{"id":{"repo_id":"tu-berlin","oai_identifier":"oai:depositonce.tu-berlin.de:11303/23253"},"canonical_url":"https://search.dev.ndltd.org/etd/tu-berlin/oai:depositonce.tu-berlin.de:11303/23253","repository":{"repo_id":"tu-berlin","name":"Technische Universität Berlin","base_url":"https://api-depositonce.tu-berlin.de/server/oai/request"},"display":{"title":"Oxocarbon-derived porous carbonaceous materials for electrocatalysis","abstract":"The rising global demand for efficient energy conversion technologies underscores the necessity for advanced carbon materials with specific structural and functional attributes. Porous carbon materials, characterized by their high specific surface area and tunable pore structures, are particularly promising for electrocatalysis. However, the rational design of functional carbons, the development of new synthesis routes, and the exploration of the structure-activity relationship still remain challenging. This dissertation contributes to the development of novel oxygen-doped functional porous carbon materials derived from diverse oxocarbons. It focuses on tailoring their structures and properties to enhance the electrocatalytic performance, amming to elucidate the structure-activity relationships and provide new insights of developing advanced carbonaceous materials for electrocatalysis. In Chapter 2, red carbon oligomer was used as the precursor for the synthesis of carbons. This precursor without inactive C-H bond can undergo crosslinking with the only release of edge CO2 groups, facilitating the formation of porous oxocarbons at temperatures as low as 400°C without templating agents. Owing to the microporous structures, the carbon materials act as metal-free electrocatalysts presenting good performance for oxygen reduction reaction. Additionally, it enables effective crosslinking of the precursor on non-conductive surfaces at low temperatures, yielding thin conductive carbon films resistant to corrosive environments. SnCl2 was used as salt melt in Chapter 3 to further lower the temperature requirement of thermal condensation of red carbon oligomer, resulting in higher specific surface area and porosity. SnCl2 as a reactive salt melt can intercept the oxygen atoms of red carbon, causing the removal of oxygen atoms and favoring the thermal condensation process. Moreover, the in-situ formation of SnO2 nanoparticles acted as hard templates, further leading to highly porous structures. Such pore formation mechanism was confirmed also applicable for other oxygen-rich precursors. The obtained carbons with oxygen functionalities presented high activity and selectivity for electrocatalytic nitrate hydrogenation to ammonia, overpassing other carbon materials, even the carbon-supported metals. In Chapter 4, THQ molecule, an oxygen-rich compound, was utilized as a precursor for the preparation of oxocarbons and oxocarbon-supported Cu SACs in the presence of MgCl2∙6H2O. The interaction between MgCl2∙6H2O and the hydroxyl groups of THQ contributed to the specific growth of the structures, leading to homogeneous 2D flake structures. Moreover, Mg can intercept oxygen from the THQ molecule, forming MgO secondary hard templates and resulting in mesoporous structures with a high specific surface area of 1177 m²/g at 600°C. Furthermore, THQ served as a ligand in the synthesis of THQ-Cu MOFs, which were subsequently employed to design oxygen-stabilized Cu SACs on oxygen-rich carbon supports. The Cu SACs exhibited high activity in glycerol oxidation, achieving high Faradaic efficiency and selectivity, superior to many other Cu-based catalysts, which suggested the promising utilization as a catalyst for converting byproducts into valuable formic acid.","abstract_html":"The rising global demand for efficient energy conversion technologies underscores the necessity for advanced carbon materials with specific structural and functional attributes. Porous carbon materials, characterized by their high specific surface area and tunable pore structures, are particularly promising for electrocatalysis. However, the rational design of functional carbons, the development of new synthesis routes, and the exploration of the structure-activity relationship still remain challenging. This dissertation contributes to the development of novel oxygen-doped functional porous carbon materials derived from diverse oxocarbons. It focuses on tailoring their structures and properties to enhance the electrocatalytic performance, amming to elucidate the structure-activity relationships and provide new insights of developing advanced carbonaceous materials for electrocatalysis. In Chapter 2, red carbon oligomer was used as the precursor for the synthesis of carbons. This precursor without inactive C-H bond can undergo crosslinking with the only release of edge CO2 groups, facilitating the formation of porous oxocarbons at temperatures as low as 400°C without templating agents. Owing to the microporous structures, the carbon materials act as metal-free electrocatalysts presenting good performance for oxygen reduction reaction. Additionally, it enables effective crosslinking of the precursor on non-conductive surfaces at low temperatures, yielding thin conductive carbon films resistant to corrosive environments. SnCl2 was used as salt melt in Chapter 3 to further lower the temperature requirement of thermal condensation of red carbon oligomer, resulting in higher specific surface area and porosity. SnCl2 as a reactive salt melt can intercept the oxygen atoms of red carbon, causing the removal of oxygen atoms and favoring the thermal condensation process. Moreover, the in-situ formation of SnO2 nanoparticles acted as hard templates, further leading to highly porous structures. Such pore formation mechanism was confirmed also applicable for other oxygen-rich precursors. The obtained carbons with oxygen functionalities presented high activity and selectivity for electrocatalytic nitrate hydrogenation to ammonia, overpassing other carbon materials, even the carbon-supported metals. In Chapter 4, THQ molecule, an oxygen-rich compound, was utilized as a precursor for the preparation of oxocarbons and oxocarbon-supported Cu SACs in the presence of MgCl2∙6H2O. The interaction between MgCl2∙6H2O and the hydroxyl groups of THQ contributed to the specific growth of the structures, leading to homogeneous 2D flake structures. Moreover, Mg can intercept oxygen from the THQ molecule, forming MgO secondary hard templates and resulting in mesoporous structures with a high specific surface area of 1177 m²/g at 600°C. Furthermore, THQ served as a ligand in the synthesis of THQ-Cu MOFs, which were subsequently employed to design oxygen-stabilized Cu SACs on oxygen-rich carbon supports. The Cu SACs exhibited high activity in glycerol oxidation, achieving high Faradaic efficiency and selectivity, superior to many other Cu-based catalysts, which suggested the promising utilization as a catalyst for converting byproducts into valuable formic acid.","abstract_has_math":false,"creators":["Zheng, Xinyue"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Thomas, Arne","Antonietti, Markus"],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024","date_published":"2024","updated_at":"2026-07-27T21:28:42Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":["https://creativecommons.org/licenses/by/4.0/"],"identifier_entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://doi.org/10.14279/depositonce-22067"],"render_values":[{"text":"https://doi.org/10.14279/depositonce-22067","href":"https://doi.org/10.14279/depositonce-22067","code":true}]}]},"links":{"outbound_url":"https://depositonce.tu-berlin.de/handle/11303/23253","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Thomas, Arne","Antonietti, Markus"]},{"key":"dc:creator","label":"Author","values":["Zheng, Xinyue"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2024-11-21T11:19:01Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2024-11-21T11:19:01Z"]},{"key":"dc:date.issued","label":"Date","values":["2024"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral Thesis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://creativecommons.org/licenses/by/4.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://depositonce.tu-berlin.de/handle/11303/23253","https://doi.org/10.14279/depositonce-22067"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The rising global demand for efficient energy conversion technologies underscores the necessity for advanced carbon materials with specific structural and functional attributes. Porous carbon materials, characterized by their high specific surface area and tunable pore structures, are particularly promising for electrocatalysis. However, the rational design of functional carbons, the development of new synthesis routes, and the exploration of the structure-activity relationship still remain challenging. This dissertation contributes to the development of novel oxygen-doped functional porous carbon materials derived from diverse oxocarbons. It focuses on tailoring their structures and properties to enhance the electrocatalytic performance, amming to elucidate the structure-activity relationships and provide new insights of developing advanced carbonaceous materials for electrocatalysis. In Chapter 2, red carbon oligomer was used as the precursor for the synthesis of carbons. This precursor without inactive C-H bond can undergo crosslinking with the only release of edge CO2 groups, facilitating the formation of porous oxocarbons at temperatures as low as 400°C without templating agents. Owing to the microporous structures, the carbon materials act as metal-free electrocatalysts presenting good performance for oxygen reduction reaction. Additionally, it enables effective crosslinking of the precursor on non-conductive surfaces at low temperatures, yielding thin conductive carbon films resistant to corrosive environments. SnCl2 was used as salt melt in Chapter 3 to further lower the temperature requirement of thermal condensation of red carbon oligomer, resulting in higher specific surface area and porosity. SnCl2 as a reactive salt melt can intercept the oxygen atoms of red carbon, causing the removal of oxygen atoms and favoring the thermal condensation process. Moreover, the in-situ formation of SnO2 nanoparticles acted as hard templates, further leading to highly porous structures. Such pore formation mechanism was confirmed also applicable for other oxygen-rich precursors. The obtained carbons with oxygen functionalities presented high activity and selectivity for electrocatalytic nitrate hydrogenation to ammonia, overpassing other carbon materials, even the carbon-supported metals. In Chapter 4, THQ molecule, an oxygen-rich compound, was utilized as a precursor for the preparation of oxocarbons and oxocarbon-supported Cu SACs in the presence of MgCl2∙6H2O. The interaction between MgCl2∙6H2O and the hydroxyl groups of THQ contributed to the specific growth of the structures, leading to homogeneous 2D flake structures. Moreover, Mg can intercept oxygen from the THQ molecule, forming MgO secondary hard templates and resulting in mesoporous structures with a high specific surface area of 1177 m²/g at 600°C. Furthermore, THQ served as a ligand in the synthesis of THQ-Cu MOFs, which were subsequently employed to design oxygen-stabilized Cu SACs on oxygen-rich carbon supports. The Cu SACs exhibited high activity in glycerol oxidation, achieving high Faradaic efficiency and selectivity, superior to many other Cu-based catalysts, which suggested the promising utilization as a catalyst for converting byproducts into valuable formic acid.","Die weltweit steigende Nachfrage nach effizienten Energieumwandlungstechnologien unterstreicht die Notwendigkeit moderner Kohlenstoffmaterialien mit spezifischen strukturellen und funktionellen Eigenschaften. Poröse Kohlenstoffmaterialien, die sich durch ihre hohe spezifische Oberfläche und abstimmbare Porenstrukturen auszeichnen, sind besonders vielversprechend für die Elektrokatalyse. Das rationale Design funktioneller Kohlenstoffe, die Entwicklung neuer Synthesewege und die Erforschung der Struktur-Aktivitäts-Beziehung sind jedoch nach wie vor eine Herausforderung. Diese Dissertation trägt zur Entwicklung neuartiger sauerstoffdotierter funktioneller poröser Kohlenstoffmaterialien bei, die aus verschiedenen Oxokohlenstoffen gewonnen werden. Sie konzentriert sich auf die Anpassung ihrer Strukturen und Eigenschaften, um die elektrokatalytische Leistung zu verbessern, die Struktur-Aktivitäts-Beziehungen aufzuklären und neue Einblicke in die Entwicklung fortschrittlicher kohlenstoffhaltiger Materialien für die Elektrokatalyse zu gewinnen. In Kapitel 2 wurde ein rotes Kohlenstoff-Oligomer als Vorläufer für die Synthese von Kohlenstoffen verwendet. Dieser Vorläufer ohne inaktive C-H-Bindung kann vernetzt werden, wobei nur die CO2-Randgruppen freigesetzt werden, was die Bildung von porösen Oxokohlenstoffen bei Temperaturen von nur 400 °C ohne Schablonenmittel ermöglicht. Aufgrund der mikroporösen Strukturen wirken die Kohlenstoffmaterialien als metallfreie Elektrokatalysatoren mit guter Leistung bei der Sauerstoffreduktionsreaktion. Darüber hinaus ermöglicht es eine effektive Vernetzung des Vorläufers auf nichtleitenden Oberflächen bei niedrigen Temperaturen, wodurch dünne leitfähige Kohlenstofffilme entstehen, die gegen korrosive Umgebungen resistent sind. SnCl2 wurde in Kapitel 3 als Salzschmelze verwendet, um die Temperaturanforderungen für die thermische Kondensation des roten Kohlenstoffoligomers weiter zu senken, was zu einer höheren spezifischen Oberfläche und Porosität führt. SnCl2 als reaktive Salzschmelze kann die Sauerstoffatome des roten Kohlenstoffs abfangen, was die Entfernung von Sauerstoffatomen bewirkt und den thermischen Kondensationsprozess begünstigt. Darüber hinaus wirkte die In-situ-Bildung von SnO2-Nanopartikeln als harte Schablone, was zu hochporösen Strukturen führte. Es wurde bestätigt, dass dieser Porenbildungsmechanismus auch für andere sauerstoffreiche Ausgangsstoffe anwendbar ist. Die erhaltenen Kohlenstoffe mit Sauerstofffunktionalitäten zeigten eine hohe Aktivität und Selektivität für die elektrokatalytische Nitrat-Hydrierung zu Ammoniak und übertrafen andere Kohlenstoffmaterialien, sogar die kohlenstoffgestützten Metalle. In Kapitel 4 wurde das THQ-Molekül, eine sauerstoffreiche Verbindung, als Vorläufer für die Herstellung von Oxokohlenstoffen und Oxokohlenstoff-gestützten Cu-SACs in Gegenwart von MgCl2∙6H2O verwendet. Die Wechselwirkung zwischen MgCl2∙6H2O und den Hydroxylgruppen von THQ trug zum spezifischen Wachstum der Strukturen bei und führte zu homogenen 2D-Flockenstrukturen. Darüber hinaus kann Mg den Sauerstoff aus dem THQ-Molekül abfangen, wodurch sekundäre MgO-Hartschablonen gebildet werden und mesoporöse Strukturen mit einer hohen spezifischen Oberfläche von 1177 m²/g bei 600 °C entstehen. Darüber hinaus diente THQ als Ligand bei der Synthese von THQ-Cu-MOFs, die anschließend zur Entwicklung sauerstoffstabilisierter Cu-SACs auf sauerstoffreichen Kohlenstoffträgern eingesetzt wurden. Die Cu-SACs zeigten eine hohe Aktivität bei der Oxidation von Glycerin und erreichten eine hohe Faradaic-Effizienz und Selektivität, die vielen anderen Katalysatoren auf Cu-Basis überlegen war, was auf eine vielversprechende Nutzung als Katalysator für die Umwandlung von Nebenprodukten in wertvolle Ameisensäure hindeutet."]},{"key":"dc:title","label":"Title","values":["Oxocarbon-derived porous carbonaceous materials for electrocatalysis"]}]}],"canonical_facts":{"dc:contributor.advisor":["Thomas, Arne","Antonietti, Markus"],"dc:creator":["Zheng, Xinyue"],"dc:date.accessioned":["2024-11-21T11:19:01Z"],"dc:date.available":["2024-11-21T11:19:01Z"],"dc:date.issued":["2024"],"dc:description.abstract":["The rising global demand for efficient energy conversion technologies underscores the necessity for advanced carbon materials with specific structural and functional attributes. Porous carbon materials, characterized by their high specific surface area and tunable pore structures, are particularly promising for electrocatalysis. However, the rational design of functional carbons, the development of new synthesis routes, and the exploration of the structure-activity relationship still remain challenging. This dissertation contributes to the development of novel oxygen-doped functional porous carbon materials derived from diverse oxocarbons. It focuses on tailoring their structures and properties to enhance the electrocatalytic performance, amming to elucidate the structure-activity relationships and provide new insights of developing advanced carbonaceous materials for electrocatalysis. In Chapter 2, red carbon oligomer was used as the precursor for the synthesis of carbons. This precursor without inactive C-H bond can undergo crosslinking with the only release of edge CO2 groups, facilitating the formation of porous oxocarbons at temperatures as low as 400°C without templating agents. Owing to the microporous structures, the carbon materials act as metal-free electrocatalysts presenting good performance for oxygen reduction reaction. Additionally, it enables effective crosslinking of the precursor on non-conductive surfaces at low temperatures, yielding thin conductive carbon films resistant to corrosive environments. SnCl2 was used as salt melt in Chapter 3 to further lower the temperature requirement of thermal condensation of red carbon oligomer, resulting in higher specific surface area and porosity. SnCl2 as a reactive salt melt can intercept the oxygen atoms of red carbon, causing the removal of oxygen atoms and favoring the thermal condensation process. Moreover, the in-situ formation of SnO2 nanoparticles acted as hard templates, further leading to highly porous structures. Such pore formation mechanism was confirmed also applicable for other oxygen-rich precursors. The obtained carbons with oxygen functionalities presented high activity and selectivity for electrocatalytic nitrate hydrogenation to ammonia, overpassing other carbon materials, even the carbon-supported metals. In Chapter 4, THQ molecule, an oxygen-rich compound, was utilized as a precursor for the preparation of oxocarbons and oxocarbon-supported Cu SACs in the presence of MgCl2∙6H2O. The interaction between MgCl2∙6H2O and the hydroxyl groups of THQ contributed to the specific growth of the structures, leading to homogeneous 2D flake structures. Moreover, Mg can intercept oxygen from the THQ molecule, forming MgO secondary hard templates and resulting in mesoporous structures with a high specific surface area of 1177 m²/g at 600°C. Furthermore, THQ served as a ligand in the synthesis of THQ-Cu MOFs, which were subsequently employed to design oxygen-stabilized Cu SACs on oxygen-rich carbon supports. The Cu SACs exhibited high activity in glycerol oxidation, achieving high Faradaic efficiency and selectivity, superior to many other Cu-based catalysts, which suggested the promising utilization as a catalyst for converting byproducts into valuable formic acid.","Die weltweit steigende Nachfrage nach effizienten Energieumwandlungstechnologien unterstreicht die Notwendigkeit moderner Kohlenstoffmaterialien mit spezifischen strukturellen und funktionellen Eigenschaften. Poröse Kohlenstoffmaterialien, die sich durch ihre hohe spezifische Oberfläche und abstimmbare Porenstrukturen auszeichnen, sind besonders vielversprechend für die Elektrokatalyse. Das rationale Design funktioneller Kohlenstoffe, die Entwicklung neuer Synthesewege und die Erforschung der Struktur-Aktivitäts-Beziehung sind jedoch nach wie vor eine Herausforderung. Diese Dissertation trägt zur Entwicklung neuartiger sauerstoffdotierter funktioneller poröser Kohlenstoffmaterialien bei, die aus verschiedenen Oxokohlenstoffen gewonnen werden. Sie konzentriert sich auf die Anpassung ihrer Strukturen und Eigenschaften, um die elektrokatalytische Leistung zu verbessern, die Struktur-Aktivitäts-Beziehungen aufzuklären und neue Einblicke in die Entwicklung fortschrittlicher kohlenstoffhaltiger Materialien für die Elektrokatalyse zu gewinnen. In Kapitel 2 wurde ein rotes Kohlenstoff-Oligomer als Vorläufer für die Synthese von Kohlenstoffen verwendet. Dieser Vorläufer ohne inaktive C-H-Bindung kann vernetzt werden, wobei nur die CO2-Randgruppen freigesetzt werden, was die Bildung von porösen Oxokohlenstoffen bei Temperaturen von nur 400 °C ohne Schablonenmittel ermöglicht. Aufgrund der mikroporösen Strukturen wirken die Kohlenstoffmaterialien als metallfreie Elektrokatalysatoren mit guter Leistung bei der Sauerstoffreduktionsreaktion. Darüber hinaus ermöglicht es eine effektive Vernetzung des Vorläufers auf nichtleitenden Oberflächen bei niedrigen Temperaturen, wodurch dünne leitfähige Kohlenstofffilme entstehen, die gegen korrosive Umgebungen resistent sind. SnCl2 wurde in Kapitel 3 als Salzschmelze verwendet, um die Temperaturanforderungen für die thermische Kondensation des roten Kohlenstoffoligomers weiter zu senken, was zu einer höheren spezifischen Oberfläche und Porosität führt. SnCl2 als reaktive Salzschmelze kann die Sauerstoffatome des roten Kohlenstoffs abfangen, was die Entfernung von Sauerstoffatomen bewirkt und den thermischen Kondensationsprozess begünstigt. Darüber hinaus wirkte die In-situ-Bildung von SnO2-Nanopartikeln als harte Schablone, was zu hochporösen Strukturen führte. Es wurde bestätigt, dass dieser Porenbildungsmechanismus auch für andere sauerstoffreiche Ausgangsstoffe anwendbar ist. Die erhaltenen Kohlenstoffe mit Sauerstofffunktionalitäten zeigten eine hohe Aktivität und Selektivität für die elektrokatalytische Nitrat-Hydrierung zu Ammoniak und übertrafen andere Kohlenstoffmaterialien, sogar die kohlenstoffgestützten Metalle. In Kapitel 4 wurde das THQ-Molekül, eine sauerstoffreiche Verbindung, als Vorläufer für die Herstellung von Oxokohlenstoffen und Oxokohlenstoff-gestützten Cu-SACs in Gegenwart von MgCl2∙6H2O verwendet. Die Wechselwirkung zwischen MgCl2∙6H2O und den Hydroxylgruppen von THQ trug zum spezifischen Wachstum der Strukturen bei und führte zu homogenen 2D-Flockenstrukturen. Darüber hinaus kann Mg den Sauerstoff aus dem THQ-Molekül abfangen, wodurch sekundäre MgO-Hartschablonen gebildet werden und mesoporöse Strukturen mit einer hohen spezifischen Oberfläche von 1177 m²/g bei 600 °C entstehen. Darüber hinaus diente THQ als Ligand bei der Synthese von THQ-Cu-MOFs, die anschließend zur Entwicklung sauerstoffstabilisierter Cu-SACs auf sauerstoffreichen Kohlenstoffträgern eingesetzt wurden. Die Cu-SACs zeigten eine hohe Aktivität bei der Oxidation von Glycerin und erreichten eine hohe Faradaic-Effizienz und Selektivität, die vielen anderen Katalysatoren auf Cu-Basis überlegen war, was auf eine vielversprechende Nutzung als Katalysator für die Umwandlung von Nebenprodukten in wertvolle Ameisensäure hindeutet."],"dc:identifier.uri":["https://depositonce.tu-berlin.de/handle/11303/23253","https://doi.org/10.14279/depositonce-22067"],"dc:language.iso":["en"],"dc:rights.uri":["https://creativecommons.org/licenses/by/4.0/"],"dc:title":["Oxocarbon-derived porous carbonaceous materials for electrocatalysis"],"dc:type":["Doctoral Thesis"]},"updated_at":"2026-07-27T21:28:42Z"}