Phthalocyanine-nanoparticle conjugates supported on inorganic nanofibers as photocatalysts for the treatment of biological and organic pollutants as well as for hydrogen generation

This thesis reports on the synthesis, photophysicochemical and photocatalytic properties of various zinc phthalocyanines (Pcs). For enhanced properties and catalyst support, the reported Pcs were conjugated to different nanoparticles (NPs) through chemisorption as well as amide bond formation to yield Pc-NP conjugates. For increased catalyst surface area and catalyst reusability, the Pcs and some of their conjugates were also supported on electrospun inorganic nanofibers i.e. SiO2, hematite (abbreviated Hem and has formula α-Fe2O3), ZnO and TiO2 nanofibers. The effect that the number of charges on a Pc has on its antimicrobial activities was evaluated by comparing the photoactivities of neutral, octacationic and hexadecacationic Pcs against S. aureus, E. coli and C. albicans. The extent of enhancement of their antimicrobial activities upon conjugation (through chemisorption) to Ag NPs was also studied in solution and when supported on SiO2 nanofibers. The results showed that the hexadecacationic complex 3 possessed the best antimicrobial activity against all three microorganisms, in solution and when supported on the SiO2 nanofibers. Covalent conjugation of Pcs with carboxylic acid moieties (complexes 4-6) to amine functionalised NPs (Cys-Ag, NH2-Fe3O4 and Cys-Fe3O4@Ag) resulted in enhanced singlet oxygen generation and thus antibacterial efficiencies. Comparison of the photodegradation efficiencies of semiconductor nanofibers (hematite, ZnO and TiO2) when bare and when modified with a Pc (complex 6) were evaluated. Modification of the nanofibers with the Pc resulted in enhanced photoactivities for the nanofibers with the hematite nanofibers being the best. Modification of the hematite nanofibers with two different Pcs i.e. monosubstituted (complex 5) and an asymmetrical tetrasubstituted Pc (complex 6) showed that complex 6 better enhanced the activity of the nanofibers. Evaluation of the hydrogen generation efficiencies of the bare and modified TiO2 nanofibers calcined at different temperatures demonstrated that the anatase nanofibers calcined at 500 oC possessed the best catalytic efficiency. The efficiency of the TiO2 nanofibers was enhanced in the presence of the Co and Pd NPs as well as a Pc (complex 7), with the extent of enhancement being the greatest for the nanofibers modified with the Pd NPs. The reported findings therefore demonstrate the versatility of applications of Pcs for different water purification techniques when supported on different nanomaterials.Thesis (PhD) -- Faculty of Science, Chemistry, 202

Photocatalytic treatment of organic and inorganic water pollutants using zinc phthalocyanine-cobalt ferrite magnetic nanoparticle conjugates

This work explores the synthesis and photophysicochemical properties of zinc phthalocyanines when conjugated to cobalt ferrite magnetic nanoparticles. Phthalocyanines with amine and carboxylic acid functional groups were synthesised so as to covalently link them via amide bonds to cobalt ferrite magnetic nanoparticles with carboxylic acid and amine groups, respectively. Spectroscopic and microscopic studies confirmed the formation and purity of the phthalocyanine-cobalt ferrite magnetic nanoparticle conjugates which exhibited enhanced triplet and singlet quantum yields compared to the phthalocyanines alone. The studies showed that the presence of cobalt ferrite nanoparticles significantly lowered fluorescence quantum yields and lifetimes. The conjugates not only showed much higher singlet oxygen quantum yields compared to the phthalocyanines alone but were also attractive because of their magnetic regeneration and hence reusability properties, making them appealing for photocatalytic applications. The photocatalytic ability of some of the phthalocyanines and their conjugates were then tested based on their photooxidation and photoreduction abilities on Methyl Orange and hexavalent chromium, respectively. For catalyst support, some of the zinc phthalocyanines, cobalt ferrite magnetic nanoparticles and their respective conjugates were successfully incorporated into electrospun polystyrene and polyamide-6 fibers. Spectral characteristics of the functionalized electrospun fibers confirmed the incorporation of the photocatalysts and indicated that the phthalocyanines and their respective conjuagates remained intact with their integrity maintained within the polymeric fiber matrices. The photochemical properties of the complexes were equally maintained within the electrospun fibers hence they were applied in the photooxidation of azo dyes using Orange G and Methyl Orange as model organic compounds

Development of phthalocyanine functionalised TiO 2 and ZnO nanofibers for photodegradation of methyl orange

The photocatalytic activity of TiO2 and ZnO based catalysts, which is based on their ability to generate electron–hole pairs upon photoillumination is limited due to their wide band gaps and lack of efficient retrievability post-application. This work reports on the fabrication, characterisation and comparison of electrospun TiO2 and ZnO nanofibers when bare vs when functionalised with a phthalocyanine. The generated photocatalysts are attractive because they absorb visible light and are easily retrievable and hence reusable. With the Pc anchored onto their surfaces, the anatase TiO2 nanofibers and the wurzite ZnO nanofibers possessed singlet oxygen quantum yields of 0.22 and 0.16 in water, respectively. Evaluation of the photocatalytic efficiencies of the nanofibers was conducted by studying the photodegradation of methyl orange. The Pc decorated nanofibers were found to be more effective photocatalysts than the bare ones with the phthalocyanine TiO2 nanofibers being the best. The degradation kinetics were found to follow pseudo first order kinetics and obeyed the Langmuir Hinshelwood model. The nanocatalysts reported herein are therefore feasible candidates for real-life water purification applications

The photocatalytic properties of zinc phthalocyanines supported on hematite nanofibers for use against methyl orange and Staphylococcus aureus

Heterogeneous photocatalysis is a promising approach for environmental remediation from contaminants including microorganisms and organic pollutants. In this work, hematite nanofibers are fabricated and modified with a novel monosubstituted Pc (4) as well as an asymmetrical tetrasubstituted Pc (5) with the aim of creating hybrid photocatalysts. The photocatalytic activities of the unmodified and phthalocyanine modified hematite nanofibers were compared based on their efficiencies in the photoinactivation of S. aureus and photooxidation of methyl orange. For both applications, the hybrid nanofibers were found to be more efficient photocatalysts than the unmodified hematite nanofibers. Comparison of the modified nanofibers (4-Fe2O3 and 5-Fe2O3) showed that they have comparable antibacterial activity while the 5-Fe2O3 nanofibers are the best for the photooxidation of methyl orange. The singlet oxygen generation efficiency, high activity, versatility, regenerability and thus reusability of the fabricated hybrid nanofibers makes them ideal candidates for real life water treatment studies

The improved antibacterial efficiency of a zinc phthalocyanine when embedded on silver nanoparticle modified silica nanofibers

This work reports on the fabrication and modification of electrospun polymer free silica nanofibers (SiO2 NFs) with the aim of creating heterogeneous antibacterial catalysts. The optical and photophysical properties of the obtained NFs i.e. bare SiO2, Ag-SiO2, Pc-SiO2 and Pc@Ag-SiO2 NFs (Pc = phthalocyanine) were compared and reported. The singlet oxygen quantum yields of the Pc-SiO2 and Pc@Ag-SiO2 NFs were also quantified and found to be 0.08 and 0.12, respectively, in water. All the modified SiO2 NFs were found to possess photoactivity against S. aureus with the most effective being the Pc@Ag-SiO2 NFs due to the synergy between the Pc and Ag nanoparticles. The bare SiO2 NFs do not exhibit any antibacterial activity while the Ag-SiO2 and Pc@Ag-SiO2 NFs were found to also exhibit dark toxicity. The generated photocatalysts are attractive because they are active against bacteria and they are easily retrievable post-application. The nanocatalysts reported herein are therefore feasible candidates for real-life antibacterial applications

Decorated titania fibers as photocatalysts for hydrogen generation and organic matter degradation

Heterogenous photocatalysts based on electrospun fibers composed of polyvinylpyrrolidone and titanium propoxide were prepared and heated at 500, 750 and 950 °C to obtain anatase and rutile fibers. The fibers were then decorated with Pd and Co nanoparticles as well as a symmetrical zinc phthalocyanine (Pc). The fibrous materials obtained have a paper-like macroscopic appearance allowing for easy handling and separation. The photocatalytic activities of the new materials were evaluated for the generation of H2 upon UV (368 nm) or visible (630 nm) light excitation. Depending on the heat treatment or the post-synthetic decoration method, the materials show higher, or similar, activity compared to P25-TiO2, with superior ease of separation. The catalysts showed ability to degrade organic matter, with MeOH used as a model compound. This is of considerable importance for potential water treatment applications that will require flow-compatible materials

Advances on sonophotocatalysis as a water and wastewater treatment technique: efficiency, challenges and process optimisation

Due to water shortage and increased water pollution, various methods are being explored to improve water quality by treating contaminants. Sonophotocatalysis is a combination of two individual water treatment processes i.e., photocatalysis and sonocatalysis. With advantages including shorter reaction times and enhanced activity, this technique shows possible futuristic applications as an efficient water treatment technology. Herein, background insight on sonophotocalysis as a water and wastewater treatment technique as well as the general mechanism of activity is explained. The commonly used catalysts for sonophotocatalytic applications as well as their synthesis pathways are also briefly discussed. Additionally, the utilisation of sonophotocatalysis for the disinfection of various microbial species as well as treatment of wastewater pollutants including organic (dyes, pharmaceuticals and pesticides) and inorganic species (heavy metals) is deliberated. This review also gives a critical analysis of the efficiency, enhancement strategies as well as challenges and outlooks in this field. It is thus intended to give insight to researchers in the context of facilitating future developments in the field of water treatment, and advancing sonophotocatalysis towards large-scale implementation and commercialization

Fibrous TiO2 Alternatives for Semiconductor-Based Catalysts for Photocatalytic Water Remediation Involving Organic Contaminants

Water decontamination remains a challenge in several developed and developing countries. Affordable and efficient approaches are needed urgently. In this scenario, heterogeneous photocatalysts appear as one of the most promising alternatives. This justifies the extensive attention that semiconductors, such as TiO2, have gained over the last decades. Several studies have evaluated their efficiency for environmental applications; however, most of these tests rely on the use of powder materials that have minimal to no applicability for large-scale applications. In this work, we investigated three fibrous TiO2 photocatalysts, TiO2 nanofibers (TNF), TiO2 on glass wool (TGW), and TiO2 in glass fiber filters (TGF). All materials have macroscopic structures that can be easily separated from solutions or that can work as fixed beds under flow conditions. We evaluated and compared their ability to bleach a surrogate dye molecule, crocin, under batch and flow conditions. Using black light (UVA/visible), our catalysts were able to bleach a minimum of 80% of the dye in batch experiments. Under continuous flow experiments, all catalysts could decrease dye absorption under shorter irradiation times: TGF, TNF, and TGW could, respectively, bleach 15, 18, and 43% of the dye with irradiation times as short as 35 s. Catalyst comparison was based on the selection of physical and chemical criteria relevant for application on water remediation. Their relative performance was ranked and applied in a radar plot. The features evaluated here had two distinct groups, chemical performance, which related to the dye degradation, and mechanical properties, which described their applicability in different systems. This comparative analysis gives insights into the selection of the right flow-compatible photocatalyst for water remediation

The photodynamic antimicrobial chemotherapy of Stapphylococcus aureus using an asymmetrical zinc phthalocyanine conjugated to silver and iron oxide based nanoparticles

The synthesis and characterisation of asymmetrical zinc(II) 2(3)-mono-isophthalic acid-9(10),16(17),23 (24)-tri (tert-butylphenoxy) phthalocyanine (complex 4) are reported. The phthalocyanine is conjugated to cysteamine capped silver nanoparticles (Cys-Ag NPs), amine functionalised iron oxide magnetic nanoparticles (NH2-Fe3O4 NPs) and a core-shell composite of the two (Cys-Fe3O4@Ag) via amide bonds. The photo-physico-chemical properties of complex 4 and its respective nanoconjugates (4-Ag, 4-Fe3O4 NPs and 4-Fe3O4@Ag NPs) are also reported. The nanoconjugates showed improved triplet and singlet oxygen quantum yields compared to complex 4. The antibacterial activity of complex 4 and its nanoconjugates were also evaluated on S. aureus wherein their activity was found to be mainly visible light driven with the best catalyst being 4-Fe3O4@Ag. The work therefore demonstrates the feasibility of phthalocyanine-nanoparticle based compounds as potential agents in real life antibacterial treatmen

Dual phototransformation of the pollutants methyl orange and Cr (VI) using phthalocyanine-cobalt ferrite based magnetic nanocomposites

Bifunctional nanocomposites based on zinc phthalocyanines and glutathione capped CoFe2O4 magnetic nanoparticles (GSH-CoFe2O4 MNPs) are applied in a binary system wherein simultaneous photooxidation of methyl orange (MO) and photoreduction of Cr (VI) are conducted. The photoactivity of two zinc Pcs with different functional moieties are compared based on their interactions with GSH-CoFe2O4 MNPs. Conjugation of the Pcs to the GSH-CoFe2O4 MNPs not only enhanced their singlet oxygen production but also their photocatalytic activity in both photooxidation and photoreduction experiments. Using electron paramagnetic resonance (EPR) spectroscopy, the Pc-MNP conjugates reported herein were found to exhibit superparamagnetic behaviour, giving the advantage of easy separation using an external magnetic field post application, an attractive attribute for heterogeneous catalysis. The catalysts reported herein are therefore good candidates as catalysts for real life water purification analyses as they facilitate the treatment of both organic and inorganic water pollutants