{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/29556"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/29556","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Encapsulation of iron(III) protoporphyrin IX and tetraphenylporphyrin in metal-organic frameworks for application as heterogeneous oxidation catalysts","abstract":"Two MOFs, [H2N(CH3)2][Zn3(TATB2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and ZnHKUST-1 (2) (TATB = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate) were investigated as potential hosts to encapsulate Fe(III) protoporphyrin IX (ferrihaem = Fe(III)PPIX) and Fe(III) tetraphenylporphyrin (Fe(III)TPP). Methyl orange (MO) adsorption was used as an initial model for substrate uptake in MOFs 1 and 2. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg.g-1 ) which could undergo in situ protonation upon exposure to aqueous HCl vapour. By contrast MO uptake by 2 was much lower (2 ± 1 mg.g-1 ) and PXRD indicated structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX incorporation into 1 were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (6 ± 1 mg.g1 ) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-visible spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-visible spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a µ-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modelling of the porphine core. For comparison, Fe(III)PPIX was further encapsulated in 2, forming Fe(III)PPIX-2. Reaction ABSTRACT of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) with H2O2, catalysed by Fe(III)PPIX-1 and -2 showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl due to the faster initial rate of reaction as well as the greater conversion of ABTS to ABTS●+ . Both frameworks 1 and 2 were also investigated as potential hosts to encapsulate Fe(III) tetraphenylporphyrin (Fe(III)TPP). Attempts to encapsulate Fe(III)TPP into 1 were unsuccessful, but Fe(III)TPP was successfully encapsulated into 2, forming Fe(III)TPP-2. The framework was characterised by PXRD and SEM-EDS confirmed uniform distribution of Fe(III)TPP through the framework. The loading of Fe(III)TPP determined using ICP-OES (0.604 ± 0.008 Fe mass %) agreed well with SEM-EDS data. Single crystals of Fe(III)TPP-2 were obtained and structure determination showed that the Fe(III) porphyrin was positionally disordered over three positions. The instability of Fe(III)TPP-2 in the presence of H2O resulted in it being an inappropriate choice as an oxidation catalyst. The kinetics of ABTS oxidation by H2O2 catalysed by Fe(III)PPIX-1 were further investigated. The peroxidatic activity of this heterogeneous system conforms to a rate law identical to that observed in solution with no discernible influence of particle size, suggesting that the MOF system closely mimics the solution state. The proposed rate law indicates a reaction mechanism with two possible pathways, as suggested for the same reaction in solution. The major pathway describes the coordination of H2O2 to the Fe(III) centre and subsequent formation of a high valent intermediate, while the minor pathway describes the same process preceded by ABTS coordination to the Fe(III) centre forming a six-coordinate complex. The further application of Fe(III)PPIX-1 as an oxidation catalyst was probed by investigating the catalytic oxidation of hydroquinone, thymol, benzyl alcohol and phenyl ethanol by tert-butyl-hydroperoxide ( tBuOOH). Reactions were successful and showed t1/2 values that increase with increasing substrate molecular volume.","abstract_html":"Two MOFs, [H2N(CH3)2][Zn3(TATB2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and ZnHKUST-1 (2) (TATB = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate) were investigated as potential hosts to encapsulate Fe(III) protoporphyrin IX (ferrihaem = Fe(III)PPIX) and Fe(III) tetraphenylporphyrin (Fe(III)TPP). Methyl orange (MO) adsorption was used as an initial model for substrate uptake in MOFs 1 and 2. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg.g-1 ) which could undergo in situ protonation upon exposure to aqueous HCl vapour. By contrast MO uptake by 2 was much lower (2 ± 1 mg.g-1 ) and PXRD indicated structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX incorporation into 1 were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (6 ± 1 mg.g1 ) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-visible spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-visible spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a µ-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modelling of the porphine core. For comparison, Fe(III)PPIX was further encapsulated in 2, forming Fe(III)PPIX-2. Reaction ABSTRACT of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) with H2O2, catalysed by Fe(III)PPIX-1 and -2 showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl due to the faster initial rate of reaction as well as the greater conversion of ABTS to ABTS●+ . Both frameworks 1 and 2 were also investigated as potential hosts to encapsulate Fe(III) tetraphenylporphyrin (Fe(III)TPP). Attempts to encapsulate Fe(III)TPP into 1 were unsuccessful, but Fe(III)TPP was successfully encapsulated into 2, forming Fe(III)TPP-2. The framework was characterised by PXRD and SEM-EDS confirmed uniform distribution of Fe(III)TPP through the framework. The loading of Fe(III)TPP determined using ICP-OES (0.604 ± 0.008 Fe mass %) agreed well with SEM-EDS data. Single crystals of Fe(III)TPP-2 were obtained and structure determination showed that the Fe(III) porphyrin was positionally disordered over three positions. The instability of Fe(III)TPP-2 in the presence of H2O resulted in it being an inappropriate choice as an oxidation catalyst. The kinetics of ABTS oxidation by H2O2 catalysed by Fe(III)PPIX-1 were further investigated. The peroxidatic activity of this heterogeneous system conforms to a rate law identical to that observed in solution with no discernible influence of particle size, suggesting that the MOF system closely mimics the solution state. The proposed rate law indicates a reaction mechanism with two possible pathways, as suggested for the same reaction in solution. The major pathway describes the coordination of H2O2 to the Fe(III) centre and subsequent formation of a high valent intermediate, while the minor pathway describes the same process preceded by ABTS coordination to the Fe(III) centre forming a six-coordinate complex. The further application of Fe(III)PPIX-1 as an oxidation catalyst was probed by investigating the catalytic oxidation of hydroquinone, thymol, benzyl alcohol and phenyl ethanol by tert-butyl-hydroperoxide ( tBuOOH). Reactions were successful and showed t1/2 values that increase with increasing substrate molecular volume.","abstract_has_math":false,"creators":["Dare, Nicola A"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Egan, Timothy John","Bourne, Susan"],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018","date_published":"2018","updated_at":"2026-07-22T22:23:22Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/29556","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Egan, Timothy John","Bourne, Susan"]},{"key":"dc:creator","label":"Author","values":["Dare, Nicola A"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2019-02-15T08:01:42Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2019-02-15T08:01:42Z"]},{"key":"dc:date.issued","label":"Date","values":["2018"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cape Town"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11427/29556"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Two MOFs, [H2N(CH3)2][Zn3(TATB2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and ZnHKUST-1 (2) (TATB = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate) were investigated as potential hosts to encapsulate Fe(III) protoporphyrin IX (ferrihaem = Fe(III)PPIX) and Fe(III) tetraphenylporphyrin (Fe(III)TPP). Methyl orange (MO) adsorption was used as an initial model for substrate uptake in MOFs 1 and 2. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg.g-1 ) which could undergo in situ protonation upon exposure to aqueous HCl vapour. By contrast MO uptake by 2 was much lower (2 ± 1 mg.g-1 ) and PXRD indicated structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX incorporation into 1 were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (6 ± 1 mg.g1 ) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-visible spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-visible spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a µ-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modelling of the porphine core. For comparison, Fe(III)PPIX was further encapsulated in 2, forming Fe(III)PPIX-2. Reaction ABSTRACT of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) with H2O2, catalysed by Fe(III)PPIX-1 and -2 showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl due to the faster initial rate of reaction as well as the greater conversion of ABTS to ABTS●+ . Both frameworks 1 and 2 were also investigated as potential hosts to encapsulate Fe(III) tetraphenylporphyrin (Fe(III)TPP). Attempts to encapsulate Fe(III)TPP into 1 were unsuccessful, but Fe(III)TPP was successfully encapsulated into 2, forming Fe(III)TPP-2. The framework was characterised by PXRD and SEM-EDS confirmed uniform distribution of Fe(III)TPP through the framework. The loading of Fe(III)TPP determined using ICP-OES (0.604 ± 0.008 Fe mass %) agreed well with SEM-EDS data. Single crystals of Fe(III)TPP-2 were obtained and structure determination showed that the Fe(III) porphyrin was positionally disordered over three positions. The instability of Fe(III)TPP-2 in the presence of H2O resulted in it being an inappropriate choice as an oxidation catalyst. The kinetics of ABTS oxidation by H2O2 catalysed by Fe(III)PPIX-1 were further investigated. The peroxidatic activity of this heterogeneous system conforms to a rate law identical to that observed in solution with no discernible influence of particle size, suggesting that the MOF system closely mimics the solution state. The proposed rate law indicates a reaction mechanism with two possible pathways, as suggested for the same reaction in solution. The major pathway describes the coordination of H2O2 to the Fe(III) centre and subsequent formation of a high valent intermediate, while the minor pathway describes the same process preceded by ABTS coordination to the Fe(III) centre forming a six-coordinate complex. The further application of Fe(III)PPIX-1 as an oxidation catalyst was probed by investigating the catalytic oxidation of hydroquinone, thymol, benzyl alcohol and phenyl ethanol by tert-butyl-hydroperoxide ( tBuOOH). Reactions were successful and showed t1/2 values that increase with increasing substrate molecular volume."]},{"key":"dc:title","label":"Title","values":["Encapsulation of iron(III) protoporphyrin IX and tetraphenylporphyrin in metal-organic frameworks for application as heterogeneous oxidation catalysts"]}]}],"canonical_facts":{"dc:contributor.advisor":["Egan, Timothy John","Bourne, Susan"],"dc:creator":["Dare, Nicola A"],"dc:date.accessioned":["2019-02-15T08:01:42Z"],"dc:date.available":["2019-02-15T08:01:42Z"],"dc:date.issued":["2018"],"dc:description.abstract":["Two MOFs, [H2N(CH3)2][Zn3(TATB2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and ZnHKUST-1 (2) (TATB = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate) were investigated as potential hosts to encapsulate Fe(III) protoporphyrin IX (ferrihaem = Fe(III)PPIX) and Fe(III) tetraphenylporphyrin (Fe(III)TPP). Methyl orange (MO) adsorption was used as an initial model for substrate uptake in MOFs 1 and 2. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg.g-1 ) which could undergo in situ protonation upon exposure to aqueous HCl vapour. By contrast MO uptake by 2 was much lower (2 ± 1 mg.g-1 ) and PXRD indicated structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX incorporation into 1 were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (6 ± 1 mg.g1 ) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-visible spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-visible spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a µ-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modelling of the porphine core. For comparison, Fe(III)PPIX was further encapsulated in 2, forming Fe(III)PPIX-2. Reaction ABSTRACT of 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) with H2O2, catalysed by Fe(III)PPIX-1 and -2 showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl due to the faster initial rate of reaction as well as the greater conversion of ABTS to ABTS●+ . Both frameworks 1 and 2 were also investigated as potential hosts to encapsulate Fe(III) tetraphenylporphyrin (Fe(III)TPP). Attempts to encapsulate Fe(III)TPP into 1 were unsuccessful, but Fe(III)TPP was successfully encapsulated into 2, forming Fe(III)TPP-2. The framework was characterised by PXRD and SEM-EDS confirmed uniform distribution of Fe(III)TPP through the framework. The loading of Fe(III)TPP determined using ICP-OES (0.604 ± 0.008 Fe mass %) agreed well with SEM-EDS data. Single crystals of Fe(III)TPP-2 were obtained and structure determination showed that the Fe(III) porphyrin was positionally disordered over three positions. The instability of Fe(III)TPP-2 in the presence of H2O resulted in it being an inappropriate choice as an oxidation catalyst. The kinetics of ABTS oxidation by H2O2 catalysed by Fe(III)PPIX-1 were further investigated. The peroxidatic activity of this heterogeneous system conforms to a rate law identical to that observed in solution with no discernible influence of particle size, suggesting that the MOF system closely mimics the solution state. The proposed rate law indicates a reaction mechanism with two possible pathways, as suggested for the same reaction in solution. The major pathway describes the coordination of H2O2 to the Fe(III) centre and subsequent formation of a high valent intermediate, while the minor pathway describes the same process preceded by ABTS coordination to the Fe(III) centre forming a six-coordinate complex. The further application of Fe(III)PPIX-1 as an oxidation catalyst was probed by investigating the catalytic oxidation of hydroquinone, thymol, benzyl alcohol and phenyl ethanol by tert-butyl-hydroperoxide ( tBuOOH). Reactions were successful and showed t1/2 values that increase with increasing substrate molecular volume."],"dc:identifier.uri":["http://hdl.handle.net/11427/29556"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Encapsulation of iron(III) protoporphyrin IX and tetraphenylporphyrin in metal-organic frameworks for application as heterogeneous oxidation catalysts"],"dc:type":["Doctoral Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-22T22:23:22Z"}