{"id":{"repo_id":"southwales","oai_identifier":"oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"},"canonical_url":"https://search.dev.ndltd.org/etd/southwales/oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b","repository":{"repo_id":"southwales","name":"University of South Wales","base_url":"https://pure.southwales.ac.uk/ws/oai"},"display":{"title":"Metal Complexes of Functionalised Phenanthroline-based Ligands and Their Application Towards the Transformation of CO₂","abstract":"The increase in global carbon dioxide (CO2) emissions since the start of the industrial revolution has led to a marked increase in global average temperature. If emissions continue to rise, the damage to the environment could become irreparable. To achieve a global net zero before this, it is essential to reduce CO2 emissions either by storage or transformation into value commodity chemicals. The production of a chemical that can be sold provides a valuable economic benefit which is crucial if the process is to be adopted by industry. This work aims to provide a suitable method for the valorisation of CO2 which can be applied for use in the steel industry. The capture and separation of CO2 is not addressed as the focus is on the transformation of isolated gaseous CO2. As such, this work could also be applied to other industries outside of steel production. There is a wealth of research into the valorisation of CO2, and it can be transformed into numerous products.
Chapter 1 provides an overview of the mechanisms for the activation of CO2 by the use of transition metal catalysts. The discussion focuses on the homogeneous catalytic hydrogenation of CO2 into products such as carbon monoxide (CO), formic acid/formate, formaldehyde, methanol and methane. Further discussion highlights industrial processes that use CO2, including for the production of organic carbonates.
Chapter 2 describes the project design which focused on utilising metal complexes of functionalised phenanthroline-based ligands. Pendant amine groups were incorporated into the phenanthroline backbone with the vision to facilitate ligand cooperativity mechanisms to assist in the activation of CO2. This chapter focused on the synthesis of zinc halide complexes of these ligands and their characterisation. The isolated complexes were tested for further reactivity and catalytic applications, however they did not show catalytic capability and produced challenges in their reactivity tests.
Chapter 3 describes the synthesis, characterisation and catalytic testing of ruthenium based complexes based on the functionalised phenanthroline ligands prepared in the previous chapter. An investigation into the catalytic activity of these complexes was conducted to compare with similar catalysts reported in the literature. A range of ruthenium-based complexes have been prepared which have shown activity for the catalytic hydrogenation of CO2 into formate. The greatest activity achieved featured the catalyst [(p-cymene)Ru(Cl)(PhNHPhen)]Cl under dry conditions which gave 2790 TON. Some efforts were made to perform this reaction under more sustainable conditions; however, all changes reduced the activity significantly. The ligands produced herein were designed with pendant –NHR groups which could assist in the activation of the CO2 or molecular hydrogen (H2). No evidence was observed to confirm the reaction pathway, however there was a marked (11x) reduction in activity when the –NHPh moiety was replaced with a hydroxyl (–OH) group. The zinc halide complexes, and the ruthenium based complexes have been fully characterised using 1H and 13C NMR, ATR-FTIR, Mass Spectrometry and Elemental analysis. Single crystals suitable for X-ray diffraction were obtained for six of these complexes. A range of additional complexes featuring zinc and nickel metal centres was also explored during this study.","abstract_html":"The increase in global carbon dioxide (CO<sub>2</sub>) emissions since the start of the industrial revolution has led to a marked increase in global average temperature. If emissions continue to rise, the damage to the environment could become irreparable. To achieve a global net zero before this, it is essential to reduce CO<sub>2</sub> emissions either by storage or transformation into value commodity chemicals. The production of a chemical that can be sold provides a valuable economic benefit which is crucial if the process is to be adopted by industry. This work aims to provide a suitable method for the valorisation of CO<sub>2</sub> which can be applied for use in the steel industry. The capture and separation of CO<sub>2</sub> is not addressed as the focus is on the transformation of isolated gaseous CO<sub>2</sub>. As such, this work could also be applied to other industries outside of steel production. There is a wealth of research into the valorisation of CO<sub>2</sub>, and it can be transformed into numerous products. <br/><br/><b>Chapter 1</b> provides an overview of the mechanisms for the activation of CO<sub>2</sub> by the use of transition metal catalysts. The discussion focuses on the homogeneous catalytic hydrogenation of CO<sub>2</sub> into products such as carbon monoxide (CO), formic acid/formate, formaldehyde, methanol and methane. Further discussion highlights industrial processes that use CO<sub>2</sub>, including for the production of organic carbonates. <br/><br/><b>Chapter 2 </b>describes the project design which focused on utilising metal complexes of functionalised phenanthroline-based ligands. Pendant amine groups were incorporated into the phenanthroline backbone with the vision to facilitate ligand cooperativity mechanisms to assist in the activation of CO<sub>2</sub>. This chapter focused on the synthesis of zinc halide complexes of these ligands and their characterisation. The isolated complexes were tested for further reactivity and catalytic applications, however they did not show catalytic capability and produced challenges in their reactivity tests. <br/><br/><b>Chapter 3</b> describes the synthesis, characterisation and catalytic testing of ruthenium based complexes based on the functionalised phenanthroline ligands prepared in the previous chapter. An investigation into the catalytic activity of these complexes was conducted to compare with similar catalysts reported in the literature. A range of ruthenium-based complexes have been prepared which have shown activity for the catalytic hydrogenation of CO<sub>2</sub> into formate. The greatest activity achieved featured the catalyst [(p-cymene)Ru(Cl)(<sup>PhNH</sup>Phen)]Cl under dry conditions which gave 2790 TON. Some efforts were made to perform this reaction under more sustainable conditions; however, all changes reduced the activity significantly. The ligands produced herein were designed with pendant –NHR groups which could assist in the activation of the CO<sub>2</sub> or molecular hydrogen (H<sub>2</sub>). No evidence was observed to confirm the reaction pathway, however there was a marked (11x) reduction in activity when the –NHPh moiety was replaced with a hydroxyl (–OH) group. The zinc halide complexes, and the ruthenium based complexes have been fully characterised using <sup>1</sup>H and <sup>13</sup>C NMR, ATR-FTIR, Mass Spectrometry and Elemental analysis. Single crystals suitable for X-ray diffraction were obtained for six of these complexes. A range of additional complexes featuring zinc and nickel metal centres was also explored during this study.","abstract_has_math":false,"creators":["Goldsworthy, Joseph"],"institution":null,"degree_name":"Doctoral Thesis","degree_level":"Student thesis","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Da Costa, Rosenildo","Owen, Gareth","Guwy, Alan"],"committee_chairs":[],"committee_members":[],"year":2026,"date_issued":"2026","date_published":"2026","updated_at":"2026-07-24T04:39:57Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"],"render_values":[{"text":"oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b","href":null,"code":true}]}]},"links":{"outbound_url":"https://pure.southwales.ac.uk/en/studentTheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Da Costa, Rosenildo","Owen, Gareth","Guwy, Alan"]},{"key":"dc:creator","label":"Author","values":["Goldsworthy, Joseph"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2026"]},{"key":"dc:date.issued","label":"Date","values":["2026"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://pure.southwales.ac.uk/en/studentTheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Student thesis"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["Doctoral Thesis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b","https://pure.southwales.ac.uk/en/studentTheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://pure.southwales.ac.uk/files/36406442/Joseph_Goldsworthy_Final_Thesis_Dec_25.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The increase in global carbon dioxide (CO2) emissions since the start of the industrial revolution has led to a marked increase in global average temperature. If emissions continue to rise, the damage to the environment could become irreparable. To achieve a global net zero before this, it is essential to reduce CO2 emissions either by storage or transformation into value commodity chemicals. The production of a chemical that can be sold provides a valuable economic benefit which is crucial if the process is to be adopted by industry. This work aims to provide a suitable method for the valorisation of CO2 which can be applied for use in the steel industry. The capture and separation of CO2 is not addressed as the focus is on the transformation of isolated gaseous CO2. As such, this work could also be applied to other industries outside of steel production. There is a wealth of research into the valorisation of CO2, and it can be transformed into numerous products.
Chapter 1 provides an overview of the mechanisms for the activation of CO2 by the use of transition metal catalysts. The discussion focuses on the homogeneous catalytic hydrogenation of CO2 into products such as carbon monoxide (CO), formic acid/formate, formaldehyde, methanol and methane. Further discussion highlights industrial processes that use CO2, including for the production of organic carbonates.
Chapter 2 describes the project design which focused on utilising metal complexes of functionalised phenanthroline-based ligands. Pendant amine groups were incorporated into the phenanthroline backbone with the vision to facilitate ligand cooperativity mechanisms to assist in the activation of CO2. This chapter focused on the synthesis of zinc halide complexes of these ligands and their characterisation. The isolated complexes were tested for further reactivity and catalytic applications, however they did not show catalytic capability and produced challenges in their reactivity tests.
Chapter 3 describes the synthesis, characterisation and catalytic testing of ruthenium based complexes based on the functionalised phenanthroline ligands prepared in the previous chapter. An investigation into the catalytic activity of these complexes was conducted to compare with similar catalysts reported in the literature. A range of ruthenium-based complexes have been prepared which have shown activity for the catalytic hydrogenation of CO2 into formate. The greatest activity achieved featured the catalyst [(p-cymene)Ru(Cl)(PhNHPhen)]Cl under dry conditions which gave 2790 TON. Some efforts were made to perform this reaction under more sustainable conditions; however, all changes reduced the activity significantly. The ligands produced herein were designed with pendant –NHR groups which could assist in the activation of the CO2 or molecular hydrogen (H2). No evidence was observed to confirm the reaction pathway, however there was a marked (11x) reduction in activity when the –NHPh moiety was replaced with a hydroxyl (–OH) group. The zinc halide complexes, and the ruthenium based complexes have been fully characterised using 1H and 13C NMR, ATR-FTIR, Mass Spectrometry and Elemental analysis. Single crystals suitable for X-ray diffraction were obtained for six of these complexes. A range of additional complexes featuring zinc and nickel metal centres was also explored during this study."]},{"key":"dc:title","label":"Title","values":["Metal Complexes of Functionalised Phenanthroline-based Ligands and Their Application Towards the Transformation of CO₂"]}]}],"canonical_facts":{"dc:contributor.advisor":["Da Costa, Rosenildo","Owen, Gareth","Guwy, Alan"],"dc:creator":["Goldsworthy, Joseph"],"dc:date":["2026"],"dc:date.issued":["2026"],"dc:description.abstract":["The increase in global carbon dioxide (CO2) emissions since the start of the industrial revolution has led to a marked increase in global average temperature. If emissions continue to rise, the damage to the environment could become irreparable. To achieve a global net zero before this, it is essential to reduce CO2 emissions either by storage or transformation into value commodity chemicals. The production of a chemical that can be sold provides a valuable economic benefit which is crucial if the process is to be adopted by industry. This work aims to provide a suitable method for the valorisation of CO2 which can be applied for use in the steel industry. The capture and separation of CO2 is not addressed as the focus is on the transformation of isolated gaseous CO2. As such, this work could also be applied to other industries outside of steel production. There is a wealth of research into the valorisation of CO2, and it can be transformed into numerous products.
Chapter 1 provides an overview of the mechanisms for the activation of CO2 by the use of transition metal catalysts. The discussion focuses on the homogeneous catalytic hydrogenation of CO2 into products such as carbon monoxide (CO), formic acid/formate, formaldehyde, methanol and methane. Further discussion highlights industrial processes that use CO2, including for the production of organic carbonates.
Chapter 2 describes the project design which focused on utilising metal complexes of functionalised phenanthroline-based ligands. Pendant amine groups were incorporated into the phenanthroline backbone with the vision to facilitate ligand cooperativity mechanisms to assist in the activation of CO2. This chapter focused on the synthesis of zinc halide complexes of these ligands and their characterisation. The isolated complexes were tested for further reactivity and catalytic applications, however they did not show catalytic capability and produced challenges in their reactivity tests.
Chapter 3 describes the synthesis, characterisation and catalytic testing of ruthenium based complexes based on the functionalised phenanthroline ligands prepared in the previous chapter. An investigation into the catalytic activity of these complexes was conducted to compare with similar catalysts reported in the literature. A range of ruthenium-based complexes have been prepared which have shown activity for the catalytic hydrogenation of CO2 into formate. The greatest activity achieved featured the catalyst [(p-cymene)Ru(Cl)(PhNHPhen)]Cl under dry conditions which gave 2790 TON. Some efforts were made to perform this reaction under more sustainable conditions; however, all changes reduced the activity significantly. The ligands produced herein were designed with pendant –NHR groups which could assist in the activation of the CO2 or molecular hydrogen (H2). No evidence was observed to confirm the reaction pathway, however there was a marked (11x) reduction in activity when the –NHPh moiety was replaced with a hydroxyl (–OH) group. The zinc halide complexes, and the ruthenium based complexes have been fully characterised using 1H and 13C NMR, ATR-FTIR, Mass Spectrometry and Elemental analysis. Single crystals suitable for X-ray diffraction were obtained for six of these complexes. A range of additional complexes featuring zinc and nickel metal centres was also explored during this study."],"dc:identifier":["oai:pure.atira.dk:studenttheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b","https://pure.southwales.ac.uk/en/studentTheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"],"dc:identifier.uri":["https://pure.southwales.ac.uk/files/36406442/Joseph_Goldsworthy_Final_Thesis_Dec_25.pdf"],"dc:language":["eng"],"dc:relation.isreferencedby":["https://pure.southwales.ac.uk/en/studentTheses/a8b63b37-1e31-42a3-9af3-c48864f6f59b"],"dc:title":["Metal Complexes of Functionalised Phenanthroline-based Ligands and Their Application Towards the Transformation of CO₂"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["Student thesis"],"dc:type.qualificationname":["Doctoral Thesis"]},"updated_at":"2026-07-24T04:39:57Z"}