species.
- Full Text:
- Date Issued: 2016
Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine, Multi‐walled Carbon Nanotubes and Gold Nanoparticles
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: 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.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: 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.
- Full Text:
- Date Issued: 2016
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Okujima, Tetsuo, Mack, John, Nakamura, Jun, Kubheka, Gugu, Nyokong, Tebello, Zhu, Hua, Komobuchi, Naoki, Ono, Noboru, Yamada, Hiroko, Uno, Hidemitsu, Kobayashi, Nagao
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
A chiral hemiporphyrazine derivative
- Wu, Yanping, Gai, Lizhi, Xiao, Xuqiong, Lu, Hua, Li, Zhifang, Mack, John, Harris, Jessica, Nyokong, Tebello, Shen, Zhen
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
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