Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7244 , http://hdl.handle.net/10962/d1020248
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface. , Original publication is available at http://dx.doi.org/10.1016/j.jallcom.2015.05.083
- Full Text: false
- Date Issued: 2015
Optical properties of water-soluble L-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193609 , vital:45352 , xlink:href="https://doi.org/10.1016/j.optmat.2015.05.024"
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing L-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed L-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties.
- Full Text:
- Date Issued: 2015
Optical properties of water-soluble l-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7260 , http://hdl.handle.net/10962/d1020269
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.024
- Full Text: false
- Date Issued: 2015
Deposition of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shells around CdSeTe alloyed core quantum dots: effects on optical properties
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7289 , http://hdl.handle.net/10962/d1020342
- Description: In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. , Original publication is available at http://dx.doi.org/10.1002/bio.3013
- Full Text: false
- Date Issued: 2015
Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193575 , vital:45349 , xlink:href="https://doi.org/10.1016/j.jallcom.2015.05.083"
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface.
- Full Text:
- Date Issued: 2015
Photophysical and nonlinear optical studies of tetraakynyl zincphthalocyanine and its “clicked” analogue
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189325 , vital:44837 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.01.048"
- Description: We report here for the first time on the photophysical and nonlinear optical behavior of tetra-substituted alkynyl zinc phthalocyanine and its “clicked” analogue (4 and 5). The compounds exhibited high triplet quantum yields in dimethylsulphoxide (DMSO). Nonlinear optical (NLO) properties were also evaluated for the two compounds at 532 nm and 10 ns in DMSO. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The presence of electron acceptor groups fused with triazole linkers in the peripheral positions of 4 provide excellent coexistent features, such as enhanced triplet quantum yields and lifetimes compared to 5. Large third-order susceptibility (2.09 × 10−11 and 3.53 × 10−9 esu) and hyperpolarizability (1.09 × 10−30 and 9.13 × 10−29 esu) were estimated for complexs 4 and 5, respectively.
- Full Text:
- Date Issued: 2015
Mercaptopyridine-substituted indium, zinc, and metal-free phthalocyanines: nonlinear optical studies in solution and on polymer matrices
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7278 , http://hdl.handle.net/10962/d1020313
- Description: In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl3, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10−9 esu and 7.74 × 10−10 esu) and hyperpolarizability (2.13 × 10−28 and 8.37 × 10−29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1077237
- Full Text: false
- Date Issued: 2015
The effects of gold coated and uncoated zinc oxide nanohexagons on the photophysicochemical properties of the low symmetry zinc phthalocyanine
- Authors: D'Souza, Sarah , Ogbodu, Rachael , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189077 , vital:44814 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.06.088"
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results.
- Full Text:
- Date Issued: 2015
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
- Full Text:
- Date Issued: 2015
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7272 , http://hdl.handle.net/10962/d1020287 , Original publication is available at http://dx.doi.org/10.1016/j.saa.2014.12.070
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text: false
- Date Issued: 2015
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189537 , vital:44855 , xlink:href="https://doi.org/10.1016/j.saa.2014.12.070"
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text:
- Date Issued: 2015
Nonlinear optical response of tetra and mono substituted zinc phthalocyanine complexes
- Authors: Fashina, Adedayo , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7281 , http://hdl.handle.net/10962/d1020318 , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2015.06.003
- Description: The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied.
- Full Text: false
- Date Issued: 2015
The development of palladium (II)-specific amine-functionalized silica-based microparticles
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241083 , vital:50903 , xlink:href="https://doi.org/10.1080/01496395.2014.978017"
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources.
- Full Text:
- Date Issued: 2015
The Development of Palladium(II)-Specific Amine-Functionalized Silica-Based Microparticles: Adsorption and Column Separation Studies
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7269 , http://hdl.handle.net/10962/d1020278
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
- Date Issued: 2015
The development of Palladium(II)-specific amine-functionalized silica-based microparticles : adsorption and column separation studies
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7270 , http://hdl.handle.net/10962/d1020285
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
- Date Issued: 2015
Organosilicon compounds as fluorescent chemosensors for fluoride anion recognition
- Authors: Gai, Lizhi , Mack, John , Lu, Hua , Nyokong, Tebello , Li, Zhifang , Kobayashi, Nagao , Shen, Zhen
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241424 , vital:50938 , xlink:href="https://doi.org/10.1016/j.ccr.2014.10.009"
- Description: Recent developments in organosilicon-based chemosensors for F− recognition are reviewed. The design strategies for improving the photophysical properties of organosilicon-based chemosensors are elaborated, with an emphasis placed on their utility for biological applications. The photophysical properties and electronic structures are analyzed in depth with reference made to the results of molecular modeling calculation and possible future research directions are assessed.
- Full Text:
- Date Issued: 2015
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.
- Full Text:
- Date Issued: 2015