Characterization and application of phthalocyanine-gold nanoparticle conjugates
- Authors: Tombe, Sekai Lana
- Date: 2013
- Subjects: Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4293 , http://hdl.handle.net/10962/d1004517 , Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Description: This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. , Microsoft� Word 2010 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai Lana
- Date: 2013
- Subjects: Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4293 , http://hdl.handle.net/10962/d1004517 , Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Description: This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. , Microsoft� Word 2010 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
Photophysicochemical and photodynamic antimicrobial chemotherapeutic studies of novel phthalocyanines conjugated to silver nanoparticles
- Authors: Rapulenyane, Nomasonto
- Date: 2013 , 2013-06-10
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Cancer -- Photochemotherapy , Anti-infective agents , Escherichia coli , Nanoparticles , Silver , Zinc
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4291 , http://hdl.handle.net/10962/d1003912 , Phthalocyanines , Photochemistry , Photochemotherapy , Cancer -- Photochemotherapy , Anti-infective agents , Escherichia coli , Nanoparticles , Silver , Zinc
- Description: This work reports on the synthesis, characterization and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines: namely tris{11,19, 27-(1,2- diethylaminoethylthiol)-2-(captopril) phthalocyanine Zn ((ZnMCapPc (1.5)), hexakis{8,11,16,19,42,27-(octylthio)-1-(4-phenoxycarboxy) phthalocyanine} Zn (ZnMPCPc(1.7)) and Tris {11, 19, 27-(1,2-diethylaminoethylthiol)-1,2(caffeic acid) phthalocyanine} Zn ((ZnMCafPc (1.3)). Symmetrically substituted counterparts (tetrakis(diethylamino)zinc phthalocyaninato (3.8), octakis(octylthio)zinc phthalocyaninato (3.9) and tetrakis (carboxyphenoxy)zinc phthalocyaninato (3.10) complexes) were also synthesized for comparison of the photophysicochemical properties and to investigate the effect of the substituents on the low symmetry Pcs. The complexes were successfully characterized by IR, NMR, mass spectral and elemental analyses. All the complexes showed the ability to produce singlet oxygen, while the highest triplet quantum yields were obtained for 1.7, 1.5 and 3.9 (0.80, 0.65 and 0.62 respectively and the lowest were obtained for 1.3 and 3.10 (0.57 and 0.47 respectively). High triplet lifetimes (109-286 μs) were also obtained for all complexes, with 1.7 being the highest (286 μs) which also corresponds to its triplet and singlet quantum yields (0.80 and 0.77 respectively). The photosensitizing properties of low symmetry derivatives, ZnMCapPc and ZnMCafPc were investigated by conjugating glutathione (GSH) capped silver nanoparticles (AgNP). The formation of the amide bond was confirmed by IR and UV-Vis spectroscopies. The photophysicochemical behaviour of the novel phthalocyanine-GSH-AgNP conjugates and the simple mixture of the Ag NPs with low the symmetry phthalocyanines were investigated. It was observed that upon conjugation of the phthalocyanines to the GSH-AgNPs, a blue shift in the Q band was induced. The triplet lifetimes and quantum yields improved upon conjugation as compared to the phthalocyanines (Pc) alone. Complex 1.5 triplet lifetimes increased from 109 to 148 and triplet quantum yield from 0.65 to 0.86 upon conjugation. Fluorescence lifetimes and quantum yields decreased for the conjugates compared to the phthalocyanines alone, due to the quenching caused by the Ag NPs. The antimicrobial activity of the zinc phthalocyanines (complexes 1.3 and 1.5) and their conjugates against Escherichia coli was investigated. Only 1.3 and 1.5 complexes were investigated because of the availability of the sample. In general phthalocyanines showed increase in antibacterial activity with the increase in phthalocyanines concentration in the presence and absence of light. The Pc complexes and their Ag NP conjugates showed an increase in antibacterial activity, due to the synergistic effect afforded by Ag NP and Pcs. Improved antibacterial properties were obtained upon irradiation. 1.5-AgNPs had the highest antibacterial activity compared to 1.3-AgNPs conjugate; these results are in agreement with the photophysical behaviour. This work demonstrates improved photophysicochemical properties of low symm
- Full Text:
- Date Issued: 2013
- Authors: Rapulenyane, Nomasonto
- Date: 2013 , 2013-06-10
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Cancer -- Photochemotherapy , Anti-infective agents , Escherichia coli , Nanoparticles , Silver , Zinc
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4291 , http://hdl.handle.net/10962/d1003912 , Phthalocyanines , Photochemistry , Photochemotherapy , Cancer -- Photochemotherapy , Anti-infective agents , Escherichia coli , Nanoparticles , Silver , Zinc
- Description: This work reports on the synthesis, characterization and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines: namely tris{11,19, 27-(1,2- diethylaminoethylthiol)-2-(captopril) phthalocyanine Zn ((ZnMCapPc (1.5)), hexakis{8,11,16,19,42,27-(octylthio)-1-(4-phenoxycarboxy) phthalocyanine} Zn (ZnMPCPc(1.7)) and Tris {11, 19, 27-(1,2-diethylaminoethylthiol)-1,2(caffeic acid) phthalocyanine} Zn ((ZnMCafPc (1.3)). Symmetrically substituted counterparts (tetrakis(diethylamino)zinc phthalocyaninato (3.8), octakis(octylthio)zinc phthalocyaninato (3.9) and tetrakis (carboxyphenoxy)zinc phthalocyaninato (3.10) complexes) were also synthesized for comparison of the photophysicochemical properties and to investigate the effect of the substituents on the low symmetry Pcs. The complexes were successfully characterized by IR, NMR, mass spectral and elemental analyses. All the complexes showed the ability to produce singlet oxygen, while the highest triplet quantum yields were obtained for 1.7, 1.5 and 3.9 (0.80, 0.65 and 0.62 respectively and the lowest were obtained for 1.3 and 3.10 (0.57 and 0.47 respectively). High triplet lifetimes (109-286 μs) were also obtained for all complexes, with 1.7 being the highest (286 μs) which also corresponds to its triplet and singlet quantum yields (0.80 and 0.77 respectively). The photosensitizing properties of low symmetry derivatives, ZnMCapPc and ZnMCafPc were investigated by conjugating glutathione (GSH) capped silver nanoparticles (AgNP). The formation of the amide bond was confirmed by IR and UV-Vis spectroscopies. The photophysicochemical behaviour of the novel phthalocyanine-GSH-AgNP conjugates and the simple mixture of the Ag NPs with low the symmetry phthalocyanines were investigated. It was observed that upon conjugation of the phthalocyanines to the GSH-AgNPs, a blue shift in the Q band was induced. The triplet lifetimes and quantum yields improved upon conjugation as compared to the phthalocyanines (Pc) alone. Complex 1.5 triplet lifetimes increased from 109 to 148 and triplet quantum yield from 0.65 to 0.86 upon conjugation. Fluorescence lifetimes and quantum yields decreased for the conjugates compared to the phthalocyanines alone, due to the quenching caused by the Ag NPs. The antimicrobial activity of the zinc phthalocyanines (complexes 1.3 and 1.5) and their conjugates against Escherichia coli was investigated. Only 1.3 and 1.5 complexes were investigated because of the availability of the sample. In general phthalocyanines showed increase in antibacterial activity with the increase in phthalocyanines concentration in the presence and absence of light. The Pc complexes and their Ag NP conjugates showed an increase in antibacterial activity, due to the synergistic effect afforded by Ag NP and Pcs. Improved antibacterial properties were obtained upon irradiation. 1.5-AgNPs had the highest antibacterial activity compared to 1.3-AgNPs conjugate; these results are in agreement with the photophysical behaviour. This work demonstrates improved photophysicochemical properties of low symm
- Full Text:
- Date Issued: 2013
Photophysicochemical properties of aluminium phthalocyanine-platinum conjugates
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
Polymer based electrospun nanofibers as diagnostic probes for the detection of toxic metal ions in water
- Authors: Ondigo, Dezzline Adhiambo
- Date: 2013
- Subjects: Heavy metals , Nanofibers , Nanoparticles , Colorimetric analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4557 , http://hdl.handle.net/10962/d1018261
- Description: The thesis presents the development of polymer based electrospun nanofibers as diagnostic probes for the selective detection of toxic metal ions in water. Through modification of the chemical characteristics of nanofibers by pre- and post-electrospinning treatments, three different diagnostic probes were successfully developed. These were the fluorescent pyridylazo-2-naphthol-poly(acrylic acid) nanofiber probe, the colorimetric probe based on glutathione-stabilized silver/copper alloy nanoparticles and the colorimetric probe based on 2-(2’-Pyridyl)-imidazole functionalized nanofibers. The probes were characterized by Fourier transform infrared spectroscopy (FTIR), Energy dispersive x-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The fluorescent nanofiber probe was developed towards the determination of Ni²⁺. Covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymeric nanofibers were employed. The solid state Ni²⁺ probe exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 mg/mL based on the Stern-Volmer mechanism. The detection limit of the nanofiber probe was found to be 0.07 ng/mL. The versatility of the fluorescent probe was demonstrated by affording a simple, rapid and selective detection of Ni²⁺ in the presence of other competing metal ions by direct analysis without employing any sample handling steps. For the second part of the study, a simple strategy based on the in-situ synthesis of the glutathione stabilized silver/copper alloy nanoparticles (Ag/Cu alloy NPs) in nylon 6 provided a fast procedure for fabricating a colorimetric probe for the detection of Ni²⁺ in water samples. The electrospun nanofiber composites responded to Ni²⁺ ions but did not suffer any interference from the other metal ions. The effect of Ni²⁺ concentration on the nanocomposite fibers was considered and the “eye-ball” limit of detection was found to be 5.8 μg/mL. Lastly, the third probe was developed by covalently linking an imidazole derivative; 2-(2′-Pyridyl)-imidazole (PIMH) to Poly(vinylbenzyl chloride) (PVBC) and nylon 6 nanofibers by post-electrospinning treatments using a wet chemical method and graft copolymerization technique, respectively. The post-electrospinning modifications of the nanofibers were achieved without altering their fibrous morphology. The color change to red-orange in the presence of Fe²⁺ for both the grafted nylon 6 (white) and the chemically modified PVBC (yellow) nanofibers was instantaneous. The developed diagnostic probes exhibited the desired selectivity towards the targeted metal ions.
- Full Text:
- Date Issued: 2013
- Authors: Ondigo, Dezzline Adhiambo
- Date: 2013
- Subjects: Heavy metals , Nanofibers , Nanoparticles , Colorimetric analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4557 , http://hdl.handle.net/10962/d1018261
- Description: The thesis presents the development of polymer based electrospun nanofibers as diagnostic probes for the selective detection of toxic metal ions in water. Through modification of the chemical characteristics of nanofibers by pre- and post-electrospinning treatments, three different diagnostic probes were successfully developed. These were the fluorescent pyridylazo-2-naphthol-poly(acrylic acid) nanofiber probe, the colorimetric probe based on glutathione-stabilized silver/copper alloy nanoparticles and the colorimetric probe based on 2-(2’-Pyridyl)-imidazole functionalized nanofibers. The probes were characterized by Fourier transform infrared spectroscopy (FTIR), Energy dispersive x-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The fluorescent nanofiber probe was developed towards the determination of Ni²⁺. Covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymeric nanofibers were employed. The solid state Ni²⁺ probe exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 mg/mL based on the Stern-Volmer mechanism. The detection limit of the nanofiber probe was found to be 0.07 ng/mL. The versatility of the fluorescent probe was demonstrated by affording a simple, rapid and selective detection of Ni²⁺ in the presence of other competing metal ions by direct analysis without employing any sample handling steps. For the second part of the study, a simple strategy based on the in-situ synthesis of the glutathione stabilized silver/copper alloy nanoparticles (Ag/Cu alloy NPs) in nylon 6 provided a fast procedure for fabricating a colorimetric probe for the detection of Ni²⁺ in water samples. The electrospun nanofiber composites responded to Ni²⁺ ions but did not suffer any interference from the other metal ions. The effect of Ni²⁺ concentration on the nanocomposite fibers was considered and the “eye-ball” limit of detection was found to be 5.8 μg/mL. Lastly, the third probe was developed by covalently linking an imidazole derivative; 2-(2′-Pyridyl)-imidazole (PIMH) to Poly(vinylbenzyl chloride) (PVBC) and nylon 6 nanofibers by post-electrospinning treatments using a wet chemical method and graft copolymerization technique, respectively. The post-electrospinning modifications of the nanofibers were achieved without altering their fibrous morphology. The color change to red-orange in the presence of Fe²⁺ for both the grafted nylon 6 (white) and the chemically modified PVBC (yellow) nanofibers was instantaneous. The developed diagnostic probes exhibited the desired selectivity towards the targeted metal ions.
- Full Text:
- Date Issued: 2013
Structural analysis of synthetic ferrihydrite nanoparticles and its reduction in a hydrogen atmosphere
- Authors: Masina, Colani John
- Date: 2013
- Subjects: Ferric hydroxides , Minerals -- Analysis , Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10555 , http://hdl.handle.net/10948/d1020796
- Description: Ferrihydrite (FHYD), a nanocrystalline material has long been described as a poorly crystalline disordered mineral mainly due to its small crystal size which is typically 2−6 𝑛𝑚. The three-dimensional structure of the mineral has long been described by a multi-phase structural model that consists of Fe3+ only in octahedral (Oh) coordination. In this model ferrihydrite is described as a mixture of two major phases (akaganeite/goethite-like f-phase and feroxyhite-like d-phase) and a minor ultradispersed nanohematite phase. This model has been recently challenged and a new, single-phase model was proposed, having a basic structural motif closely related to the Baker-Figgs δ-Keggin cluster and is isostructural with the mineral akdalaite, Al10O14(OH)2. In its ideal form, the proposed new structure of FHYD consist of 80 % Oh and 20 % tetrahedral (Td) Fe3+ polyhedra which can be adequately described by a single-domain model with the hexagonal spacegroup 𝑃63𝑚𝑐 and unit cell dimensions 𝑎=5.95 Å and 𝑐=9.06 Å. In this study, nanoparticles of 2-line FHYD (FHYD2), 2-line FHYD deposited onto SiO2 (FHYD2/SiO2) and 6-line FHYD (FHYD6) synthesised using rapid hydrolysis of Fe(NO3)3.9H2O solutions were characterized using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), Mössbauer spectroscopy (MS) as well as magnetization and magnetic susceptibility measurements. The coordination environment of iron atoms in the structure of FHYD was investigated using TEM and MS. The thermal transformation of FHYD nanoparticles was monitored through changes in the magnetization as a function of temperature and the reduction behaviour in hydrogen environment was studied using temperature programmed reduction (TPR), in-situ XRD and MS. Electron diffraction, TEM/ scanning TEM (STEM) imaging, and electron energy loss (EELS) measurements were carried out on three different microscopes viz. JEOL JEM-2100 LaB6 TEM, aberration corrected Schottky-FEG JEOL JEM-ARM200F HRTEM and cold-FEG Zeiss SESAM TEM. EELS studies were concentrated mainly on the iron 𝐿-edge of FHYD and iron oxides reference spectra with well known crystal structures. The iron oxide Fe 𝐿-edge is usually characterized by two intense sharp peaks termed “white lines”. The fine structures introduced by the crystal field effect on the 𝐿- edge contain information that is highly specific to the Fe3+ site symmetry.
- Full Text:
- Date Issued: 2013
- Authors: Masina, Colani John
- Date: 2013
- Subjects: Ferric hydroxides , Minerals -- Analysis , Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10555 , http://hdl.handle.net/10948/d1020796
- Description: Ferrihydrite (FHYD), a nanocrystalline material has long been described as a poorly crystalline disordered mineral mainly due to its small crystal size which is typically 2−6 𝑛𝑚. The three-dimensional structure of the mineral has long been described by a multi-phase structural model that consists of Fe3+ only in octahedral (Oh) coordination. In this model ferrihydrite is described as a mixture of two major phases (akaganeite/goethite-like f-phase and feroxyhite-like d-phase) and a minor ultradispersed nanohematite phase. This model has been recently challenged and a new, single-phase model was proposed, having a basic structural motif closely related to the Baker-Figgs δ-Keggin cluster and is isostructural with the mineral akdalaite, Al10O14(OH)2. In its ideal form, the proposed new structure of FHYD consist of 80 % Oh and 20 % tetrahedral (Td) Fe3+ polyhedra which can be adequately described by a single-domain model with the hexagonal spacegroup 𝑃63𝑚𝑐 and unit cell dimensions 𝑎=5.95 Å and 𝑐=9.06 Å. In this study, nanoparticles of 2-line FHYD (FHYD2), 2-line FHYD deposited onto SiO2 (FHYD2/SiO2) and 6-line FHYD (FHYD6) synthesised using rapid hydrolysis of Fe(NO3)3.9H2O solutions were characterized using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), Mössbauer spectroscopy (MS) as well as magnetization and magnetic susceptibility measurements. The coordination environment of iron atoms in the structure of FHYD was investigated using TEM and MS. The thermal transformation of FHYD nanoparticles was monitored through changes in the magnetization as a function of temperature and the reduction behaviour in hydrogen environment was studied using temperature programmed reduction (TPR), in-situ XRD and MS. Electron diffraction, TEM/ scanning TEM (STEM) imaging, and electron energy loss (EELS) measurements were carried out on three different microscopes viz. JEOL JEM-2100 LaB6 TEM, aberration corrected Schottky-FEG JEOL JEM-ARM200F HRTEM and cold-FEG Zeiss SESAM TEM. EELS studies were concentrated mainly on the iron 𝐿-edge of FHYD and iron oxides reference spectra with well known crystal structures. The iron oxide Fe 𝐿-edge is usually characterized by two intense sharp peaks termed “white lines”. The fine structures introduced by the crystal field effect on the 𝐿- edge contain information that is highly specific to the Fe3+ site symmetry.
- Full Text:
- Date Issued: 2013
The development of platinum and palladium-selective polymeric materials
- Authors: Fayemi, Omolola Esther
- Date: 2013 , 2013-05-03
- Subjects: Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4287 , http://hdl.handle.net/10962/d1002964 , Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species (PtCl₆²⁻ and PdCl₄²⁻) on polystyrene-based beads and nanofibers as well as silica microparticles functionalized with polyamine centres derived from ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) is described. The functionalized sorbent materials were characterized by using microanalysis, SEM, XPS, BET and FTIR. The nanofiber sorbent material functionalized with ethylenediamine (F-EDA) had the highest loading capacity which was attributed to its high nitrogen content (10.83%) and larger surface area (241.3m²/g). The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies in 1 M HCI. The adsorption studies for both PtCl₆²⁻ and PdCl₄²⁻ on the polystyrene-based sorbent materials fit the Langmuir isotherm while the silica-based sorbents fitted the Freundlich isotherm with R² values > 0.99. In the column experiment the highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively on the nanofiber sorbent material based on ethylenediamine (EDA). The polystyrene and silica-based resins with triethylenetetramine (TETA) functionality (M-TETA and S-TETA) showed selectivity for platinum and palladium, respectively. Metal chlorido complexes loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as teh eluting agent with quantitative desorption efficiency under the selected experimental conditions. The separation of platinum from palladium was partially achieved by selective stripping of PtCl₆²⁻ with 0.5 M of NaClO₄ in 1.0 M HCI with PdCl₄²⁻ was eluted with 0.5 M thiourea in 1.0 M HCI. The selectivity of the M-TETA and S-TETA sorbent materials was proved by column separation of platinum(IV) and palladium(II), respectively, from synthetic solutions containing iridium(IV) and rhodium(III). The loading capacity for platinum on M-TETA was 0.09 mg/g while it was 0.27 mg/g for palladium on S-TETA. , Acrobat PDFMaker 10.1 for Word , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- Authors: Fayemi, Omolola Esther
- Date: 2013 , 2013-05-03
- Subjects: Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4287 , http://hdl.handle.net/10962/d1002964 , Polymers , Platinum , Palladium , Adsorption , Sorbents , Nanofibers , Amines , Nanoparticles
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species (PtCl₆²⁻ and PdCl₄²⁻) on polystyrene-based beads and nanofibers as well as silica microparticles functionalized with polyamine centres derived from ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) is described. The functionalized sorbent materials were characterized by using microanalysis, SEM, XPS, BET and FTIR. The nanofiber sorbent material functionalized with ethylenediamine (F-EDA) had the highest loading capacity which was attributed to its high nitrogen content (10.83%) and larger surface area (241.3m²/g). The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies in 1 M HCI. The adsorption studies for both PtCl₆²⁻ and PdCl₄²⁻ on the polystyrene-based sorbent materials fit the Langmuir isotherm while the silica-based sorbents fitted the Freundlich isotherm with R² values > 0.99. In the column experiment the highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively on the nanofiber sorbent material based on ethylenediamine (EDA). The polystyrene and silica-based resins with triethylenetetramine (TETA) functionality (M-TETA and S-TETA) showed selectivity for platinum and palladium, respectively. Metal chlorido complexes loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as teh eluting agent with quantitative desorption efficiency under the selected experimental conditions. The separation of platinum from palladium was partially achieved by selective stripping of PtCl₆²⁻ with 0.5 M of NaClO₄ in 1.0 M HCI with PdCl₄²⁻ was eluted with 0.5 M thiourea in 1.0 M HCI. The selectivity of the M-TETA and S-TETA sorbent materials was proved by column separation of platinum(IV) and palladium(II), respectively, from synthetic solutions containing iridium(IV) and rhodium(III). The loading capacity for platinum on M-TETA was 0.09 mg/g while it was 0.27 mg/g for palladium on S-TETA. , Acrobat PDFMaker 10.1 for Word , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- «
- ‹
- 1
- ›
- »