Photolytic changes in the morphology of porphyrin-phthalocyanine nanostructures (P-PcNs) in the presence of platinum and gold salts
- Authors: George, Reama C , D'Souza, Sarah , Durmus, Mahmut , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190416 , vital:44992 , xlink:href="https://doi.org/10.1080/24701556.2017.1284085"
- Description: Porphyrin-phthalocyanine nanostructures (P-PcNs) have been fabricated by electrostatic self-assembly of two oppositely charged molecules. The negatively charged molecule, meso-tetra-(4-phenylsulphonate)porphyrin (HT) and the positively charged species; {1,(4)-tetrakis-[(N-methyl(3-pyridyloxy) phthlocyaninato] chloro gallium(III)} sulphate, {2,(3)-tetrakis-[(N-methyl{(2-mercaptopyridine) phthalocyaninato} hydroxy manganese(III)} sulphate, {1,(4)-tetrakis-[(N-methyl-(3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate, {2,3-octakis-{[(N-methyl-2-mercaptopyridine) phthalocyaninato] acetato manganese(III)} sulphate, {2,(3)-tetrakis-[(N-methyl(3-pyridyloxy) phthlocyaninato] choro gallium(III)} sulphate, {2,3-octakis-[(N-methy-3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate, and {2,(3)-tetrakis-[(N-methyl (3-pyridyloxy) phthalocyaninato] chloro indium(III)} sulphate. Transmission electron microscopic (TEM) images showed that the formed nanostructures ranged from nanosheets to nanorods and nanotubes. The UV-Vis spectra confirmed that the molecules formed J-aggregates. The P-PcNs were exposed to incandescence light in the presence of platinum and gold salts. It was observed that the presence of platinum salts resulted in the destruction of the P-PcNs with possible formation of a Pt-Pc complex. While with the gold salt, the structures of P-PcNs were not only retained but were also enhanced to longer nanorods and nanofibers with the formation of gold nanoparticles.
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- Date Issued: 2017
Characterization of porphyrin nanorods on fluorine doped tin oxide glass sheet
- Authors: George, Reama C , Falgenhauer, Jane , Geis, Clemens , Nyokong, Tebello , Schlettwein, Derck
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193542 , vital:45344 , xlink:href="https://doi.org/10.1142/S1088424615500923"
- Description: Porphyrin nanorods (PNR) have been fabricated by electrostatic self-assembly of two oppositely charged porphyrin molecules. The free base meso-tetra-(4-phenylsulphonate) porphyrin (TPPS4)4) served as negatively charged counterpart for the positively charged metallo meso-tetra(4-NN-methylpyridyl) porphyrins (MTM’PyP) with either Sn, Co, Mn or In as central metal M. Films of PNR were prepared on fluorine doped tin oxide glass sheets (FTO) by using a drop-dry method. The electronic spectra revealed J-aggregation of the charged molecules for the colloid PNR as well as for the films. Transmission electron microscopy confirmed the formation of porphyrin nanorods. The laser microscope and scanning electron microscope (SEM) images of the PNR/FTO films showed the formation of three kinds of structures in the films which consist of differently branched or linear needles with their main axis grown in the direction of the solvent flow during preparation. During cyclic voltammetry either applying negative potentials from 0.0 V to -1.0 V or positive potentials from 0.0 V to ++2.2 V irreversible reduction or oxidation reactions were detected for the films. Consistently, SEM images taken following cyclic voltammetry showed the disintegration of the PNR on the films into smaller subunits. Spectroelectrochemical measurements showed the formation of porphyrin anionic radicals during oxidation by a decrease in the absorption intensities and broadening of spectra with an additional band appearing around 900 nm. A similar trend was observed when negative potentials were applied but in this case the cationic radical was produced. In both cases the decrease of the intensity of the J-aggregate confirms a loss of intermolecular coupling, again consistent with the smaller subunits observed in SEM analysis.
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- Date Issued: 2015
Porphyrin nanorods modified glassy carbon electrode for the electrocatalysis of dioxygen, methanol and hydrazine
- Authors: George, Reama C , Mugadza, Tawanda , Khene, Samson , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247388 , vital:51576 , xlink:href="https://doi.org/10.1002/elan.201100081"
- Description: Porphyrin nanorods (PNR) were prepared by ionic self-assembly of two oppositely charged porphyrin molecules consisting of free base meso-tetraphenylsulfonate porphyrin (H4TPPS42−) and meso-tetra(N-methyl-4-pyridyl) porphyrin (MTMePyP4+M=Sn, Mn, In, Co). These consist of H4TPPS42−SnTMePyP4+, H4TPPS42−CoTMePyP4+, H4TPPS42−InTMePyP4+ and H4TPPS42−MnTMePyP4+ porphyrin nanorods. The absorption spectra and transmission electron microscopic (TEM) images of these structures were obtained. These porphyrin nanostructures were used to modify a glassy carbon electrode for the electrocatalytic reduction of oxygen, and the oxidation of hydrazine and methanol at low pH. The cyclic voltammogram of PNR-modified GCE in pH 2 buffer solution has five irreversible processes, two distinct reduction processes and three oxidation processes. The porphyrin nanorods modified GCE produce good responses especially towards oxygen reduction at −0.50 V vs. Ag|AgCl (3 M KCl). The process of electrocatalytic oxidation of methanol using PNR-modified GCE begins at 0.71 V vs. Ag|AgCl (3 M KCl). The electrochemical oxidation of hydrazine began at around 0.36 V on H4TPPS42−SnTMePyP4+ modified GCE. The GCE modified with H4TPPS42−CoTMePyP4+ H4TPPS42−InTMePyP4+ and H4TPPS42−MnTMePyP4+ porphyrin nanorods began oxidizing hydrazine at 0.54 V, 0.59 V and 0.56 V, respectively.
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- Date Issued: 2011
Spectroscopic studies of nanostructures of negatively charged free base porphyrin and positively charged tin porphyrins
- Authors: George, Reama C , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261661 , vital:53432 , xlink:href="https://doi.org/10.1016/j.poly.2010.01.028"
- Description: Spectroscopic studies were carried out on the homoaggregates of negatively charged free base meso-tetraphenylsulfonated porphyrin ([H2TPPS4]4−) and heteroaggregates of a mixture of protonated ([H4TPPS4]2−) and tin meso-tetra (N-methyl-4-pyridyl) porphyrin ([SnTMPyP]4+). The spectroscopic studies were done to determine the optimal conditions required for the fabrication of porphyrin nanorods by ionic self assembly of two oppositely charged porphyrins. In addition, the various spectral changes of [H4TPPS4]2− with concurrent change in pH and concentration are also investigated. In acid media at pH more than 3, and at concentrations less than 1 × 10−5 M, [H4TPPS4]2− molecules form J aggregates. A mixture of [H4TPPS4]2− and [SnTMPyP]4+ forms heteroaggregates of the J type in acid media. At pH’s 2 to 3, the optimum ratio for the formation of J aggregates is 3:1 and for pH 1, the optimum ratio is 2:1. Transmission electron microscope images of the nanostructures formed show that they are of cylindrical shape.
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- Date Issued: 2010
Electrostatic self-assembly of quaternized 2,(3)-tetra (oxo-pyridine) phthalocyaninato chloroindium (III) with a series of tetrasulfonated phthalocyanines
- Authors: George, Reama C , Durmus, Mahmut , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263330 , vital:53618 , xlink:href="https://doi.org/10.1016/j.poly.2009.07.035"
- Description: The self-assembly of oppositely charged phthalocyanines, fabricated using quaternized 2,(3)-tetra(oxo-pyridine) phthalocyaninato chloroindium (III) (QInPyPc) as the positively charge molecule and a series of tetrasulfonate phthalocyanine (MTSPc), M = 2H, Mn, Fe, Co and Ni as negatively charged molecules are reported. The self-assembly results in the formation of heteroaggregates. The metallated sulfonated phthalocyanines form nanorod and nanoleaf shaped structures as evidenced by transmission electron microscopy (TEM). The UV–Vis spectra showed blue shifted Q bands, suggesting that these structures were in a face-to-face arrangement. The Raman spectra of the heteroaggregates showed shifting compared to the spectra of the precursors.
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- Date Issued: 2009